CN102653570A - Prepolymerization method, prepolymerized catalyst component for addition polymerization, and method for producing addition polymer using the same - Google Patents
Prepolymerization method, prepolymerized catalyst component for addition polymerization, and method for producing addition polymer using the same Download PDFInfo
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- CN102653570A CN102653570A CN2012100529088A CN201210052908A CN102653570A CN 102653570 A CN102653570 A CN 102653570A CN 2012100529088 A CN2012100529088 A CN 2012100529088A CN 201210052908 A CN201210052908 A CN 201210052908A CN 102653570 A CN102653570 A CN 102653570A
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Abstract
o provide a method which gives a prepolymerized catalyst component for addition polymerization with less fine powders.A method for prepolymerizing monomers capable of addition polymerization, wherein the method comprises the following steps:a step of preparing a mixture by mixing a solvent for polymerization with an organic compound (D) represented by Formula [21,a step of prepolymerizing the monomers in the mixture in the presence of a catalyst prepared by bringing a compound (A) selected from amongtransition metal compounds represented by Formula [1] and their p.-oxo type transition metal compound dimers, and an activating agent (B) into contact with each other.[err]
Description
Technical field
The present invention relates to prepolymerization method, through prepolymerized addition polymerization with catalyst component and use the method for manufacture of its addition polymer.
Background technology
Addition polymer such as Vestolen PP 7052 or Vilaterm is excellent at aspects such as mechanical properties, resistances to chemical reagents, and the balance of above-mentioned in addition characteristic and economy is excellent, thereby is widely used in various shapings field.
These addition polymers are in recent years through using catalyzer that polymerization such as alkene is made, said catalyst combination transiting metal component that comprises transistion metal compound and the organo-metallic composition that comprises aikyiaiurnirsoxan beta etc.
Known because above-mentioned catalyzer is a solubility for reaction system, thus in the polymerization of following the addition polymer particle to form during applications catalyst, through using specific particle as one of catalyst component, can be with the shape setting of the addition polymer that generates.For example; Put down in writing the particle that uses silica gel, organic zinc compound, trifluoro-benzene phenols and water and get in the patent documentation 1, and put down in writing and used the catalyst that this particle, transistion metal compound and organo-aluminium combination are formed and be used for olefin polymerization through modification (upgrading).
In addition, during the known polymerization that in industry, implement to generate particle shape addition polymer,, effectively carry out the prepolymerization operation as the leading portion of formal polymerization process.For example; Put down in writing in the patent documentation 2 utilize will specific particle as one of catalyst component catalyzer, alkene is carried out prepolymerization and obtains use catalyst component through prepolymerized olefin polymerization, and use is somebody's turn to do and was carried out formal polymeric method through the pre-polymerized catalyst composition.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2003-171413 communique
Patent documentation 2: TOHKEMY 2002-293817 communique.
Summary of the invention
The technical problem that invention will solve
But, in the aforesaid method, generate little powdered sometimes and use catalyst component through prepolymerized addition polymerization.When the catalyst component that use contains micro mist carries out formal polymerization, then there is the situation of the undercapacity of situation that its steady running property has problems or addition polymer.The object of the present invention is to provide can obtain micro mist few through the method for prepolymerized addition polymerization with catalyst component.
The method that is used for the technical solution problem
But first aspect of the present invention relates to the prepolymerized method of the monomer of addition polymerization, and it has following operation:
(1) mixed polymerization forms the operation of mixture with the organic cpds (D) shown in solvent and the formula ［ 2 ］
(2) compound (A) in the transistion metal compound dimer that makes transistion metal compound shown in the formula of being selected from ［ 1 ］ and mu-oxo type thereof, acvator (B) contact with organo-aluminium compound (C) and the catalyzer that forms in the presence of, with aforementioned monomer prepolymerized operation in aforementioned mixture
L
1 aM
1X
1 b ［1］
M
1Transition metal atoms for IVB family; L
1For group or contain heteroatomic group with cyclopentadiene shape anion frame; X
1Be halogen atom,-oxyl or alkyl (wherein, getting rid of group) with cyclopentadiene shape anion frame; A is for satisfying the number of 0＜a≤3; B is for satisfying the number of 0＜b≤3; A is greater than 1 o'clock, 1 L
1Can with other L
1Directly perhaps link each other through the group that contains carbon atom, Siliciumatom, nitrogen-atoms, Sauerstoffatom, sulphur atom or phosphorus atom,
R
1C（＝O）NR
2 2 ［2］
R
1For having the alkyl of substituent carbonatoms 1～30; R
2For having the alkyl of substituent carbonatoms 1～30; Two R
2Can be identical or different each other.
Second aspect of the present invention relates to through what aforementioned prepolymerization method got uses catalyst component through prepolymerized addition polymerization.
The third aspect of the invention relate to use aforementioned through prepolymerized addition polymerization with catalyst component, and the method for manufacture of the addition polymer of as required organo-aluminium compound (C).
The invention effect
According to the method for the invention, can make micro mist few use catalyst component through prepolymerized addition polymerization.When using this catalyst component to carry out formal polymerization, can stablize and carry out formal polymerization continuously.
Embodiment
Below, the present invention is elaborated.
Compound (A): the transistion metal compound dimer of transistion metal compound or its mu-oxo type
The compound that uses among the present invention (A) is selected from the transistion metal compound dimer of transistion metal compound and mu-oxo type thereof.As the transistion metal compound dimer (A) of transistion metal compound or its mu-oxo type, but the dimer of the transistion metal compound of the transistion metal compound shown in the following formula of illustration ［ 1 ］ or its mu-oxo type.
L
1 aM
1X
1 b ?［1］
In the formula, M
1Transition metal atoms for IVB family; L
1For group or contain heteroatomic group with cyclopentadiene shape anion frame; X
1Be halogen atom,-oxyl or alkyl (wherein, getting rid of group) with cyclopentadiene shape anion frame; A is for satisfying the number of 0＜a≤3; B is for satisfying the number of 0＜b≤3; A is greater than 1 o'clock, 1 L
1Can with other L
1Directly perhaps link each other through the group that contains carbon atom, Siliciumatom, nitrogen-atoms, Sauerstoffatom, sulphur atom or phosphorus atom.
The M of formula ［ 1 ］
1Be titanium atom, zirconium atom, hafnium atom, more preferably zirconium atom.
L as formula ［ 1 ］
1The group with cyclopentadiene shape anion frame, for example can enumerate (replacement) cyclopentadienyl moiety, (replacement) indenyl and (replacement) fluorenyl.But concrete illustration: cyclopentadienyl moiety, methyl cyclopentadienyl, ethyl cyclopentadienyl moiety, n-butyl cyclopentadienyl, tertiary butyl cyclopentadienyl moiety, 1; 2-dimethyl-cyclopentadienyl moiety, 1,3-dimethyl-cyclopentadienyl moiety, 1-methyl-2-ethyl cyclopentadienyl moiety, 1-methyl-3-ethyl cyclopentadienyl moiety, the 1-tertiary butyl-2-methyl cyclopentadienyl, the 1-tertiary butyl-3-methyl cyclopentadienyl, 1-methyl-2-sec.-propyl cyclopentadienyl moiety, 1-methyl-3-sec.-propyl cyclopentadienyl moiety, 1-methyl-2-n-butyl cyclopentadienyl, 1-methyl-3-n-butyl cyclopentadienyl, η
5-1,2,3-trimethylammonium cyclopentadienyl moiety, η
5-1,2,4-trimethylammonium cyclopentadienyl moiety, tetramethyl-ring pentadienyl, pentamethyl-cyclopentadienyl moiety, indenyl, 4; 5,6,7-tetrahydro indenyl, 2-methyl indenyl, 3-methyl indenyl, 4-methyl indenyl, 5-methyl indenyl, 6-methyl indenyl, 7-methyl indenyl, 2-tertiary butyl indenyl, 3-tertiary butyl indenyl, 4-tertiary butyl indenyl, 5-tertiary butyl indenyl, 6-tertiary butyl indenyl, 7-tertiary butyl indenyl, 2; 3-dimethyl-indenyl, 4; 7-dimethyl-indenyl, 2,4,7-trimethylammonium indenyl, 2-methyl-4-sec.-propyl indenyl, 4; 5-benzo indenyl, 2-methyl-4; 5-benzo indenyl, 4-phenyl indenyl, 2-methyl-5-phenyl indenyl, 2-methyl-4-phenyl indenyl, 2-methyl-4-naphthyl indenyl, fluorenyl, 2,7-dimethyl-fluorenyl and 2,7-di-t-butyl fluorenyl.
The L of formula ［ 1 ］
1In not special qualification of multiple tooth property (many property) η of the group that uses with Cyclopeutadiene type anion frame, can be to have the value arbitrarily that the group of Cyclopeutadiene type anion frame can be taked.For example can enumerate: 5 teeth, 4 teeth, 3 teeth, 2 teeth, monodentate are preferably 5 teeth, 3 teeth or monodentate, more preferably 5 teeth or 3 teeth.
As the L in the formula ［ 1 ］
1Contain the heteroatoms in the heteroatomic group; For example can enumerate: Sauerstoffatom, sulphur atom, nitrogen-atoms, phosphorus atom; As above-mentioned group, have the aromatic heterocyclic group or the aliphatic heterocyclic group of Sauerstoffatom, sulphur atom, nitrogen-atoms and/or phosphorus atom in preferred alkoxyl group, aryloxy, thio alkoxy, thio-aryloxy, alkylamino, arylamino, alkyl phosphino-, aryl phosphino-, chelating property ligand or the ring.
As the L in the formula ［ 1 ］
1Contain heteroatomic group, for example can enumerate: methoxyl group, oxyethyl group, propoxy-, butoxy, phenoxy, 2-methylphenoxy, 2; 6-dimethyl phenoxy, 2,4,6-trimethylammonium phenoxy, 2-ethyl phenoxy, 4-n-propyl phenoxy, 2-sec.-propyl phenoxy, 2; 6-di-isopropyl phenoxy, 4-sec.-butyl phenoxy, 4-tertiary butyl phenoxy, 2,6-di-secondary butyl phenoxy, the 2-tertiary butyl-4-methylphenoxy, 2,6-di-t-butyl phenoxy, 4-methoxyl group phenoxy, 2; 6-dimethoxy phenoxy, 3,5-dimethoxy phenoxy, 2-chlorophenoxy, 4-nitroso-group phenoxy, 4-nitrophenoxy, 2-amino-benzene oxygen, 3-amino-benzene oxygen, the amino sulfo-phenoxy of 4-, 2,3; 6-Trichlorophenoxy, 2,4,6-trifluoromethoxy phenoxy base, sulfo-methoxyl group, dimethylamino, diethylamino, dipropyl amino, diphenyl amino, sec.-propyl are amino, the tertiary butyl is amino, pyrryl, dimethyl-phosphino-, 2-(2-oxygen-1-propyl group) phenoxy, pyrocatechol, Resorcinol, 4-isopropylcatechol, 3-methoxyl group pyrocatechol, 1; 8-dihydroxyl naphthyl, 1,2-dihydroxyl naphthyl, 2,2 '-biphenyl glycol-based, 1; 1 '-two-beta naphthal base, 2,2 '-dihydroxyl-6,6 '-dimethyl diphenyl base, 4; 4 ', 6,6 '-tetra-tert-2; 2 ' methylene radical, two phenoxys and 4,4 ', 6; 6 '-tetramethyl--2,2 '-isobutylene, two phenoxys.
In addition, contain heteroatomic group, for example also can enumerate the group shown in the following formula ［ 6 ］ as above-mentioned,
R
9 3P＝N- ［6］
(in the formula, R
9Represent Wasserstoffatoms, halogen atom or alkyl independently of one another, a plurality of R
9Can be identical or different each other, a plurality of R
9In, any bonding each other more than two can form ring structure.）
As the R in the aforementioned formula ［ 6 ］
9Concrete example, but illustration: Wasserstoffatoms, fluorine atom, chlorine atom, bromine atoms, iodine atom, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, cyclopropyl, cyclobutyl, suberyl, cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl and benzyl.
And then, contain heteroatomic group as aforementioned, but the group shown in the following formula of illustration [7] also,
(in the formula, R
5Represent Wasserstoffatoms, halogen atom, alkyl, halo alkyl,-oxyl, silyl or amino independently of one another, a plurality of R
5Can be identical or different each other, a plurality of R
5In, any bonding each other more than two can form ring structure)
As the R in the formula [7]
5Concrete example; But illustration: Wasserstoffatoms, fluorine atom, chlorine atom, bromine atoms, iodine atom, phenyl, 1-naphthyl, 2-naphthyl, the tertiary butyl, 2; 6-3,5-dimethylphenyl, 2-fluorenyl, 2-aminomethyl phenyl, 4-trifluoromethyl, 4-p-methoxy-phenyl, 4-pyridyl, cyclohexyl, 2-isopropyl phenyl, benzyl, methyl, triethylsilyl, diphenyl methyl silyl, 1-methyl isophthalic acid-phenylethyl, 1,1-dimethyl propyl, 2-chloro-phenyl-and pentafluorophenyl group.
L in the formula ［ 1 ］
1Chelating property ligand be meant ligand with a plurality of coordinations position, as this ligand, for example can enumerate: acetylacetonate, diimine,
Azoles quinoline, two
Azoles quinoline, three pyridines, acylhydrazone, NSC 446, Triethylenetetramine (TETA), porphyrin, crown ether and cave ether.
As the L in the formula ［ 1 ］
1Heterocyclic group, for example can enumerate: pyridyl, N-substituted imidazole base and N-substituted indazolyl, wherein, preferred pyridyl.
In the formula ［ 1 ］, a plurality of L
1When linking (, when group with cyclopentadiene shape anion frame links through this residue each other, when containing heteroatomic group and linking through this residue each other or the group with cyclopentadiene shape anion frame when containing heteroatomic group) through this residue binding through the residue that contains carbon atom, Siliciumatom, nitrogen-atoms, Sauerstoffatom, sulphur atom or phosphorus atom; As this residue, preferably with two L
1The atom of bonding is carbon atom, Siliciumatom, nitrogen-atoms, Sauerstoffatom, sulphur atom or phosphorus atom and makes two L
1The minimum atomicity of bonding is the divalent residue below 3.As this residue, but illustration: alkylidene groups such as methylene radical, ethylidene and propylidene; Substituted alkylenes such as dimethylated methylene base (isopropylidene) and phenylbenzene methylene radical; Silicylene, dimethylated methylene siloyl group, diethylammonium silicylene, phenylbenzene silicylene, tetramethyl-two silicylene and dimethoxy silicylene etc. replace silicylene; Heteroatomss such as nitrogen-atoms, Sauerstoffatom, sulphur atom and phosphorus atom.Wherein, preferred especially methylene radical, ethylidene, dimethylated methylene base (isopropylidene), phenylbenzene methylene radical, dimethylated methylene siloyl group, diethylammonium silicylene, phenylbenzene silicylene or dimethoxy silicylene.
As the X in the formula ［ 1 ］
1Halogen atom, for example can enumerate fluorine atom, chlorine atom, bromine atoms and iodine atom.As X
1Alkyl, for example can enumerate: alkyl, aralkyl, aryl and thiazolinyl, wherein, alkyl, the aralkyl of carbonatoms 7～20, the aryl of carbonatoms 6～20 or the thiazolinyl of carbonatoms 3～20 of preferred carbonatoms 1～20.
As X
1The alkyl of carbonatoms 1～20; For example can enumerate: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec.-butyl, the tertiary butyl, isobutyl-, n-pentyl, neo-pentyl, amyl group, n-hexyl, n-octyl, positive decyl, dodecyl, Pentadecane base and NSC 62789 base; Wherein, more preferably methyl, ethyl, sec.-propyl, the tertiary butyl, isobutyl-or amyl group.These alkyl all can be replaced by halogen atoms such as fluorine atom, chlorine atom, bromine atoms and iodine atoms.As by the substituted alkyl of halogen atom, for example can enumerate: methyl fluoride, trifluoromethyl, chloromethyl, trichloromethyl, fluoro ethyl, pentafluoroethyl group, perfluoro propyl, perfluoro butyl, perfluoro hexyl, perfluoro capryl, perchloro-propyl group, perchloro-butyl and perbromo-propyl group.In addition, these alkyl can also have aralkoxies such as aryloxy such as alkoxyl groups such as methoxyl group and oxyethyl group, phenoxy or benzyloxy etc. as substituting group.
As X
1The aralkyl of carbonatoms 7～20, for example can enumerate: benzyl, (2-aminomethyl phenyl) methyl, (3-aminomethyl phenyl) methyl, (4-aminomethyl phenyl) methyl, (2, the 3-3,5-dimethylphenyl) methyl, (2, the 4-3,5-dimethylphenyl) methyl, (2; The 5-3,5-dimethylphenyl) methyl, (2, the 6-3,5-dimethylphenyl) methyl, (3, the 4-3,5-dimethylphenyl) methyl, (3; The 5-3,5-dimethylphenyl) methyl, (2,3, the 4-trimethylphenyl) methyl, (2; 3, the 5-trimethylphenyl) methyl, (2,3; The 6-trimethylphenyl) methyl, (3,4, the 5-trimethylphenyl) methyl, (2; 4, the 6-trimethylphenyl) methyl, (2,3; 4, the 5-tetramethylphenyl) methyl, (2,3; 4, the 6-tetramethylphenyl) methyl, (2,3; 5,6-tetramethylphenyl) methyl, (pentamethyl-phenyl) methyl, (ethylphenyl) methyl, (n-propyl phenyl) methyl, (isopropyl phenyl) methyl, (n-butylphenyl) methyl, (secondary butyl phenenyl) methyl, (tert-butyl-phenyl) methyl, (n-pentyl phenyl) methyl, (neo-pentyl phenyl) methyl, (n-hexyl phenyl) methyl, (n-octyl phenyl) methyl, (positive decyl phenyl) methyl, (dodecyl phenyl) methyl, naphthyl methyl and anthryl methyl, more preferably benzyl.These aralkyl can also have aralkoxies such as aryloxy such as alkoxyl groups such as halogen atom, methoxyl group and oxyethyl group, phenoxys such as fluorine atom, chlorine atom, bromine atoms and iodine atom or benzyloxy etc. as substituting group.
As X
1The aryl of carbonatoms 6～20, for example can enumerate: phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl, 2; 5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl, 2; 3,4-trimethylphenyl, 2,2; 3,6-trimethylphenyl, 2,4,6-trimethylphenyl, 3; 4,5-trimethylphenyl, 2,3,4; 5-tetramethylphenyl, 2,3,4,6-tetramethylphenyl, 2; 3,5,6-tetramethylphenyl, pentamethyl-phenyl, ethylphenyl, n-propyl phenyl, isopropyl phenyl, n-butylphenyl, secondary butyl phenenyl, tert-butyl-phenyl, n-pentyl phenyl, neo-pentyl phenyl, n-hexyl phenyl, n-octyl phenyl, positive decyl phenyl, dodecyl phenyl, n-tetradecane base phenyl, naphthyl and anthryl, more preferably phenyl.These aryl can also have aralkoxies such as aryloxy such as alkoxyl groups such as halogen atom, methoxyl group and oxyethyl group, phenoxys such as fluorine atom, chlorine atom, bromine atoms, iodine atom or benzyloxy etc. as substituting group.
As X
1The thiazolinyl of carbonatoms 3～20, for example can enumerate: allyl group, methylallyl, crot(on)yl, 1,3-phenylbenzene-2-propenyl, wherein, more preferably allyl group or methylallyl.
As the X in the formula ［ 1 ］
1-oxyl, for example can enumerate: alkoxyl group, aralkoxy and aryloxy, wherein, alkoxyl group, the aralkoxy of carbonatoms 7～20 or the aryloxy of carbonatoms 6～20 of preferred carbonatoms 1～20.
As X
1The alkoxyl group of carbonatoms 1～20; For example can enumerate: 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, preferred methoxyl group, oxyethyl group, isopropoxy or tert.-butoxy.These alkoxyl groups can also have aralkoxies such as aryloxy such as alkoxyl groups such as halogen atom, methoxyl group and oxyethyl group, phenoxys such as fluorine atom, chlorine atom, bromine atoms and iodine atom or benzyloxy etc. as substituting group.
As X
1The aralkoxy of carbonatoms 7～20, for example can enumerate: benzyloxy, (2-aminomethyl phenyl) methoxyl group, (3-aminomethyl phenyl) methoxyl group, (4-aminomethyl phenyl) methoxyl group, (2,3-3,5-dimethylphenyl) methoxyl group, (2,4-3,5-dimethylphenyl) methoxyl group, (2,5-3,5-dimethylphenyl) methoxyl group, (2,6-3,5-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) 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, wherein, more preferably benzyloxy.These aralkoxies can also have aralkoxies such as aryloxy such as alkoxyl groups such as halogen atom, methoxyl group and oxyethyl group, phenoxys such as fluorine atom, chlorine atom, bromine atoms and iodine atom or benzyloxy etc. as substituting group.
As X
1The aryloxy of carbonatoms 6～20, for example can enumerate: phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 2,3-dimethyl phenoxy, 2,4-dimethyl phenoxy, 2,5-dimethyl phenoxy, 2,6-dimethyl phenoxy, 3,4-dimethyl phenoxy, 3,5-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, 2,3,5-trimethylammonium phenoxy, 2; 3,6-trimethylammonium phenoxy, 2,4,5-trimethylammonium phenoxy, 2; 4,6-trimethylammonium phenoxy, the 2-tertiary butyl-3,4-dimethyl phenoxy, the 2-tertiary butyl-3,5-dimethyl phenoxy, the 2-tertiary butyl-3; 6-dimethyl phenoxy, 2,6-di-t-butyl-3-methylphenoxy, the 2-tertiary butyl-4,5-dimethyl phenoxy, 2,6-di-t-butyl-4-methylphenoxy, 3; 4,5-trimethylammonium phenoxy, 2,3,4; 5-tetramethyl-phenoxy, the 2-tertiary butyl-3,4,5-trimethylammonium phenoxy, 2,3; 4,6-tetramethyl-phenoxy, the 2-tertiary butyl-3,4,6-trimethylammonium phenoxy, 2; 6-di-t-butyl-3,4-dimethyl phenoxy, 2,3; 5,6-tetramethyl-phenoxy, the 2-tertiary butyl-3,5; 6-trimethylammonium phenoxy, 2,6-di-t-butyl-3,5-dimethyl phenoxy, pentamethyl-phenoxy, ethyl phenoxy, n-propyl phenoxy, sec.-propyl phenoxy, normal-butyl phenoxy, sec.-butyl phenoxy, tertiary butyl phenoxy, n-hexyl phenoxy, n-octyl phenoxy, positive decyl phenoxy, n-tetradecane phenoxyl, naphthyloxy and anthracene oxygen base.These aryloxy can also have aralkoxies such as aryloxy such as alkoxyl groups such as halogen atom, methoxyl group and oxyethyl group, phenoxys such as fluorine atom, chlorine atom, bromine atoms and iodine atom or benzyloxy etc. as substituting group.
As the X in the formula ［ 1 ］
1More preferably chlorine atom, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, trifluoromethoxy, phenyl, phenoxy, 2,6-di-t-butyl phenoxy, 3,4; 5-trifluoromethoxy phenoxy base, penta fluoro benzene oxygen base, 2; 3,5,6-tetrafluoro-4-pentafluorophenyl group phenoxy or benzyl.
A in the formula ［ 1 ］ is for satisfying the number of 0＜a≤3, and b is for satisfying the number of 0＜b≤3.A and b are corresponding to M
1Valence mumber and suitable the selection.M
1During for titanium atom, zirconium atom or hafnium atom, a is preferably 2, and b also is preferably 2.
As the transistion metal compound shown in the formula ［ 1 ］; For example can enumerate: two (cyclopentadienyl moiety) titanium dichloride, two (methyl cyclopentadienyl) titanium dichloride, two (ethyl cyclopentadienyl moiety) titanium dichloride, two (n-butyl cyclopentadienyl) titanium dichloride, two (tertiary butyl cyclopentadienyl moiety) titanium dichloride, two (1; 2-dimethyl-cyclopentadienyl moiety) titanium dichloride, two (1; 3-dimethyl-cyclopentadienyl moiety) titanium dichloride, two (1-methyl-2-ethyl cyclopentadienyl moiety) titanium dichloride, two (1-methyl-3-ethyl cyclopentadienyl moiety) titanium dichloride, two (1-methyl-2-n-butyl cyclopentadienyl) titanium dichloride, two (1-methyl-3-n-butyl cyclopentadienyl) titanium dichloride, two (1-methyl-2-sec.-propyl cyclopentadienyl moiety) titanium dichloride, two (1-methyl-3-sec.-propyl cyclopentadienyl moiety) titanium dichloride, two (the 1-tertiary butyl-2-methyl cyclopentadienyl) titanium dichloride, two (the 1-tertiary butyl-3-methyl cyclopentadienyl) titanium dichloride, two (1; 2; 3-trimethylammonium cyclopentadienyl moiety) titanium dichloride, two (1; 2; 4-trimethylammonium cyclopentadienyl moiety) titanium dichloride, two (tetramethyl-ring pentadienyl) titanium dichloride, two (pentamethyl-cyclopentadienyl moiety) titanium dichloride, two (indenyl) titanium dichloride, two (4; 5; 6,7-tetrahydro indenyl) titanium dichloride, two (fluorenyl) titanium dichloride, two (2-phenyl indenyl) titanium dichloride,
It is two that ［ 2-(two-3; The 5-trifluoromethyl) indenyl ］ titanium dichloride, two ［ 2-(4-tert-butyl-phenyl) indenyl ］ titanium dichloride, two ［ 2-(4-trifluoromethyl) indenyl ］ titanium dichloride, two ［ 2-(4-aminomethyl phenyl) indenyl ］ titanium dichloride, two ［ 2-(3, the 5-3,5-dimethylphenyl) indenyl ］ titanium dichloride, two ［ 2-(pentafluorophenyl group) indenyl ］ titanium dichloride, cyclopentadienyl moiety (pentamethyl-cyclopentadienyl moiety) titanium dichloride, cyclopentadienyl moiety (indenyl) titanium dichloride, cyclopentadienyl moiety (fluorenyl) titanium dichloride, indenyl (fluorenyl) titanium dichloride, pentamethyl-cyclopentadienyl moiety (indenyl) titanium dichloride, pentamethyl-cyclopentadienyl moiety (fluorenyl) titanium dichloride, cyclopentadienyl moiety (2-phenyl indenyl) titanium dichloride, pentamethyl-cyclopentadienyl moiety (2-phenyl indenyl) titanium dichloride,
Two (cyclopentadienyl moiety) titanium dichloride of dimethylated methylene siloyl group, two (2-methyl cyclopentadienyl) the titanium dichloride of dimethylated methylene siloyl group, two (3-methyl cyclopentadienyl) the titanium dichloride of dimethylated methylene siloyl group, two (2-n-butyl cyclopentadienyl) the titanium dichloride of dimethylated methylene siloyl group, two (3-n-butyl cyclopentadienyl) the titanium dichloride of dimethylated methylene siloyl group, dimethylated methylene siloyl group two (2; 3-dimethyl-cyclopentadienyl moiety) titanium dichloride, dimethylated methylene siloyl group two (2; 4-dimethyl-cyclopentadienyl moiety) titanium dichloride, dimethylated methylene siloyl group two (2; 5-dimethyl-cyclopentadienyl moiety) titanium dichloride, dimethylated methylene siloyl group two (3; 4-dimethyl-cyclopentadienyl moiety) titanium dichloride, dimethylated methylene siloyl group two (2; 3-ethyl-methyl cyclopentadienyl moiety) titanium dichloride, dimethylated methylene siloyl group two (2; 4-ethyl-methyl cyclopentadienyl moiety) titanium dichloride, dimethylated methylene siloyl group two (2; 5-ethyl-methyl cyclopentadienyl moiety) titanium dichloride, dimethylated methylene siloyl group two (3; 5-ethyl-methyl cyclopentadienyl moiety) titanium dichloride, two (2,3,4-trimethylammonium cyclopentadienyl moiety) the titanium dichloride of dimethylated methylene siloyl group, dimethylated methylene siloyl group two (2; 3,5-trimethylammonium cyclopentadienyl moiety) titanium dichloride, two (tetramethyl-ring pentadienyl) the titanium dichloride of dimethylated methylene siloyl group,
Two (indenyl) titanium dichloride of dimethylated methylene siloyl group, two (2-methyl indenyl) the titanium dichloride of dimethylated methylene siloyl group, two (2-tertiary butyl indenyl) the titanium dichloride of dimethylated methylene siloyl group, dimethylated methylene siloyl group two (2; 3-dimethyl-indenyl) titanium dichloride, dimethylated methylene siloyl group two (2; 4; 7-trimethylammonium indenyl) titanium dichloride, two (2-methyl-4-sec.-propyl indenyl) the titanium dichloride of dimethylated methylene siloyl group, dimethylated methylene siloyl group two (4; 5-benzo indenyl) titanium dichloride, two (the 2-methyl-4 of dimethylated methylene siloyl group; 5-benzo indenyl) titanium dichloride, two (2-phenyl indenyl) the titanium dichloride of dimethylated methylene siloyl group, two (4-phenyl indenyl) the titanium dichloride of dimethylated methylene siloyl group, two (2-methyl-4-phenyl indenyl) the titanium dichloride of dimethylated methylene siloyl group, two (2-methyl-5-phenyl indenyl) the titanium dichloride of dimethylated methylene siloyl group, two (2-methyl-4-naphthyl indenyl) the titanium dichloride of dimethylated methylene siloyl group, dimethylated methylene siloyl group two (4; 5; 6, the 7-tetrahydro indenyl) the titanium dichloride,
Dimethylated methylene siloyl group (cyclopentadienyl moiety) (indenyl) titanium dichloride; Dimethylated methylene siloyl group (methyl cyclopentadienyl) (indenyl) titanium dichloride; Dimethylated methylene siloyl group (n-butyl cyclopentadienyl) (indenyl) titanium dichloride; Dimethylated methylene siloyl group (tetramethyl-ring pentadienyl) (indenyl) titanium dichloride; Dimethylated methylene siloyl group (cyclopentadienyl moiety) (fluorenyl) titanium dichloride; Dimethylated methylene siloyl group (methyl cyclopentadienyl) (fluorenyl) titanium dichloride; Dimethylated methylene siloyl group (n-butyl cyclopentadienyl) (fluorenyl) titanium dichloride; Dimethylated methylene siloyl group (tetramethyl-ring pentadienyl) (indenyl) titanium dichloride; Dimethylated methylene siloyl group (indenyl) (fluorenyl) titanium dichloride; Two (fluorenyl) titanium dichloride of dimethylated methylene siloyl group; Dimethylated methylene siloyl group (cyclopentadienyl moiety) (tetramethyl-ring pentadienyl) titanium dichloride; Dimethylated methylene siloyl group (tetramethyl-ring pentadienyl) (fluorenyl) titanium dichloride; The cyclopentadienyltitanium trichloride; Pentamethyl-cyclopentadienyltitanium trichloride; Cyclopentadienyl moiety (dimethylformamide) titanium dichloride;
Cyclopentadienyl moiety (phenoxy) titanium dichloride, cyclopentadienyl moiety (2; The 6-3,5-dimethylphenyl) titanium dichloride, cyclopentadienyl moiety (2; The 6-diisopropyl phenyl) titanium dichloride, cyclopentadienyl moiety (2, the 6-di-tert-butyl-phenyl) titanium dichloride, pentamethyl-cyclopentadienyl moiety (2, the 6-3,5-dimethylphenyl) titanium dichloride, pentamethyl-cyclopentadienyl moiety (2; The 6-diisopropyl phenyl) titanium dichloride, pentamethyl-cyclopentadienyl moiety (2; The 6-tert-butyl-phenyl) titanium dichloride, indenyl (2, the 6-diisopropyl phenyl) titanium dichloride, fluorenyl (2, the 6-diisopropyl phenyl) titanium dichloride,
Dimethylated methylene siloyl group (cyclopentadienyl moiety) (2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (cyclopentadienyl moiety) (3-methyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (cyclopentadienyl moiety) (3; 5-dimethyl--2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (cyclopentadienyl moiety) (the 3-tertiary butyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (cyclopentadienyl moiety) (the 3-tertiary butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (cyclopentadienyl moiety) (3; 5-di-t-butyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (cyclopentadienyl moiety) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (cyclopentadienyl moiety) (3-t-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (cyclopentadienyl moiety) (5-methyl-3-trimethyl silyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (cyclopentadienyl moiety) (the 3-tertiary butyl-5-methoxyl group-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (cyclopentadienyl moiety) (the 3-tertiary butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (cyclopentadienyl moiety) (3,5-diamyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (cyclopentadienyl moiety) (3-phenyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (cyclopentadienyl moiety) (1-naphthyloxy-2-yl) titanium dichloride,
Dimethylated methylene siloyl group (methyl cyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (methyl cyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (methyl cyclopentadienyl) (3; 5-dimethyl--2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (methyl cyclopentadienyl) (the 3-tertiary butyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (methyl cyclopentadienyl) (the 3-tertiary butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (methyl cyclopentadienyl) (3; 5-di-t-butyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (methyl cyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (methyl cyclopentadienyl) (3-t-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (methyl cyclopentadienyl) (5-methyl-3-trimethyl silyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (methyl cyclopentadienyl) (the 3-tertiary butyl-5-methoxyl group-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (methyl cyclopentadienyl) (the 3-tertiary butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (methyl cyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (methyl cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (methyl cyclopentadienyl) (1-naphthyloxy-2-yl) titanium dichloride,
Dimethylated methylene siloyl group (n-butyl cyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (n-butyl cyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (n-butyl cyclopentadienyl) (3; 5-dimethyl--2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (n-butyl cyclopentadienyl) (the 3-tertiary butyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (n-butyl cyclopentadienyl) (the 3-tertiary butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (n-butyl cyclopentadienyl) (3; 5-di-t-butyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (n-butyl cyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (n-butyl cyclopentadienyl) (3-t-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (n-butyl cyclopentadienyl) (5-methyl-3-trimethyl silyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (n-butyl cyclopentadienyl) (the 3-tertiary butyl-5-methoxyl group-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (n-butyl cyclopentadienyl) (the 3-tertiary butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (n-butyl cyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (n-butyl cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (n-butyl cyclopentadienyl) (1-naphthyloxy-2-yl) titanium dichloride,
Dimethylated methylene siloyl group (tertiary butyl cyclopentadienyl moiety) (2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (tertiary butyl cyclopentadienyl moiety) (3-methyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (tertiary butyl cyclopentadienyl moiety) (3; 5-dimethyl--2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (tertiary butyl cyclopentadienyl moiety) (the 3-tertiary butyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (tertiary butyl cyclopentadienyl moiety) (the 3-tertiary butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (tertiary butyl cyclopentadienyl moiety) (3; 5-di-t-butyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (tertiary butyl cyclopentadienyl moiety) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (tertiary butyl cyclopentadienyl moiety) (3-t-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (tertiary butyl cyclopentadienyl moiety) (5-methyl-3-trimethyl silyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (tertiary butyl cyclopentadienyl moiety) (the 3-tertiary butyl-5-methoxyl group-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (tertiary butyl cyclopentadienyl moiety) (the 3-tertiary butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (tertiary butyl cyclopentadienyl moiety) (3,5-diamyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (tertiary butyl cyclopentadienyl moiety) (3-phenyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (tertiary butyl cyclopentadienyl moiety) (1-naphthyloxy-2-yl) titanium dichloride,
Dimethylated methylene siloyl group (tetramethyl-ring pentadienyl) (2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (tetramethyl-ring pentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (tetramethyl-ring pentadienyl) (3; 5-dimethyl--2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (tetramethyl-ring pentadienyl) (the 3-tertiary butyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (tetramethyl-ring pentadienyl) (the 3-tertiary butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (tetramethyl-ring pentadienyl) (3; 5-di-t-butyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (tetramethyl-ring pentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (tetramethyl-ring pentadienyl) (3-t-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (tetramethyl-ring pentadienyl) (5-methyl-3-trimethyl silyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (tetramethyl-ring pentadienyl) (the 3-tertiary butyl-5-methoxyl group-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (tetramethyl-ring pentadienyl) (the 3-tertiary butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (tetramethyl-ring pentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (tetramethyl-ring pentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (tetramethyl-ring pentadienyl) (1-naphthyloxy-2-yl) titanium dichloride,
Dimethylated methylene siloyl group (trimethyl silyl cyclopentadienyl moiety) (2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (trimethyl silyl cyclopentadienyl moiety) (3-methyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (trimethyl silyl cyclopentadienyl moiety) (3; 5-dimethyl--2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (trimethyl silyl cyclopentadienyl moiety) (the 3-tertiary butyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (trimethyl silyl cyclopentadienyl moiety) (the 3-tertiary butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (trimethyl silyl cyclopentadienyl moiety) (3; 5-di-t-butyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (trimethyl silyl cyclopentadienyl moiety) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (trimethyl silyl cyclopentadienyl moiety) (3-t-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (trimethyl silyl cyclopentadienyl moiety) (5-methyl-3-trimethyl silyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (trimethyl silyl cyclopentadienyl moiety) (the 3-tertiary butyl-5-methoxyl group-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (trimethyl silyl cyclopentadienyl moiety) (the 3-tertiary butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (trimethyl silyl cyclopentadienyl moiety) (3,5-diamyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (trimethyl silyl cyclopentadienyl moiety) (3-phenyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (trimethyl silyl cyclopentadienyl moiety) (1-naphthyloxy-2-yl) titanium dichloride,
Dimethylated methylene siloyl group (indenyl) (2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (indenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (indenyl) (3; 5-dimethyl--2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (indenyl) (the 3-tertiary butyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (indenyl) (the 3-tertiary butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (indenyl) (3; 5-di-t-butyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (indenyl) (3-t-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (indenyl) (5-methyl-3-trimethyl silyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (indenyl) (the 3-tertiary butyl-5-methoxyl group-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (indenyl) (the 3-tertiary butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (indenyl) (3,5-diamyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (indenyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (indenyl) (1-naphthyloxy-2-yl) titanium dichloride,
Dimethylated methylene siloyl group (fluorenyl) (2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (fluorenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (fluorenyl) (3; 5-dimethyl--2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (fluorenyl) (the 3-tertiary butyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (fluorenyl) (the 3-tertiary butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (fluorenyl) (3; 5-di-t-butyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (fluorenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (fluorenyl) (3-t-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (fluorenyl) (5-methyl-3-trimethyl silyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (fluorenyl) (the 3-tertiary butyl-5-methoxyl group-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (fluorenyl) (the 3-tertiary butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (fluorenyl) (3,5-diamyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylated methylene siloyl group (fluorenyl) (1-naphthyloxy-2-yl) titanium dichloride,
(tert-butylamides) tetramethyl-ring pentadienyl-1; 2-ethane two basic titanium dichloride, (methyl nitrosourea) tetramethyl-ring pentadienyl-1; 2-ethane two basic titanium dichloride, (buserelin) tetramethyl-ring pentadienyl-1; 2-ethane two basic titanium dichloride, (tert-butylamides) tetramethyl-ring pentadienyl dimethylsilane titanium dichloride, (benzyl acid amides) tetramethyl-ring pentadienyl dimethylsilane titanium dichloride, (phenyl phosphide) tetramethyl-ring pentadienyl dimethylsilane titanium dichloride, (tert-butylamides) indenyl-1; 2-ethane two basic titanium dichloride, (tert-butylamides) tetrahydro indenyl-1; 2-ethane two basic titanium dichloride, (tert-butylamides) fluorenyl-1,2-ethane two basic titanium dichloride, (tert-butylamides) indenyl dimethylsilane titanium dichloride, (tert-butylamides) tetrahydro indenyl dimethylsilane titanium dichloride, (tert-butylamides) fluorenyl dimethylsilane titanium dichloride,
(dimethylaminomethyl) tetramethyl-cyclopentadienyltitanium (III) dichloride, (dimethyl aminoethyl) tetramethyl-cyclopentadienyltitanium (III) dichloride, (dimethylaminopropyl) tetramethyl-cyclopentadienyltitanium (III) dichloride, (N-pyrrolidyl ethyl) tetramethyl-cyclopentadienyltitanium dichloride, (B-dimethylamino boron mix benzene) cyclopentadienyltitanium dichloride, cyclopentadienyl moiety (9-Lay base boron mix anthryl) titanium dichloride,
2,2 '-thiobis ［ 4-methyl-6-tert butyl phenoxy ］ titanium dichloride, 2,2 '-thiobis ［ 4-methyl-6-(1-methylethyl) phenoxy ］ titanium dichloride, 2; 2 '-thiobis (4, the 6-dimethyl phenoxy) titanium dichloride, 2,2 '-thiobis (4-methyl-6-tert butyl 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, two (4-methyl-6-tert butyl phenoxy) the titanium dichloride, 2 of 2 '-sulfoxide group; 2 '-(4,4 ', 6; 6 '-tetra-tert-1; 1 ' two phenoxys) titanium dichloride, (di-t-butyl-1,3-Malonodiamide) titanium dichloride, (dicyclohexyl-1,3-Malonodiamide) titanium dichloride,
［ two (trimethyl silyl)-1; The 3-Malonodiamide ］ titanium dichloride, ［ two (t-butyldimethylsilyl)-1; The 3-Malonodiamide ］ titanium dichloride, ［ two (2; The 6-3,5-dimethylphenyl)-1; The 3-Malonodiamide ］ titanium dichloride, ［ two (2; The 6-diisopropyl phenyl)-1; The 3-Malonodiamide ］ titanium dichloride, ［ two (2; The 6-di-tert-butyl-phenyl)-1; The 3-Malonodiamide ］ titanium dichloride, ［ two (triisopropyl silyl) naphthalene diamide ］ titanium dichloride, ［ two (trimethyl silyl) naphthalene diamide ］ titanium dichloride, ［ two (t-butyldimethylsilyl) naphthalene diamide ］ titanium dichloride, ［ hydrogen three (3; 5-dimethyl pyrazole base) boric acid ester ］ titanium trichloride, ［ hydrogen three (3,5-diethylammonium pyrazolyl) boric acid ester ］ titanium trichloride, ［ hydrogen three (3,5-di-t-butyl pyrazolyl) boric acid ester ］ titanium trichloride, ［ three (3; 5-dimethyl pyrazole base) methyl ］ titanium trichloride, ［ three (3; 5-diethylammonium pyrazolyl) methyl ］ titanium trichloride and ［ three (3,5-di-t-butyl pyrazolyl) methyl ］ titanium trichloride, also can enumerate: with " (2-phenoxy) " in the above-claimed cpd be replaced into " (3-phenyl-2-phenoxy) ", " (3-trimethyl silyl-2-phenoxy) " or " (3-t-butyldimethylsilyl-2-phenoxy) " and compound, with " dimethylated methylene siloyl group " in the above-claimed cpd be replaced into " methylene radical ", " ethylidene ", " dimethylated methylene base (isopropylidene) ", " phenylbenzene methylene radical ", " diethylammonium silicylene ", " phenylbenzene silicylene " or " dimethoxy silicylene " and compound.
In addition, as the concrete example of the transistion metal compound shown in the formula ［ 1 ］, also can enumerate following compound.
And then, can enumerate also except that them that titanium atom with above-claimed cpd is replaced into zirconium atom or hafnium atom and compound.
And then, also can enumerate: with " dichloride " in the above-claimed cpd be replaced into " difluoride ", " dibromide ", " diiodide ", " dimethyl-, " diethylammonium ", " di-isopropyl ", " phenylbenzene ", " dibenzyl ", " diformazan oxide compound ", " diethyl oxide compound ", " two positive propoxides ", " diisopropyl oxide compound ", " diphenylate " or " two (penta fluoro benzene oxide compound) " and compound and will " trichloride " be replaced into " trifluoride ", " tribromide ", " triiodide ", " trimethylammonium ", " triethyl ", " triisopropyl ", " triphenyl ", " tribenzyl ", " front three oxide compound ", " three b-oxides ", " three positive propoxides ", " three isopropoxides ", " tricobalt tetroxide " or " three (penta fluoro benzene oxide compound) " and must compound.
That these transistion metal compounds can only use is a kind of, also can make up two or more uses.
More than in the illustrative transistion metal compound, as the compound (A) that the present invention uses, preferred M
1Be the compound of zirconium or the L in the formula ［ 1 ］
1Has the transistion metal compound that at least one has the group of cyclopentadiene shape anion frame.Wherein, the L in the special preferred formula ［ 1 ］
1Have 2 group and L with cyclopentadiene shape anion frame
1Each other through containing the group banded zirconium compounds of carbon atom, Siliciumatom, Sauerstoffatom, sulphur atom or phosphorus atom.
Transistion metal compound shown in the formula ［ 1 ］ can disclose the method for manufacture of middle records such as No. 95/00562 specification sheets through japanese kokai publication hei 6-340684 communique, japanese kokai publication hei 7-258321 communique, international monopoly and make.
Acvator (B)
The acvator that uses among the present invention (B) is so long as can get final product aforesaid compound (A) activatory; In addition; When in the polymerization (for example slurry polymerization, vapour phase polymerization, mass polymerization etc.) of the formation of following addition polymer particle to be generated, using; Preferred use specific particle, the shape of addition polymer to be generated is formalized as one of catalyst component.As specific particle, can use the particle of following (I), following (II) or following (III) aptly through modification.
(I): following (a), following (b), following (c) are contacted with following (d) and the particle through modification
(a): the compound shown in the formula ［ 3 ］
M
2L
2 2? ［3］
(b): the compound shown in the formula ［ 4 ］
R
3 t-1TH ［4］
(c): the compound shown in the formula ［ 5 ］
R
4 u-2T’H
2? ［5］
(d): inorganic oxide particle or organic polymer particle
(M
2Be IIB family element; L
2Be Wasserstoffatoms, halogen atom or alkyl, 2 L
2Can be identical or different each other; R
3For electrophilic property group or contain the group of electrophilic property group; T-1 is greater than 1 o'clock, a plurality of R
3Can be identical or different each other; R
4Be alkyl or halo alkyl; T is VA family element or VIA family element; T is the number that is equivalent to the valency of T; T ' is VA family element or VIA family element; U is the number that is equivalent to the valency of T '.）
(II): make inorganic oxide particle or organic polymer particle (d), contact with aikyiaiurnirsoxan beta (e) and the particle through modification
(III): make inorganic oxide particle or organic polymer particle (d), contact with aikyiaiurnirsoxan beta (e), compound (A) and the particle through modification
Below, successively they are further specified.
M in the formula ［ 3 ］
2The expression periodic table of elements (IUPAC inorganic chemistry nomenclature revised edition 1989) IIB family element.As its concrete example, can enumerate zinc atom, cadmium atom, mercury atom.As M
2, preferred especially zinc atom.
In the formula ［ 3 ］, L
2Be Wasserstoffatoms, halogen atom or alkyl.As L
2Halogen atom, for example can enumerate: fluorine atom, chlorine atom, bromine atoms and iodine atom.As L
2Alkyl, preferred alkyl, aryl or aralkyl.
As L
2The alkyl of alkyl; The alkyl of preferred carbonatoms 1～20; For example can enumerate: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec.-butyl, the tertiary butyl, isobutyl-, n-pentyl, neo-pentyl, n-hexyl, n-heptyl, n-octyl, positive decyl, dodecyl, Pentadecane base and NSC 62789 base, more preferably methyl, ethyl, sec.-propyl, the tertiary butyl or isobutyl-.
L
2Alkyl all can have halogen atoms such as fluorine atom, chlorine atom, bromine atoms and iodine atom as substituting group.As having the alkyl of halogen atom as substituent carbonatoms 1～20; For example can enumerate: methyl fluoride, difluoromethyl, trifluoromethyl, fluoro ethyl, two fluoro ethyls, trifluoroethyl, tetrafluoro ethyl, pentafluoroethyl group, perfluoro propyl, perfluoro butyl, perfluor amyl group, perfluoro hexyl, perfluoro capryl, perfluor dodecyl, perfluor pentadecyl, perfluor eicosyl, 1H; 1H-perfluoro propyl, 1H; 1H-perfluoro butyl, 1H, 1H-perfluor amyl group, 1H, 1H-perfluoro hexyl, 1H; 1H-perfluoro capryl, 1H; 1H-perfluor dodecyl, 1H, 1H-perfluor pentadecyl, 1H, 1H-perfluor eicosyl and with " fluorine " of these alkyl be replaced into " chlorine ", " bromine " or " iodine " and alkyl.These alkyl all can have aralkoxies such as aryloxy such as alkoxyl groups such as methoxyl group and oxyethyl group, phenoxy or benzyloxy as substituting group.
As L
2The aryl of alkyl, the aryl of preferred carbonatoms 6～20 for example can be enumerated: phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl, 2; 5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl, 2; 3,4-trimethylphenyl, 2,2; 3,6-trimethylphenyl, 2,4,6-trimethylphenyl, 3; 4,5-trimethylphenyl, 2,3,4; 5-tetramethylphenyl, 2,3,4,6-tetramethylphenyl, 2; 3,5,6-tetramethylphenyl, pentamethyl-phenyl, ethylphenyl, n-propyl phenyl, isopropyl phenyl, n-butylphenyl, secondary butyl phenenyl, tert-butyl-phenyl, isobutyl phenenyl, n-pentyl phenyl, neo-pentyl phenyl, n-hexyl phenyl, n-octyl phenyl, positive decyl phenyl, dodecyl phenyl, n-tetradecane base phenyl, naphthyl and anthryl, more preferably phenyl.These aryl all can have aralkoxies such as aryloxy such as alkoxyl groups such as halogen atom, methoxyl group and oxyethyl group, phenoxys such as fluorine atom, chlorine atom, bromine atoms and iodine atom or benzyloxy etc. as substituting group.
As L
2Aralkyl, the aralkyl of preferred carbonatoms 7～20 for example can be enumerated: benzyl, (2-aminomethyl phenyl) methyl, (3-aminomethyl phenyl) methyl, (4-aminomethyl phenyl) methyl, (2, the 3-3,5-dimethylphenyl) methyl, (2; The 4-3,5-dimethylphenyl) methyl, (2, the 5-3,5-dimethylphenyl) methyl, (2, the 6-3,5-dimethylphenyl) methyl, (3, the 4-3,5-dimethylphenyl) methyl, (3; The 5-3,5-dimethylphenyl) methyl, (2,3, the 4-trimethylphenyl) methyl, (2,3; The 5-trimethylphenyl) methyl, (2,3, the 6-trimethylphenyl) methyl, (3; 4, the 5-trimethylphenyl) methyl, (2,4; The 6-trimethylphenyl) methyl, (2,3,4; The 5-tetramethylphenyl) methyl, (2,3,4; The 6-tetramethylphenyl) methyl, (2,3,5; The 6-tetramethylphenyl) methyl, (pentamethyl-phenyl) methyl, (ethylphenyl) methyl, (n-propyl phenyl) methyl, (isopropyl phenyl) methyl, (n-butylphenyl) methyl, (secondary butyl phenenyl) methyl, (tert-butyl-phenyl) methyl, (isobutyl phenenyl) methyl, (n-pentyl phenyl) methyl, (neo-pentyl phenyl) methyl, (n-hexyl phenyl) methyl, (n-octyl phenyl) methyl, (positive decyl phenyl) methyl, naphthyl methyl and anthryl methyl, wherein, more preferably benzyl.These aralkyl all can have aralkoxies such as aryloxy such as alkoxyl groups such as halogen atom, methoxyl group and oxyethyl group, phenoxys such as fluorine atom, chlorine atom, bromine atoms and iodine atom or benzyloxy etc. as substituting group.
L as formula ［ 3 ］
2, preferred Wasserstoffatoms, alkyl or aryl, more preferably Wasserstoffatoms or alkyl, preferred alkyl especially.
T in the formula ［ 4 ］ representes the VA family element or the VIA family element of the periodic table of elements (IUPAC inorganic chemistry nomenclature revised edition 1989).As the concrete example of VA family element, can enumerate nitrogen-atoms, phosphorus atom etc., as the concrete example of VIA family element, can enumerate Sauerstoffatom, sulphur atom etc.As T, preferred nitrogen atom or Sauerstoffatom, special preferred oxygen atom.
T in the formula ［ 4 ］ representes to be equivalent to the number of the valency of T, when T is VA family element then t be 3, when T is VIA family element then t be 2.
The VA family element or the VIA family element of T ' the expression periodic table of elements (IUPAC inorganic chemistry nomenclature revised edition 1989) in the formula ［ 5 ］.As the concrete example of VA family element, can enumerate nitrogen-atoms, phosphorus atom etc., as the concrete example of VIA family element, can enumerate Sauerstoffatom, sulphur atom etc.As T ', preferred nitrogen atom or Sauerstoffatom, special preferred oxygen atom.
U in the formula ［ 5 ］ representes to be equivalent to the number of the valency of T ', T ' during for VA family element then u be 3, T ' during for VIA family element then u be 2.
R in the formula ［ 4 ］
3Expression electrophilic property group or contain the group of electrophilic property group, R
3Exist when a plurality of, they can be identical or different each other.
As the index of electrophilic property, the substituent constant σ of known Hammett rule etc., the substituent constant σ that can enumerate the Hammett rule on the occasion of the functional group as electrophilic property group.
As R
3The concrete example of electrophilic property group, can enumerate fluorine atom, chlorine atom, bromine atoms, iodine atom, cyanic acid, nitro, carbonyl, sulfo group, phenyl etc.As the group that contains electrophilic property group, can enumerate haloalkyl, halogenated aryl, (haloalkyl) aryl, cyaniding aryl, nitrated aryl, ester group (alkoxy carbonyl, aromatic alkoxy carbonyl or aryloxycarbonyl) etc.
As R
3The concrete example of haloalkyl, can enumerate: methyl fluoride, chloromethyl, brooethyl, iodomethyl, difluoromethyl, dichloromethyl, two brooethyls, diiodomethyl, trifluoromethyl, trichloromethyl, trisbromomethyl, three iodomethyls, 2,2,2-trifluoroethyl, 2,2,2-three chloroethyls, 2,2; 2-three bromomethyl, 2,2,2-triiodo ethyl, 2,2,3,3,3-five fluoropropyls, 2; 2,3,3,3-pentachloro-propyl group, 2,2,3,3; 3-pentabromo-propyl group, 2,2,3,3,3-pentaiodo propyl group, 2,2,2-three fluoro-1-trifluoromethyl ethyls, 2; 2,2-three chloro-1-trichloromethyl ethyls, 2,2,2-three bromo-1-trisbromomethyl ethyls, 2,2,2-three iodo-1-triiodo methylethyls, 1; Two (trifluoromethyl)-2,2 of 1-, 2-trifluoroethyl, 1, two (trichloromethyl)-2,2 of 1-, 2-three chloroethyls, 1; Two (trisbromomethyl)-2,2 of 1-, 2-three bromomethyl, 1, two (three iodomethyls)-2,2 of 1-, 2-triiodo ethyl etc.
As R
3The concrete example of halogenated aryl, can enumerate: 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,4 difluorobenzene base, 2,6-difluorophenyl, 3,4-difluorophenyl, 3,5-difluorophenyl, 2,4; 6-trifluorophenyl, 3,4,5-trifluorophenyl, 2,3,5,6-tetrafluoro phenyl, pentafluorophenyl group, 2,3; 5,6-tetrafluoro-4-trifluoromethyl, 2,3,5,6-tetrafluoro-4-pentafluorophenyl group phenyl, perfluor-1-naphthyl, perfluor-2-naphthyl, 2-chloro-phenyl-, 3-chloro-phenyl-, 4-chloro-phenyl-, 2,4 dichloro benzene base, 2,6-dichlorophenyl, 3; 4-dichlorophenyl, 3,5-dichlorophenyl, 2,4,6-trichlorophenyl, 3,4,5-trichlorophenyl, 2,3; 5,6-tetrachloro phenyl, five chlorophenyl, 2,3,5,6-tetrachloro-4-trichloromethyl phenyl, 2,3; 5,6-tetrachloro-4-five chlorophenyl phenyl, perchloro--1-naphthyl, perchloro--2-naphthyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2,4-dibromo phenyl, 2,6-dibromo phenyl, 3,4-dibromo phenyl, 3,5-dibromo phenyl, 2; 4,6-tribromo phenyl, 3,4,5-tribromo phenyl, 2,3,5; 6-tetrabromo phenyl, penta-bromophenyl, 2,3,5,6-tetrabromo-4-trisbromomethyl phenyl, 2,3,5; 6-tetrabromo-4-penta-bromophenyl phenyl, perbromo--1-naphthyl, perbromo--2-naphthyl, 2-iodophenyl, 3-iodophenyl, 4-iodophenyl, 2,4-diiodo-phenyl, 2,6-diiodo-phenyl, 3,4-diiodo-phenyl, 3,5-diiodo-phenyl, 2,4; 6-triiodophenyl, 3,4,5-triiodophenyl, 2,3,5,6-tetraiodo phenyl, pentaiodo phenyl, 2; 3,5, the 6-tetraiodo-4-triiodo aminomethyl phenyl, 2,3,5, the 6-tetraiodo-4-pentaiodo phenyl, periodo-1-naphthyl, periodo-2-naphthyl etc.
As R
3The concrete example of (haloalkyl) aryl; Can enumerate: 2-(trifluoromethyl) phenyl, 3-(trifluoromethyl) phenyl, 4-(trifluoromethyl) phenyl, 2, two (trifluoromethyl) phenyl, 3 of 6-, two (trifluoromethyl) phenyl, 2 of 5-; 4; 6-three (trifluoromethyl) phenyl, 3,4,5-three (trifluoromethyl) phenyl etc.
As R
3The concrete example of cyaniding aryl, can enumerate: 2-cyano-phenyl, 3-cyano-phenyl, 4-cyano-phenyl etc.
As R
3The concrete example of nitrated aryl, can enumerate: 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl etc.
As R
3The concrete example of ester group, can enumerate: methoxycarbonyl, ethoxy carbonyl, positive propoxy carbonyl, isopropoxy carbonyl, phenyloxycarbonyl, trifluoromethoxy carbonyl, penta fluoro benzene oxygen base carbonyl etc.
R
3Preferred halo alkyl, more preferably haloalkyl or halogenated aryl.Further preferred methyl fluoride, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 2,2,3,3,3-five fluoropropyls, 2; 2,2-three fluoro-1-trifluoromethyl ethyls, 1, two (trifluoromethyl)-2,2 of 1-, 2-trifluoroethyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,4 difluorobenzene base, 2; 6-difluorophenyl, 3,4-difluorophenyl, 3,5-difluorophenyl, 2,4,6-trifluorophenyl, 3,4; 5-trifluorophenyl, 2,3,5,6-tetrafluoro phenyl, pentafluorophenyl group, 2,3,5; 6-tetrafluoro-4-trifluoromethyl, 2,3,5,6-tetrafluoro-4-pentafluorophenyl group phenyl, perfluor-1-naphthyl, perfluor-2-naphthyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-three chloroethyls, 2; 2,3,3,3-pentachloro-propyl group, 2,2,2-three chloro-1-trichloromethyl ethyls, 1; Two (trichloromethyl)-2,2 of 1-, 2-three chloroethyls, 4-chloro-phenyl-, 2,6-dichlorophenyl, 3.5-dichlorophenyl, 2,4,6-trichlorophenyl, 3; 4,5-trichlorophenyl or five chlorophenyl, preferred especially fluoroalkyl or fluoro aryl, trifluoromethyl, 2,2 most preferably, 2-three fluoro-1-trifluoromethyl ethyls, 1; Two (trifluoromethyl)-2,2 of 1-, 2-trifluoroethyl, 3,5-difluorophenyl, 3,4,5-trifluorophenyl or pentafluorophenyl group.
R in the formula ［ 5 ］
4Expression alkyl or halo alkyl.As R
4In alkyl, preferred alkyl, aryl or aralkyl, can use with general formula ［ 3 ］ in L
2Illustrated same alkyl.As R
4In the halo alkyl, can enumerate haloalkyl, halogenated aryl, (haloalkyl) aryl etc., can use and enumerate R as above-mentioned general formula ［ 4 ］
3In same haloalkyl, halogenated aryl, (haloalkyl) aryl of concrete example of electrophilic property group.
R in the formula ［ 5 ］
4Preferred halo alkyl, further preferred fluoro alkyl.
As the compound (a) that in the particle (I) of modification, uses, at M
2During for zinc atom, for example can enumerate: zinc halides such as haloalkyl zinc, zinc fluoride, zinc chloride, zinc bromide and zinc iodide such as dialkylene zinc such as diaryl zine, diallyl zinc such as dialkyl group zinc such as zinc methide, zinc ethyl, dipropyl zinc, di-n-butyl zinc, diisobutyl zinc, di-n-hexyl zinc, phenylbenzene zinc, dinaphthyl zinc and two (pentafluorophenyl group) zinc, two (cyclopentadienyl moiety) zinc, chloro methyl zinc, chloro zinc ethyl, chloro propyl group zinc, chloro normal-butyl zinc, chloro isobutyl-zinc, chloro n-hexyl zinc, bromomethyl zinc, bromoethyl zinc, bromo propyl group zinc, bromo normal-butyl zinc, bromo isobutyl-zinc, bromo n-hexyl zinc, iodo-methyl zinc, iodo zinc ethyl, iodo propyl group zinc, iodo normal-butyl zinc, iodo isobutyl-zinc and iodo n-hexyl zinc.
The preferred dialkyl group zinc of compound (a), more preferably zinc methide, zinc ethyl, dipropyl zinc, di-n-butyl zinc, diisobutyl zinc or di-n-hexyl zinc, especially preferably zinc methide or zinc ethyl.
Compound (b) as amine, can be enumerated two (methyl fluoride) amine, two (chloromethyl) amine, two (brooethyl) amine, two (iodomethyl) amine, two (difluoromethyl) amine, two (dichloromethyl) amine, two (two brooethyls) amine, two (diiodomethyl) amine, two (trifluoromethyl) amine, two (trichloromethyl) amine, two (trisbromomethyl) amine, two (three iodomethyls) amine, two (2,2, the 2-trifluoroethyl) amine, two (2 when being illustrated as concrete example; 2,2-three chloroethyls) amine, two (2,2, the 2-three bromomethyl) amine, two (2,2; 2-triiodo ethyl) amine, two (2,2,3,3,3-five fluoropropyls) amine, two (2; 2,3,3,3-pentachloro-propyl group) amine, two (2,2; 3,3,3-pentabromo-propyl group) amine, two (2,2,3; 3,3-pentaiodo propyl group) amine, two (2,2,2-three fluoro-1-trifluoromethyl ethyls) amine, two (2; 2,2-three chloro-1-trichloromethyl ethyls) amine, two (2,2,2-three bromo-1-trisbromomethyl ethyls) amine, two (2; 2,2-three iodo-1-triiodo methylethyls) amine, two (1, two (trifluoromethyl)-2,2 of 1-; The 2-trifluoroethyl) amine, two (1, two (trichloromethyl)-2,2 of 1-, 2-three chloroethyls) amine, two (1; Two (trisbromomethyl)-2,2 of 1-, 2-three bromomethyl) amine, two (1, two (three iodomethyls)-2 of 1-; 2,2-triiodo ethyl) amine, two (2-fluorophenyl) amine, two (3-fluorophenyl) amine, two (4-fluorophenyl) amine, two (2-chloro-phenyl-) amine, two (3-chloro-phenyl-) amine, two (4-chloro-phenyl-) amine, two (2-bromophenyl) amine, two (3-bromophenyl) amine, two (4-bromophenyl) amine, two (2-iodophenyl) amine, two (3-iodophenyl) amine, two (4-iodophenyl) amine, two (2, the 6-difluorophenyl) amine, two (3, the 5-difluorophenyl) amine, two (2; The 6-dichlorophenyl) amine, two (3, the 5-dichlorophenyl) amine, two (2, the 6-dibromo phenyl) amine, two (3, the 5-dibromo phenyl) amine, two (2; 6-diiodo-phenyl) amine, two (3,5-diiodo-phenyl) amine, two (2,4, the 6-trifluorophenyl) amine, two (2; 4,6-trichlorophenyl) amine, two (2,4,6-tribromo phenyl) amine, two (2; 4,6-triiodophenyl) amine, two (3,4, the 5-trifluorophenyl) amine, two (3; 4,5-trichlorophenyl) amine, two (3,4,5-tribromo phenyl) amine, two (3; 4,5-triiodophenyl) amine, two (pentafluorophenyl group) amine, two (five chlorophenyl) amine, two (penta-bromophenyl) amine, two (pentaiodo phenyl) amine, two (2-(trifluoromethyl) phenyl) amine, two (3-(trifluoromethyl) phenyl) amine, two (4-(trifluoromethyl) phenyl) amine, two (2,6-two (trifluoromethyl) phenyl) amine, two (3,5-two (trifluoromethyl) phenyl) amine, two (2; 4,6-three (trifluoromethyl) phenyl) amine, two (3,4,5-three (trifluoromethyl) phenyl) amine, two (2-cyano-phenyl) amine, (3-cyano-phenyl) amine, two (4-cyano-phenyl) amine, two (2-nitrophenyl) amine, two (3-nitrophenyl) amine, two (4-nitrophenyl) amine etc.In addition, also likewise the illustration nitrogen-atoms be substituted by the phosphine compound of phosphorus atom.These phosphine compounds are to be rewritten as compound that phosphine representes etc. through the amine with above-mentioned concrete example.
In addition, as the concrete example of compound (b),, can enumerate: fluorine methyl alcohol, chloromethane alcohol, bromine methyl alcohol, iodine methyl alcohol, difluoro methyl alcohol, dichloro methyl alcohol, dibromo methyl alcohol, diiodo-methyl alcohol, trifluoro methyl alcohol, trichlorine methyl alcohol, tribromo methyl alcohol, triiodo methyl alcohol, 2,2,2 tfifluoroethyl alcohol, 2,2 as alcohols; 2-ethapon, tribromo-ethanol, 2,2,2-three iodohydrin, 2,2,3; 3,3-five fluorine propyl alcohol, 2,2,3,3,3-pentachloro-propyl alcohol, 2,2; 3,3,3-pentabromo-propyl alcohol, 2,2,3,3,3-pentaiodo propyl alcohol, 2; 2,2-three fluoro-1-trifluoromethyl ethanol, 2,2,2-three chloro-1-trichloromethyl ethanol, 2,2,2-three bromo-1-trisbromomethyl ethanol, 2,2; 2-three iodo-1-triiodo methyl ethanol, 1, two (the trifluoromethyl)-2,2,2 tfifluoroethyl alcohols, 1 of 1-, two (the trichloromethyl)-trichloro-ethyl alcohol, 1 of 1-; Two (the trisbromomethyl)-tribromo-ethanol, 1 of 1-, two (three iodomethyls)-2,2 of 1-, 2-three iodohydrin etc.In addition, also likewise the illustration Sauerstoffatom be substituted by the mercaptan compound of sulphur atom.These mercaptan compounds are to be rewritten as thiomethyl alcohol, ethanol is rewritten as sulfur alcohol, propyl alcohol is rewritten as compound that propylmercaptan representes etc. through the methyl alcohol with above-mentioned concrete example.
As the concrete example of compound (b),, can enumerate: fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,4 difluorobenzene phenol, 2,6-difluorophenol, 3,4-difluorophenol, 3 as phenols; 5-difluorophenol, 2,4,6-trifluoromethyl phenol, 3,4,5-trifluoromethyl phenol, 2,3; 5,6-polytetrafluoroethylene phenol, Pentafluorophenol, 2,3,5,6-tetrafluoro-4-trifloro methyl phenol, 2,3; 5,6-tetrafluoro-4-pentafluorophenyl group phenol, perfluor-1-naphthols, perfluor-beta naphthal, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 2,4 dichloro phenol, 2,6-NSC 2879,3,4-NSC 2879,3,5-NSC 2879,2; 4,6-Trichlorophenol 98,3,4,5-Trichlorophenol 98,2,3,5; 6-chlorophenosic acid, pentachlorophenol, 2,3,5,6-tetrachloro-4-trichloromethyl phenol, 2,3,5; 6-tetrachloro-4-five chlorophenyl phenol, perchloro--1-naphthols, perchloro--beta naphthal, 2-bromophenol, 3-bromophenol, 4-bromophenol, 2,4-dibromophenol, 2,6-dibromophenol, 3,4-dibromophenol, 3,5-dibromophenol, 2,4; 6-tribromophenol, 3,4,5-tribromophenol, 2,3,5,6-tetrabromo phenol, pentabromophenol, 2; 3,5,6-tetrabromo-4-trisbromomethyl phenol, 2,3,5,6-tetrabromo-4-penta-bromophenyl phenol, perbromo--1-naphthols, perbromo--beta naphthal, 2-iodophenol, 3-iodophenol, 4-iodophenol, 2; 4-iodophenesic acid, 2,6-iodophenesic acid, 3,4-iodophenesic acid, 3,5-iodophenesic acid, 2,3; 4,5-iodophenisic acid, 2,3,5,6-tetraiodo phenol, pentaiodo phenol, 2,3; 5, the 6-tetraiodo-4-triiodo methylphenol, 2,3,5, the 6-tetraiodo-4-pentaiodo phenylphenol, periodo-1-naphthols, periodo-beta naphthal, 2-(trifluoromethyl) phenol, 3-(trifluoromethyl) phenol, 4-(trifluoromethyl) phenol, 2, two (trifluoromethyl) phenol, 3 of 6-; Two (trifluoromethyl) phenol, 2,4 of 5-, 6-three (trifluoromethyl) phenol, 3,4,5-three (trifluoromethyl) phenol, 2-cyanophenol, 3-cyanophenol, 4-cyanophenol, 2-nitrophenols, 3-nitrophenols, 4-nitrophenols etc.In addition, also likewise the illustration Sauerstoffatom be substituted by the thiol compounds of sulphur atom.These thiol compounds are to be rewritten as compound that thiophenol representes etc. through the phenol with above-mentioned concrete example.
As compound (b), preferably as two (trifluoromethyl) amine, two (2,2, the 2-trifluoroethyl) amine, two (2,2,3 of amine; 3,3-five fluoropropyls) amine, two (2,2,2-three fluoro-1-trifluoromethyl ethyls) amine, two (1, two (trifluoromethyl)-2 of 1-; 2,2-trifluoroethyl) amine or two (pentafluorophenyl group) amine, trifluoro methyl alcohol, 2,2,2 tfifluoroethyl alcohol, 2,2 as alcohols; 3,3,3-five fluorine propyl alcohol, 2,2,2-three fluoro-1-trifluoromethyl ethanol or 1; Two (the trifluoromethyl)-2,2,2 tfifluoroethyl alcohols of 1-, 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2 as phenols, 6-difluorophenol, 3,5-difluorophenol, 2; 4,6-trifluoromethyl phenol, 3,4,5-trifluoromethyl phenol, Pentafluorophenol, 2-(trifluoromethyl) phenol, 3-(trifluoromethyl) phenol, 4-(trifluoromethyl) phenol, 2, two (trifluoromethyl) phenol, 3 of 6-; Two (trifluoromethyl) phenol, 2,4 of 5-, 6-three (trifluoromethyl) phenol or 3,4,5-three (trifluoromethyl) phenol.
As compound (b), more preferably two (trifluoromethyl) amine, two (pentafluorophenyl group) amine, trifluoro methyl alcohol, 2,2,2-three fluoro-1-trifluoromethyl ethanol, 1, two (trifluoromethyl)-2 of 1-; 2,2-trifluoroethanol, 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,6-difluorophenol, 3,5-difluorophenol, 2,4; 6-trifluoromethyl phenol, 3,4,5-trifluoromethyl phenol, Pentafluorophenol, 4-(trifluoromethyl) phenol, 2, two (trifluoromethyl) phenol or 2,4 of 6-; 6-three (trifluoromethyl) phenol, further preferred 3,5-difluorophenol, 3,4; 5-trifluoromethyl phenol, Pentafluorophenol or 1, two (the trifluoromethyl)-2,2,2 tfifluoroethyl alcohols of 1-.
As compound (c), for example can enumerate: water, hydrogen sulfide, amine and aniline compound.As amine; For example can enumerate: aralkylamine, methyl fluoride amine, difluoromethyl amine, trifluoromethyl amine, 2 such as alkylamine, allyl amine, cyclopentadienyl moiety amine and benzyl amine such as methylamine, ethylamine, n-propyl amine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, isobutylamine, n-pentyl amine, neo-pentyl amine, isoamylamine, n-hexyl amine, n-octylamine, positive decyl amine, dodecyl amine, Pentadecane base amine and NSC 62789 base amine; 2,2-trifluoroethyl amine, 2,2; 3; 3,3-five fluoropropyl amine, 2,2; 2-three fluoro-1-trifluoromethyl ethylamines, 1; Two (trifluoromethyl)-2,2 of 1-, 2-trifluoroethyl amine, perfluoro propyl amine, perfluoro butyl amine, perfluor amylamine, perfluoro hexyl amine, perfluoro capryl amine, perfluor lauryl amine, perfluor pentadecyl amine, perfluor eicosyl amine and with " fluorine " of these amine be replaced into " chlorine ", " bromine " or " iodine " and haloalkyl amine.
As the aniline compound of compound (c), for example can enumerate: aniline, ALPHA-NAPHTHYL AMINE, anthryl amine, 2-tolyl amine, 3-tolyl amine, 4-tolyl amine, 2,3-xylyl amine, 2,4-xylyl amine, 2,5-xylyl amine, 2; 6-xylyl amine, 3,4-xylyl amine, 3,5-xylyl amine, 2,3,4-trimethylaniline, 2; 3,5-trimethylaniline, 2,3,6-trimethylaniline, 2,4; 6-trimethylaniline, 3,4,5-trimethylaniline, 2,3,4; 5-tetramethyl-aniline, 2,3,4,6-tetramethyl-aniline, 2,3; 5,6-tetramethyl-aniline, pentamethylaminobenzene, 2-MEA, 3-MEA, 4-MEA, 2,3-Diethyl Aniline, 2,4-Diethyl Aniline, 2,5-Diethyl Aniline, 2; 6-Diethyl Aniline, 3,4-Diethyl Aniline, 3,5-Diethyl Aniline, 2,3,4-triethyl aniline, 2; 3,5-triethyl aniline, 2,3,6-triethyl aniline, 2,4; 6-triethyl aniline, 3,4,5-triethyl aniline, 2,3,4; 5-tetraethyl-aniline, 2,3,4,6-tetraethyl-aniline, 2,3; 5,6-tetraethyl-aniline, pentaethyl benzene amine and with their " ethyl " be replaced into " n-propyl ", " sec.-propyl ", " normal-butyl ", " sec.-butyl ", " tertiary butyl ", " n-pentyl ", " neo-pentyl ", " n-hexyl ", " n-octyl ", " positive decyl ", " dodecyl " or " n-tetradecane base " and alkyl benzene amine, 2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 2,6-difluoroaniline, 3,5-difluoroaniline, 2; 4,6-trifluoromethyl aniline, 3,4, halo aniline, 2-(trifluoromethyl) aniline, 3-(trifluoromethyl) aniline, 4-(trifluoromethyl) aniline, 2 such as 5-trifluoromethyl aniline and penta fluoro benzene amine; 6-two (trifluoromethyl) aniline, 3,5-two (trifluoromethyl) aniline, 2,4,6-three (trifluoromethyl) aniline and with their " fluorine " be replaced into " chlorine ", " bromine " or " iodine " and (haloalkyl) aniline.
Compound (c) preferably water, hydrogen sulfide, methylamine, ethylamine, n-propyl amine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, isobutylamine, n-octylamine, aniline, 2,6-xylyl amine, 2,4; 6-trimethylaniline, ALPHA-NAPHTHYL AMINE, anthryl amine, benzyl amine, trifluoromethyl amine, pentafluoroethyl group amine, perfluoro propyl amine, perfluoro butyl amine, perfluor amylamine, perfluoro hexyl amine, perfluoro capryl amine, perfluor lauryl amine, perfluor pentadecyl amine, perfluor eicosyl amine, 2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 2,6-difluoroaniline, 3,5-difluoroaniline, 2; 4,6-trifluoromethyl aniline, 3,4; 5-trifluoromethyl aniline, penta fluoro benzene amine, 2-(trifluoromethyl) aniline, 3-(trifluoromethyl) aniline, 4-(trifluoromethyl) aniline, 2, two (trifluoromethyl) aniline, 3 of 6-, two (trifluoromethyl) aniline or 2 of 5-; 4,6-three (trifluoromethyl) aniline, special preferably water, trifluoromethyl amine, perfluoro butyl amine, perfluoro capryl amine, perfluor pentadecyl amine, 2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 2; 6-difluoroaniline, 3,5-difluoroaniline, 2,4; 6-trifluoromethyl aniline, 3; 4,5-trifluoromethyl aniline, penta fluoro benzene amine, 2-(trifluoromethyl) aniline, 3-(trifluoromethyl) aniline, 4-(trifluoromethyl) aniline, 2, two (trifluoromethyl) aniline, 3 of 6-; Two (trifluoromethyl) aniline or 2 of 5-; 4,6-three (trifluoromethyl) aniline, most preferably water or penta fluoro benzene amine.
As (d), can enumerate inorganic oxide particle or organic polymer particle, preferably can be used as the uniform porous granule of particle diameter of carrier among them usually.As the size distribution of (d), from the viewpoint of the size distribution of gained addition polymer, the geometric standard deviation of the volume reference of the particle diameter of preferred (d) is below 2.5, more preferably below 2.0, further is preferably below 1.7.
As the inorganic oxide particle of (d), can use any inorganic oxide, also can mix multiple inorganic substance and use.As inorganic oxide, for example can enumerate: SiO
2, Al
2O
3, MgO, ZrO
2, TiO
2, B
2O
3, CaO, ZnO, BaO and ThO
2, and their mixture, SiO
2-MgO, SiO
2-Al
2O
3, SiO
2-TiO
2, SiO
2-V
2O
5, SiO
2-Cr
2O
3, and SiO
2-TiO
2-MgO.The preferred SiO of these inorganic oxides
2And/or Al
2O
3, preferred especially SiO
2(being silicon-dioxide).Above-mentioned inorganic oxide can contain minor N a
2CO
3, K
2CO
3, CaCO
3, MgCO
3, Na
2SO
4, Al
2(SO
4)
3, BaSO
4, KNO
3, Mg (NO
3)
2, Al (NO
3)
3, Na
2O, K
2O, Li
2Carbonate such as O, vitriol, nitrate salt, oxide components.
Inorganic oxide preferably through dry, remove moisture basically, drying means is preferably heat drying.Drying temperature is for the visual inorganic oxide that can't confirm moisture, and typical temperature is 100～1500 ℃, is preferably 100～1000 ℃, more preferably 200～800 ℃.Not special qualification time of drying, but preferred 10 minutes～50 hours, more preferably 1 hour～30 hours.As the method for heat drying, for example can enumerate: adding the method etc. of pining for making exsiccant rare gas element (for example, nitrogen or argon etc.) to carry out the exsiccant method or under reduced pressure carrying out heat drying with the constant flow rate circulation.
In the inorganic oxide, though generate on the surface usually and have hydroxyl, as inorganic oxide, the reactive hydrogen that also can use surface hydroxyl replaced by various substituting group and the modified inorganic oxide compound.As the modified inorganic oxide compound; For example can enumerate: with tetraalkoxysilanes, 1 such as aryl trialkoxy silane, tetramethoxy-silicane such as alkyltrialkoxysilaneand such as diaryl dialkoxy silicane, methyltrimethoxy silane, phenyltrimethoxysila,e such as dialkyl dialkoxy silicane, dimethoxydiphenylsilane such as triaryl organoalkoxysilanes such as trialkyl organoalkoxysilanes such as aryl trichlorosilanes such as alkyl trichlorosilane, phenyl-trichloro-silicanes such as diaryl dichlorosilane, METHYL TRICHLORO SILANEs such as dialkyldichlorosilan,s such as triaryl chlorosilane, dimethyldichlorosilane(DMCS), diphenyl dichlorosilanes such as trialkylchlorosilanes such as trimethylchlorosilane, TERT-BUTYL DIMETHYL CHLORO SILANE, tri-phenyl chloride, trimethylammonium methoxy silane, triphenyl methoxy silane and dimethyldimethoxysil,ne; 1; 1; 3; 3, lithium alkylides such as dialkyl magnesium, butyllithium such as alcohol such as alkyl disilazane, tetrachloro silicane, methyl alcohol and ethanol such as 3-hexamethyldisilazane, phenol, dibutylmagnesium, butyl ethyl magnesium, butyl octyl magnesium contact the inorganic oxide of handling and getting.
And then also can enumerate: after trialkylaluminium contacts, contact the inorganic oxide of handling and getting with alcohol such as dialkylamines such as DIETHANOL AMINE, diphenylamine, methyl alcohol, ethanol, phenol.
For inorganic oxide, hydroxyl produces hydrogen bond each other makes the intensity of inorganic oxide self improve sometimes.At this moment, when the reactive hydrogen of supposing surface hydroxyl is all replaced by various substituting group, cause the reduction of particle intensity etc. sometimes.So the reactive hydrogen of the surface hydroxyl of inorganic oxide not necessarily must all replace, the replacement rate of suitable decision surface hydroxyl gets final product.Make not special qualification of method of the replacement rate change of surface hydroxyl.As this method, for example can enumerate the method for the usage quantity that changes the compound that uses in the contact processing.
The median size of inorganic oxide particle is not special to be limited, but be generally 1～5000 μ m, be preferably 5～1000 μ m, more preferably 10～500 μ m, further be preferably 10～100 μ m.Pore volume is preferably above, the 0.3～10ml/g more preferably of 0.1ml/g.Specific surface area is preferably 10～1000m
2/ g, 100～500m more preferably
2/ g.
(d) organic polymer particle can use any organic polymer, can also use the mixture of multiple organic polymer in addition.As organic polymer, be preferably the lewis base property functional group's of containing functional group with reactive hydrogen or non-proton supply property polymkeric substance.
As the functional group with reactive hydrogen, reactive hydrogen is then not special to be limited as long as have.As this functional group, for example can enumerate: primary amino, secondary amino group, imino-, carboxamido-group, hydrazide group, amidino groups, hydroxyl, hydroperoxy, carboxyl, formyl radical, formamyl, sulfonic group, sulfino, sulfeno, thiol group, thioformyl, pyrryl, imidazolyl, piperidyl, indazolyl and carbazyl.Preferred primary amino, secondary amino group, imino-, carboxamido-group, imide, hydroxyl, formyl radical, carboxyl, sulfonic group or thiol group, preferred especially primary amino, secondary amino group, carboxamido-group or hydroxyl.These groups can also have the alkyl of halogen atom or carbonatoms 1～20 as substituting group.
As the lewis base property functional group of non-proton supply property, the functional group of the Lewis base part with reactive hydrogen atom is then not special to be limited so long as contain.As this functional group; For example can enumerate: pyridyl, N-substituted imidazole base, N-substituted indazolyl, itrile group, azido-, N-substituted imido, N; N-substituted-amino, N, N-replaces aminooxy, N, N; N-replaces diazanyl, nitroso-group, nitro, nitre oxygen base, furyl, carbonyl, thiocarbonyl, alkoxyl group, alkyl oxy carbonyl, N, N-substituted-amino formyl radical, thio alkoxy, replacement sulfinyl, substituted sulphonyl and substituted sulfonic acid base.Preferred heterocyclic group more preferably has the aromatic heterocyclic group of Sauerstoffatom and/or nitrogen-atoms in the ring.Preferred especially pyridyl, N-substituted imidazole base, N-substituted indazolyl, most preferably pyridyl.These groups can also be by the hydrocarbyl substituted of halogen atom or carbonatoms 1～20.
The functional group with reactive hydrogen in the organic polymer or the lewis base property functional group's of non-proton supply property content is not special to be limited.Its content is as the molar weight with respect to the functional group of the unit gram of polymkeric substance, is preferably 0.01～50mmol/g, more preferably 0.1～20mmol/g.
As the method for manufacture of the lewis base property functional group's of containing functional group with reactive hydrogen or non-proton supply property organic polymer, for example can enumerate: the method that makes the monomer of the lewis base property functional group that comprises functional group with reactive hydrogen or non-proton supply property and 1 above polymerizability unsaturated group carry out the method for homopolymerization or make this monomer and other monomer carry out copolymerization with polymerizability unsaturated group.The crosslinking polymerization property monomer copolymerization together that further preferably also will have at this moment, 2 above polymerizability unsaturated groups.
As the polymerizability unsaturated group, for example can enumerate: alkynyls such as thiazolinyls such as vinyl, allyl group, ethynyl.As comprising the functional group with reactive hydrogen and the monomer of 1 above polymerizability unsaturated group, for example can enumerate: contain vinyl primary amine, contain vinyl secondary amine, contain the amide compound of vinyl and contain the oxy-compound of vinyl.As this monomer, for example can enumerate: N-(1-vinyl) amine, N-(2-propenyl) amine, N-(1-vinyl)-N-methylamine, N-(2-propenyl)-N-methylamine, 1-vinylamide, 2-propenyl acid amides, N-methyl-(1-vinyl) acid amides, N-methyl-(2-propenyl) acid amides, vinyl alcohol, 2-propylene-1-alcohol, 3-butene-1-alcohol.As comprising the functional group of containing Lewis base part and the monomer of 1 above polymerizability unsaturated group, for example can enumerate: vinyl pyridine, vinyl (N-replacement) imidazoles and vinyl (N-replacement) indazole with reactive hydrogen atom.
As other monomer, for example can enumerate: ethene, terminal olefin, aromatic ethenyl compound and cyclic olefin compound with polymerizability unsaturated group.As this monomer, for example can enumerate: ethene, propylene, 1-butylene, 1-hexene, 4-methyl-1-pentene, vinylbenzene, norbornylene, Dicyclopentadiene (DCPD).Optimal ethylene or vinylbenzene.These monomers can use more than 2 kinds.As crosslinking polymerization property monomer, for example can enumerate: Vinylstyrene etc. with above-mentioned 2 above polymerizability unsaturated groups.
The median size of organic polymer particle is not special to be limited, and is generally 1～5000 μ m, is preferably 5～1000 μ m, 10～500 μ m more preferably.Pore volume is not special to be limited, and is preferably above, the 0.3～10ml/g more preferably of 0.1ml/g.Specific surface area is not special to be limited, and is preferably 10～1000m
2/ g, 50～500m more preferably
2/ g.
These organic polymer particles preferably through dry, remove moisture basically, preferably carry out drying through heat drying.Drying temperature can't confirm that for visual the organic polymer of moisture is generally 30～400 ℃, is preferably 50～200 ℃, more preferably 70～150 ℃.Heat-up time, not special the qualification was preferably 10 minutes～50 hours, more preferably 1 hour～30 hours.As the method for heat drying, for example can enumerate: adding the method etc. of pining for making exsiccant rare gas element (for example, nitrogen or argon etc.) to carry out the exsiccant method or under reduced pressure carrying out heat drying with the constant flow rate circulation.
The order that mentioned component (a) and (b), (c) are contacted with (d) is not special to be limited, and for example can enumerate following order.
＜1＞(a) contacted with (c) with the contactant of (b), the gained contactant is contacted with (d).
＜2＞(a) contacted with (d) with the contactant of (b), the gained contactant is contacted with (c).
＜3＞(a) contacted with (b) with the contactant of (c), the contactant of gained is contacted with (d).
＜4＞(a) contacted with (d) with the contactant of (c), the gained contactant is contacted with (b).
＜5＞(a) contacted with (b) with the contactant of (d), the gained contactant is contacted with (c).
＜6＞(a) contacted with (c) with the contactant of (d), the gained contactant is contacted with (b).
＜7＞(b) contacted with (a) with the contactant of (c), the gained contactant is contacted with (d).
＜8＞(b) contacted with (d) with the contactant of (c), the gained contactant is contacted with (a).
＜9＞(b) contacted with (a) with the contactant of (d), the gained contactant is contacted with (c).
＜10＞(b) contacted with (c) with the contactant of (d), the gained contactant is contacted with (a).
＜11＞(c) contacted with (a) with the contactant of (d), the gained contactant is contacted with (b).
＜12＞(c) contacted with (b) with the contactant of (d), the gained contactant is contacted with (a).
As engagement sequence, preferably above-mentioned＜1＞,＜2＞,＜3＞,＜5＞,＜11＞or＜12＞.Especially preferably＜2＞or＜5＞.
Above-mentioned contact is handled and preferably under inert gas atmosphere, is carried out.Treatment temp is generally-100～300 ℃, is preferably-80～200 ℃.Treatment time is generally 1 minute～and 200 hours, be preferably 10 minutes～100 hours.In addition, above-mentioned processing can be used solvent, perhaps also can not use solvent and these compounds are directly contacted processing.
As solvent, can use above-claimed cpd (a) and (b), (c), (d) and their contactant are the inert solvent.But; When each compound is contacted; Even if the solvent that in certain stage, reacts with certain compound as long as this solvent is the solvent that in other stage, does not react with each compound, then also can use this solvent in other stage.That is the solvent in each stage, can be identical or different each other.As this solvent; For example can enumerate: non-polar solvents such as aliphatic hydrocarbon solvent, aromatic hydrocarbon solvents, halide solvent, ether series solvent, pure series solvent, phenol series solvent, carbonyl series solvent, phosphoric acid derivatives, nitrile series solvent, nitro-compound, amine series solvent and sulphur compound isopolarity solvent.For example can enumerate: butane, pentane, hexane, heptane, octane, 2; 2; Aromatic hydrocarbon solvents, methylene dichloride, methylene fluoride, chloroforms, 1 such as aliphatic hydrocarbon solvents such as 4-trimethylpentane, hexanaphthene, benzene,toluene,xylene; 2-ethylene dichloride, 1; 2-ethylene dibromide, 1; 1; 2-three chloro-1; 2; Halide solvent, dimethyl ether, Anaesthetie Ether, Di Iso Propyl Ether, di-n-butyl ether, MTBE, methyl-phenoxides, 1 such as 2-HFC-143a, zellon, chlorobenzene, bromobenzene, orthodichlorobenzene; 4-two
alkane, 1; Phenol series solvent, acetone, ethyl methyl ketone, pimelinketone, diacetyl oxide, ETHYLE ACETATE, butylacetate, ethylene carbonate, Texacar PC, N such as pure series solvent, phenol, p-cresol such as ether series solvent, methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-butanols, 2-methyl isophthalic acid-propyl alcohol, 3-methyl isophthalic acid-butanols, hexalin, benzylalcohol, terepthaloyl moietie, Ucar 35,2-methyl cellosolve, cellosolvo, glycol ether, triglycol, glycerine such as 2-glycol dimethyl ether, two (2-methoxy ethyl) ether, THF, tetrahydropyrans; Sulphur compounds such as amine series solvent, DMSO 99.8MIN., tetramethylene sulfone such as nitro-compounds such as nitrile series solvent, Nitromethane 99Min., oil of mirbane, pyridine, piperidines, morpholine such as phosphoric acid derivatives such as carbonyl series solvent, HPT, triethyl phosphate, acetonitrile, propionitrile, sym-dicyanoethane, cyanobenzene such as dinethylformamide, DMAC N,N, N-N-methyl-2-2-pyrrolidone N-.
The compound (a) and (b) are contacted with (c) and make gained contactant (f) and particle (d) when contacting; Promptly above-mentioned＜1＞,＜3＞,＜7＞each method in, the solvent (s1) when making contactant (f) is preferably above-mentioned aliphatic hydrocarbon solvent, aromatic hydrocarbon solvents or ether series solvent.
Make contactant (f) be preferably polar solvent with the solvent (s2) of particle (d) when contacting.The index of expression solvent polarity is known to have an E
T NValues (C.Reichardt, " Solvents and Solvents Effects in Organic Chemistry ", 2nd ed., VCH Verlag (1988) .) etc. especially preferably satisfy 0.8>=E
T NThe solvent of>=0.1 scope.As said polar solvent; For example can enumerate: methylene dichloride, Refrigerant 12 chloroform, 1; 2-ethylene dichloride, 1; 2-ethylene dibromide, 1; 1; 2-three chloro-1; 2; 2-HFC-143a, zellon, chlorobenzene, bromobenzene, orthodichlorobenzene, dimethyl ether, Anaesthetie Ether, Di Iso Propyl Ether, di-n-butyl ether, MTBE, methyl-phenoxide, 1; 4-two
alkane, 1; 2-glycol dimethyl ether, two (2-methoxy ethyl) ether, THF, tetrahydropyrans, methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-butanols, 2-methyl isophthalic acid-propyl alcohol, 3-methyl isophthalic acid-butanols, hexalin, benzylalcohol, terepthaloyl moietie, Ucar 35,2-methyl cellosolve, cellosolvo, glycol ether, triglycol, acetone, ethyl methyl ketone, pimelinketone, diacetyl oxide, ETHYLE ACETATE, butylacetate, ethylene carbonate, Texacar PC, N, dinethylformamide, DMAC N,N, N-N-methyl-2-2-pyrrolidone N-, HPT, triethyl phosphate, acetonitrile, propionitrile, sym-dicyanoethane, cyanobenzene, Nitromethane 99Min., oil of mirbane, quadrol, pyridine, piperidines, morpholine, DMSO 99.8MIN. and tetramethylene sulfone.The further preferred dimethyl ether of solvent (s2), Anaesthetie Ether, Di Iso Propyl Ether, di-n-butyl ether, MTBE, methyl-phenoxide, 1; 4-two
alkane, 1; 2-glycol dimethyl ether, two (2-methoxy ethyl) ether, THF, tetrahydropyrans, methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-butanols, 2-methyl isophthalic acid-propyl alcohol, 3-methyl isophthalic acid-butanols, hexalin, benzylalcohol, terepthaloyl moietie, Ucar 35,2-methyl cellosolve, cellosolvo, glycol ether or triglycol; Preferred especially di-n-butyl ether, MTBE, 1; 4-two
alkane, THF, methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-butanols, 2-methyl isophthalic acid-propyl alcohol, 3-methyl isophthalic acid-butanols or hexalin, most preferably THF, methyl alcohol, ethanol, 1-propyl alcohol or 2-propyl alcohol.
In addition, as solvent (s2), can also use the mixed solvent of these polar solvents and hydrocarbon solvent.Illustrative aliphatic hydrocarbon solvent or aromatic hydrocarbon solvents more than hydrocarbon solvent can use.As the mixed solvent of polar solvent and hydrocarbon solvent, for example can enumerate: hexane/methanol mixed solvent, hexane/alcohol mixed solvent, hexane/1-propyl alcohol mixed solvent, hexane/2-propyl alcohol mixed solvent, heptane/methanol mixed solvent, heptane/alcohol mixed solvent, heptane/1-propyl alcohol mixed solvent, heptane/2-propyl alcohol mixed solvent, toluene and methanol mixed solvent, toluene/ethanol mixed solvent, toluene/1-propyl alcohol mixed solvent, toluene/2-propyl alcohol mixed solvent, YLENE/methanol mixed solvent, YLENE/alcohol mixed solvent, YLENE/1-propyl alcohol mixed solvent and YLENE/2-propyl alcohol mixed solvent.Preferred hexane/methanol mixed solvent, hexane/alcohol mixed solvent, heptane/methanol mixed solvent, heptane/alcohol mixed solvent, toluene and methanol mixed solvent, toluene/ethanol mixed solvent, YLENE/methanol mixed solvent, YLENE/alcohol mixed solvent.More preferably hexane/methanol mixed solvent, hexane/alcohol mixed solvent, toluene and methanol mixed solvent or toluene/ethanol mixed solvent.Toluene/ethanol mixed solvent most preferably.Preferable range in the toluene/ethanol mixed solvent, proportion of ethanol is 10～50 volume %, 15～30 volume % more preferably.
The method that makes the compound (a) and (b) contact and make gained contactant (f) with (c) to contact with (d), promptly above-mentioned＜1＞,＜3＞,＜7＞each method in, as solvent (s1) and solvent (s2), can also all use hydrocarbon solvent.At this moment, after making the compound (a) and (b) and (c) contacting, the time till making gained contactant (f) and particle (d) contacts is short more preferred more.Time is preferably 0～5 hour, more preferably 0～3 hour, most preferably be 0～1 hour.In addition, make contactant (f) be generally-100 ℃～40 ℃ with the temperature of particle (d) when contacting, be preferably-20 ℃～20 ℃, most preferably be-10 ℃～10 ℃.
Above-mentioned＜2＞,＜5＞,＜6＞,＜8＞,＜9＞,＜10＞,＜11＞,＜12＞situation in, above-mentioned non-polar solvent, polar solvent all can use.Be preferably non-polar solvent.Its reason is thought owing to (a) with the contactant of (c) or (a) contact the contactant that gets with (c) with the contactant of (b) solvability with respect to non-polar solvent is low usually; Thereby these contactants when generating in the reaction system if there be (d), the contactant that then generates can be separated out the cause that is immobilized more easily to the surface of (d).
The not special restriction of the amount that each compound of above-mentioned (a) and (b), (c) is in contact with one another; Make the molar ratio of the amount that each compound is in contact with one another be designated as (a): (b): (c)=during the molar ratio of 1:y:z, then preferred y and z satisfy following formula (1) basically.
｜m-y-2z｜＜1 （1）
(in the above-mentioned formula (1), m representes M
2Valency)
Y in the above-mentioned formula (1) is preferably 0.01～1.99 number; 0.10～1.80 number more preferably; Further be preferably 0.20～1.50 number, most preferably be 0.30～1.00 number, the same preferable range of the z in the above-mentioned in addition formula (1) is decided by m, y and above-mentioned formula (1).
Compound (a) and usage quantity (d) are preferably when the typical metal atom that makes compound (a) contained in the particle (I) that derives from through modification is scaled the mole number of typical metal atom contained among the gained particle 1g and reach the amount more than the 0.05mmol, more preferably reach the amount of 0.1～20mmol.
For reaction is carried out more fast, preferably after handling, add the heating process under the higher temperature like above-mentioned contact.In the heating process, for forming more high temperature, preferably using the high solvent of boiling point, when carrying out heating process, can be the higher solvent of other boiling point with the used solvent exchange of contact operation.
For particle (I) through modification, after above-mentioned contact is handled, can be with the residual compound (a) and (b) of the form of unreacted reactant, (c) and/or (d) as raw material.But, preferably carry out the carrying out washing treatment of in advance unreacted reactant being removed.The solvent of this moment can be when contacting solvent identical or different.Above-mentioned carrying out washing treatment is preferably implemented under inert gas atmosphere.Treatment temp is generally-100～300 ℃, is preferably-80～200 ℃.
Treatment time is generally 1 minute～and 200 hours, be preferably 10 minutes～100 hours.
In addition, during above-mentioned carrying out washing treatment, preferably (I) sedimentation of the particle through modification in making solvent and amorphous or micro mist particle swim and under the state on slurries top, remove the solvent on top, to obtain particle diameter, shape uniformly through the particle (I) of modification.
In addition, after above-mentioned contact processing, the carrying out washing treatment, preferably heat up in a steamer and desolvate, under the temperature more than 0 ℃, carried out drying then under reduced pressure 1 hour～24 hours from resultant.More preferably under 0 ℃～200 ℃ the temperature 1 hour～24 hours, further preferably under 10 ℃～200 ℃ the temperature 1 hour～24 hours, particularly preferably in 10 ℃～160 ℃ temperature under 2 hours～18 hours, most preferably under 15 ℃～160 ℃ temperature 4 hours～18 hours.
For M
2For zinc atom, compound (b) are 3,4,5-trifluoromethyl phenol, compound (c) are water, and (d) are the situation of silicon-dioxide, will be illustrated in greater detail in following through the concrete example of the method for manufacture of the particle (I) of modification.THF as solvent, to the hexane solution that wherein adds zinc ethyl, is cooled to 3 ℃; To wherein dripping with respect to zinc ethyl is 3 of equimolar amount; 4, the 5-trifluoromethyl phenol is after room temperature carries out stirring in 10 minutes～24 hours; And then to drip with respect to zinc ethyl be the water of 0.5 times of molar weight, stirring at room 10 minutes～24 hours.Then, heat up in a steamer and desolvate, carried out down drying under the decompression in 8 hours at 120 ℃.Add THF, silicon-dioxide to the solids component that obtains by above operation, stirred 2 hours at 40 ℃.Solids component with after the THF washing, was carried out drying in 8 hours under 120 ℃ of decompressions.So can make the particle through modification of the present invention (I).
As the aikyiaiurnirsoxan beta of in the preparation of the particle (II) of modification, using (e), can preferably use the { Al (E that has general formula
2)-O-}
eShown in structure the cyclic aikyiaiurnirsoxan beta and/or have general formula E
3{ Al (E
3)-O-}
cAlE
3 2Shown in the aikyiaiurnirsoxan beta of wire of structure.
(wherein, E
2, and E
3Alkyl, all E respectively do for oneself
2With whole E
3Can be identical or different.E representes that number, the c more than 2 representes the number more than 1.）
E
2, or E
3In alkyl be preferably the alkyl of carbonatoms 1～8, more preferably alkyl.
As above-mentioned E
2, E
3Concrete example, but illustration: alkyl such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, n-pentyl, neo-pentyl.E is the number more than 2, and c is the number more than 1.Preferred E
2And E
3Be methyl or isobutyl-, e is 2～40, and c is 1～40.
Above-mentioned aikyiaiurnirsoxan beta can be made by the whole bag of tricks.The not special restriction of this method is as long as make according to known method.For example, trialkylaluminium (for example, trimethylaluminium etc.) is dissolved in suitable organic solvent (benzene, aliphatic alkyl etc.) and gained solution is contacted with water and makes.In addition, but also illustration make the method that the metal-salt (for example, copper sulfate hydrate etc.) that contains crystal water and trialkylaluminium (for example, trimethylaluminium etc.) contact is made.By these class methods aikyiaiurnirsoxan beta be considered to form the mixture of the aikyiaiurnirsoxan beta of cyclic aikyiaiurnirsoxan beta and wire usually.
The particle (d) that in the particle (II) of modification, uses can use and (d) the identical particle that in the particle (I) of modification, uses.
Can make aikyiaiurnirsoxan beta (e) contact the particle of making through modification (II) with particle (d) through arbitrary method.Particularly, through being scattered in the solvent and to wherein adding aikyiaiurnirsoxan beta (e), makes on particle (d).
The solvent of this moment can use arbitrary solvent of being put down in writing in the particle (I) through modification, is preferably the solvent that does not react with aikyiaiurnirsoxan beta (e), more preferably makes aikyiaiurnirsoxan beta (e) dissolved solvent.Particularly, aliphatic hydrocarbon solvents such as aromatic hydrocarbon solvents such as preferred toluene or YLENE or hexane, heptane, octane, more preferably toluene or YLENE.
Temperature, time that aikyiaiurnirsoxan beta (e) is contacted with particle (d) can be selected arbitrarily, but temperature be generally-100 ℃～200 ℃, be preferably-50 ℃～150 ℃, more preferably-20 ℃～120 ℃.Particularly initial reaction stage is preferably reacted to suppress heating at low temperatures.The amount of contact can be selected arbitrarily, will convert in the aluminium atom with respect to the aikyiaiurnirsoxan beta (e) of the unit of particle (d) gram, is generally 0.01～100mmol, is preferably 0.1～20mmol, 1～10mmol more preferably.
Through the particle (III) of modification be through the preparation of the particle (II) of modification the time, further use compound (A) and.
As compound (A), can use the transistion metal compound dimer of the transistion metal compound shown in the formula ［ 1 ］ or its mu-oxo type.
Aikyiaiurnirsoxan beta (e), particle (d) and contacting through any means of compound (A) are implemented, and make the particle (III) through modification.At this moment, preferably use solvent, this solvent can use arbitrary solvent of above-mentioned record, is preferably the solvent that does not react with aikyiaiurnirsoxan beta (e) and compound (A), more preferably dissolves the solvent of aikyiaiurnirsoxan beta (e) and compound (A).Particularly, aliphatic hydrocarbon solvents such as aromatic hydrocarbon solvents such as preferred toluene or YLENE or hexane, heptane, octane, more preferably toluene or YLENE.
Temperature, time that aikyiaiurnirsoxan beta (e), particle (d) and compound (A) are contacted can be selected arbitrarily, but temperature be generally-100 ℃～200 ℃, be preferably-50 ℃～150 ℃, more preferably-20 ℃～120 ℃.Particularly initial reaction stage is preferably reacted to suppress heating at low temperatures.The amount of contact can be selected arbitrarily, will convert in the aluminium atom with respect to the aikyiaiurnirsoxan beta (e) of the unit of particle (d) gram, is generally 0.01～100mmol, is preferably 0.1～20mmol, 1～10mmol more preferably.In addition, will convert in transition metal atoms, be generally 0.1～1000 μ mol, be preferably 1～500 μ mol, 10～200 μ mol more preferably with respect to the transistion metal compound (A) of the unit of particle (d) gram.
Organo-aluminium compound (C)
The organo-aluminium compound that uses among the present invention (C) can use known organo-aluminium compound.Be preferably the organo-aluminium compound shown in the formula ［ 8 ］.
R
6 dAlY
3-d ［8］
(in the formula, R
6Expression alkyl, all R
6Can be identical or different.Y representes Wasserstoffatoms, halogen atom, alkoxyl group, aralkoxy or aryloxy, and all Y can be identical or different.D representes to satisfy the number of 0＜d≤3.）
R in the formula ［ 8 ］
6Be preferably the alkyl of carbonatoms 1～24, more preferably the alkyl of carbonatoms 1～24.As concrete example, can enumerate methyl, ethyl, n-propyl, normal-butyl, isobutyl-, n-hexyl, 2-methyl hexyl, n-octyl etc., be preferably ethyl, normal-butyl, isobutyl-, n-hexyl or n-octyl.
In addition, the concrete example when being halogen atom as Y can be enumerated fluorine atom, chlorine atom, bromine atoms, iodine atom, is preferably the chlorine atom.
As the alkoxyl group among the Y; The alkoxyl group of preferred carbonatoms 1～24; As concrete example; For example can enumerate: 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, NSC 62789 oxygen base etc. are preferably methoxyl group, oxyethyl group or tert.-butoxy.
As the aryloxy among the Y, the aryloxy of preferred carbonatoms 6～24 as concrete example, for example can be enumerated: phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 2,3-dimethyl phenoxy, 2; 4-dimethyl phenoxy, 2,5-dimethyl phenoxy, 2,6-dimethyl phenoxy, 3,4-dimethyl phenoxy, 3,5-dimethyl phenoxy, 2; 3,4-trimethylammonium phenoxy, 2,3,5-trimethylammonium phenoxy, 2,3; 6-trimethylammonium phenoxy, 2,4,5-trimethylammonium phenoxy, 2,4; 6-trimethylammonium phenoxy, 3,4,5-trimethylammonium phenoxy, 2,3; 4,5-tetramethyl-phenoxy, 2,3,4; 6-tetramethyl-phenoxy, 2,3,5,6-tetramethyl-phenoxy, pentamethyl-phenoxy, ethyl phenoxy, n-propyl phenoxy, sec.-propyl phenoxy, normal-butyl phenoxy, sec.-butyl phenoxy, tertiary butyl phenoxy, n-hexyl phenoxy, n-octyl phenoxy, positive decyl phenoxy, n-tetradecane phenoxyl, naphthyloxy, anthracene oxygen base etc.
As the aralkoxy among the Y, the aralkoxy of preferred carbonatoms 7～24 is as concrete example; For example can enumerate: 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) methoxyl group, (2; 4, the 6-trimethylphenyl) methoxyl group, (3,4; The 5-trimethylphenyl) methoxyl group, (2,3,4; The 5-tetramethylphenyl) methoxyl group, (2,3,5; 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, (n-tetradecane base phenyl) methoxyl group, naphthyl methoxyl group, anthryl methoxyl group etc., preferred benzyloxy.
As the concrete example of the organo-aluminium compound shown in the formula ［ 8 ］, but illustration: trialkylaluminiums such as trimethylaluminium, triethyl aluminum, tri-n-n-propyl aluminum, three n-butylaluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium; Dialkyl aluminum chlorides such as dimethyl-aluminium muriate, diethyl aluminum muriate, di aluminium muriate, di-n-butyl aluminium muriate, diisobutyl aluminum muriate, di-n-hexyl aluminium muriate; Aluminum alkyls dichloride such as aluminium trimethide dichloride, ethyl aluminum dichloride, n-propyl aluminium dichloride, n-butylaluminum dichloride, aluminium isobutyl dichloride, n-hexyl aluminium dichloride; Dialkyl aluminum hydrides such as dimethyl-alanate, diethyl aluminum hydrogenate, di alanate, di-n-butyl alanate, diisobutyl alanate, di-n-hexyl alanate; Alkyl (dialkoxy) aluminium such as methyl (dimethoxy) aluminium, methyl (diethoxy) aluminium, methyl (two tert.-butoxies) aluminium; Dialkyl group (alkoxyl group) aluminium such as dimethyl-(methoxyl group) aluminium, dimethyl-(oxyethyl group) aluminium, dimethyl-(tert.-butoxy) aluminium; Alkyl (two aryloxy) aluminium such as methyl (two phenoxys) aluminium, two (2, the 6-di-isopropyl phenoxy) aluminium of methyl, two (2, the 6-phenylbenzene phenoxy) aluminium of methyl; Dialkyl group (aryloxy) aluminium such as dimethyl-(phenoxy) aluminium, dimethyl-(2,6-di-isopropyl phenoxy) aluminium, dimethyl-(2,6-phenylbenzene phenoxy) aluminium etc.
Among them, preferred trialkylaluminium, further preferred trimethylaluminium, triethyl aluminum, three n-butylaluminum, triisobutyl aluminium, tri-n-hexyl aluminum or tri-n-octylaluminium, preferred especially triisobutyl aluminium or tri-n-octylaluminium.
These organo-aluminium compounds can only use a kind of, also can make up two or more uses.
Organic cpds (D)
The organic cpds that uses among the present invention (D) is the compound shown in the following formula ［ 2 ］.
R
1C（＝O）NR
2 2 ［2］
R
1For having the alkyl of substituent carbonatoms 1～30; R
2For having the alkyl of substituent carbonatoms 1～30; Two R
2Can be identical or different each other.
As R
1The alkyl with substituent carbonatoms 1～30, can enumerate: can have substituent carbonatoms 1～30 alkyl, can have substituent carbonatoms 7～30 aralkyl, can have the aryl of substituent carbonatoms 6～30 etc.
As R
1The alkyl with substituent carbonatoms 1～30, can enumerate: the alkyl of carbonatoms 1～30, have halogen atom as the alkyl of substituent carbonatoms 1～30, have replace silyl as the alkyl of substituent carbonatoms 1～30, have substituted-amino as the alkyl of substituent carbonatoms 1～30, have-oxyl as the alkyl of substituent carbonatoms 1～30 etc.
As R
1The alkyl of carbonatoms 1～30, for example can enumerate: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec.-butyl, the tertiary butyl, n-pentyl, neo-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base, n-hexadecyl, NSC 172782 base, Octadecane base, NSC 77136 base, NSC 62789 base, heneicosane base, n-docosane base, n-tricosane base, n-tetracosane base, pentacosane base, n-hexacosane base, heptacosane base, positive octacosyl, positive nonacosyl, positive triacontyl etc.
As R
1Have the alkyl of halogen atom as substituent carbonatoms 1～30, for example can enumerate: methyl fluoride, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, brooethyl, two brooethyls, trisbromomethyl, iodomethyl, diiodomethyl, three iodomethyls, fluoro ethyl, two fluoro ethyls, trifluoroethyl, tetrafluoro ethyl, pentafluoroethyl group, chloroethyl, Dichloroethyl, three chloroethyls, tetrachloro ethyl, pentachloro-ethyl, bromotrifluoromethane, two bromotrifluoromethanes, three bromomethyl, tetrabromo ethyl, pentabromo-ethyl, perfluoro propyl, perfluoro butyl, perfluor amyl group, perfluoro hexyl, perfluoro capryl, perfluor dodecyl, perfluor pentadecyl, perfluor eicosyl, perfluor triacontyl, perchloro-propyl group, perchloro-butyl, perchloro-amyl group, perchloro-hexyl, perchloro-octyl group, perchloro-dodecyl, perchloro-pentadecyl, perchloro-eicosyl, perchloro-triacontyl, perbromo-propyl group, perbromo-butyl, perbromo-amyl group, perbromo-hexyl, perbromo-octyl group, perbromo-dodecyl, perbromo-pentadecyl, perbromo-eicosyl, perbromo-triacontyl etc.
As R
1Have and replace the alkyl of silyl as substituent carbonatoms 1～30, for example can enumerate: trimethyl silyl methyl, trimethyl silyl ethyl, trimethyl silyl propyl group, trimethyl silyl butyl, two (trimethyl silyl) methyl, two (trimethyl silyl) ethyl, two (trimethyl silyl) propyl group, two (trimethyl silyl) butyl, triphenyl silyl methyl etc.
As R
1Have the alkyl of substituted-amino as substituent carbonatoms 1～30, for example can enumerate: dimethylaminomethyl, dimethyl aminoethyl, dimethylaminopropyl, dimethylamino butyl, two (dimethylamino) methyl, two (dimethylamino) ethyl, two (dimethylamino) propyl group, two (dimethylamino) butyl, phenyl amino methyl, diphenyl amino methyl etc.
As R
1Have the alkyl of-oxyl as substituent carbonatoms 1～30, for example can enumerate: methoxymethyl, ethoxyl methyl, n-propoxymethyl, isopropoxy methyl, n-butoxy methyl, sec.-butoxy methyl, tert.-butoxy methyl, phenoxymethyl, methoxy ethyl, ethoxyethyl group, positive propoxy ethyl, isopropoxy ethyl, n-butoxy ethyl, sec.-butoxy ethyl, tert.-butoxy ethyl, phenoxy ethyl, methoxyl group n-propyl, oxyethyl group n-propyl, positive propoxy n-propyl, isopropoxy n-propyl, n-butoxy n-propyl, sec.-butoxy n-propyl, tert.-butoxy n-propyl, phenoxypropyl, methoxyl group sec.-propyl, oxyethyl group sec.-propyl, positive propoxy sec.-propyl, isopropoxy sec.-propyl, n-butoxy sec.-propyl, sec.-butoxy sec.-propyl, tert.-butoxy sec.-propyl, phenoxy sec.-propyl etc.
As R
1The aralkyl with substituent carbonatoms 7～30, can enumerate: the aralkyl of carbonatoms 7～30, have halogen atom as aralkyl of substituent carbonatoms 7～30 etc.
As R
1The aralkyl of carbonatoms 7～30, for example can enumerate: benzyl, (2-aminomethyl phenyl) methyl, (3-aminomethyl phenyl) methyl, (4-aminomethyl phenyl) methyl, (2, the 3-3,5-dimethylphenyl) methyl, (2; The 4-3,5-dimethylphenyl) methyl, (2, the 5-3,5-dimethylphenyl) methyl, (2, the 6-3,5-dimethylphenyl) methyl, (3; The 4-3,5-dimethylphenyl) methyl, (4, the 6-3,5-dimethylphenyl) methyl, (2,3; The 4-trimethylphenyl) methyl, (2) methyl, (2; 3, the 6-trimethylphenyl) methyl, (3,4; The 5-trimethylphenyl) methyl, (2,4, the 6-trimethylphenyl) methyl, (2; 3,4, the 5-tetramethylphenyl) methyl, (2; 3; 4, the 6-tetramethylphenyl) methyl, (2,3; 5,6-tetramethylphenyl) methyl, (pentamethyl-phenyl) methyl, (ethylphenyl) methyl, (n-propyl phenyl) methyl, (isopropyl phenyl) methyl, (n-butylphenyl) methyl, (secondary butyl phenenyl) methyl, (tert-butyl-phenyl) methyl, (n-pentyl phenyl) methyl, (neo-pentyl phenyl) methyl, (n-hexyl phenyl) methyl, (n-octyl phenyl) methyl, (positive decyl phenyl) methyl, (positive decyl phenyl) methyl, (n-tetradecane base phenyl) methyl, naphthyl methyl, anthryl methyl, phenylethyl, phenyl propyl, phenyl butyl, diphenyl methyl, diphenyl-ethyl, diphenyl propyl, phenylbenzene butyl etc.
As R
1Have the aralkyl of halogen atom as substituent carbonatoms 7～30, for example can enumerate: 2-luorobenzyl, 3-luorobenzyl, 4-luorobenzyl, 2-benzyl chloride base, 3-benzyl chloride base, 4-benzyl chloride base, 2-bromobenzyl, 3-bromobenzyl, 4-bromobenzyl, 2-iodine benzyl, 3-iodine benzyl, 4-iodine benzyl etc.
As R
1The aryl with substituent carbonatoms 6～30, can enumerate: the aryl of carbonatoms 6～30, have halogen atom as the aryl of substituent carbonatoms 6～30, have replace silyl as the aryl of substituent carbonatoms 6～30, have substituted-amino as the aryl of substituent carbonatoms 6～30, have-oxyl as the aryl of substituent carbonatoms 6～30 etc.
As R
1The aryl of carbonatoms 6～30, for example can enumerate: phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl, 2; 5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl, 2; 3,4-trimethylphenyl, 2,2; 3,6-trimethylphenyl, 2,4,6-trimethylphenyl, 3; 4,5-trimethylphenyl, 2,3,4; 5-tetramethylphenyl, 2,3,4,6-tetramethylphenyl, 2; 3,5,6-tetramethylphenyl, pentamethyl-phenyl, ethylphenyl, diethylammonium phenyl, triethyl phenyl, n-propyl phenyl, isopropyl phenyl, n-butylphenyl, secondary butyl phenenyl, tert-butyl-phenyl, n-pentyl phenyl, neo-pentyl phenyl, n-hexyl phenyl, n-octyl phenyl, positive decyl phenyl, dodecyl phenyl, n-tetradecane base phenyl, naphthyl, anthryl etc.
As R
1Have the aryl of halogen atom as substituent carbonatoms 6～30, for example can enumerate: 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-chloro-phenyl-, 3-chloro-phenyl-, 4-chloro-phenyl-, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2-iodophenyl, 3-iodophenyl, 4-iodophenyl etc.
As R
1Have and replace the aryl of silyl as substituent carbonatoms 6～30, for example can enumerate: trimethyl silyl phenyl, two (trimethyl silyl) phenyl etc.
As R
1Have the aryl of substituted-amino as substituent carbonatoms 6～30, for example can enumerate: dimethylaminophenyl, two (dimethylamino) phenyl, diphenyl amino phenyl etc.
As R
1Have the aryl of-oxyl as substituent carbonatoms 6～30, for example can enumerate: p-methoxy-phenyl, ethoxyl phenenyl, positive propoxy phenyl, isopropyl phenyl, n-butoxy phenyl, sec.-butoxy phenyl, tert.-butoxy phenyl, Phenoxyphenyl etc.
As the R in the aforementioned formula ［ 2 ］
1, be preferably the alkyl that can have substituent carbonatoms 1～30, more preferably the alkyl of carbonatoms 1～30.
As R
2The alkyl with substituent carbonatoms 1～30, can enumerate: can have substituent carbonatoms 1～30 alkyl, can have substituent carbonatoms 7～30 aralkyl, can have the aryl of substituent carbonatoms 6～30 etc.
As R
2The alkyl with substituent carbonatoms 1～30, can enumerate: the alkyl of carbonatoms 1～30, have halogen atom as the alkyl of substituent carbonatoms 1～30, have replace silyl as the alkyl of substituent carbonatoms 1～30, have substituted-amino as the alkyl of substituent carbonatoms 1～30, have-oxyl as the alkyl of substituent carbonatoms 1～30, have hydroxyl as the alkyl of substituent carbonatoms 1～30 etc.
As R
2Carbonatoms 1～30 alkyl, have halogen atom as the alkyl of substituent carbonatoms 1～30, have replace silyl as the alkyl of substituent carbonatoms 1～30, have substituted-amino as the alkyl of substituent carbonatoms 1～30, have the alkyl of-oxyl as substituent carbonatoms 1～30, can enumerate and R
1Carbonatoms 1～30 alkyl illustrative identical group.
As R
2Have the alkyl of hydroxyl as substituent carbonatoms 1～30, for example can enumerate: hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxyl-1-methylethyl, 2-hydroxyl-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, 1-hydroxyl-1-methyl-propyl, 2-hydroxyl-1-methyl-propyl, 3-hydroxyl-1-methyl-propyl, 1-hydroxy-2-methyl propyl group, 2-hydroxy-2-methyl propyl group, 3-hydroxy-2-methyl propyl group, 1-(hydroxymethyl) propyl group, (hydroxymethyl) dimethyl-methyl etc.
As R
2The aralkyl with substituent carbonatoms 7～30, can enumerate and R
1The aralkyl with substituent carbonatoms 7～30 illustrative identical group.
As R
2The aryl with substituent carbonatoms 6～30, can enumerate and R
1The aryl with substituent carbonatoms 6～30 illustrative identical group.
As the R in the aforementioned formula ［ 2 ］
2Preferably have the alkyl of hydroxyl as substituent carbonatoms 1～30; More preferably hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxyl-1-methylethyl, 2-hydroxyl-1-methylethyl, preferred especially hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl.
As organic cpds (D), preferred N, two (2-hydroxyethyl) ethanamides of N-, N; Two (2-hydroxyethyl) the propane acid amides of N-, N, two (2-hydroxyethyl) butane amides of N-, N, two (2-hydroxyethyl) the pentane acid amides of N-, N; Two (2-hydroxyethyl) the hexane acid amides of N-, N, two (2-hydroxyethyl) the heptane acid amides of N-, N, two (2-hydroxyethyl) the octane acid amides of N-, N; Two (2-hydroxyethyl) the nonane acid amides of N-, N, two (2-hydroxyethyl) the decane acid amides of N-, N, two (2-hydroxyethyl) undecanoic amides of N-, N; Two (2-hydroxyethyl) the dodecyl acid amides of N-, N, two (2-hydroxyethyl) the tridecane acid amides of N-, N, two (2-hydroxyethyl) myristamides of N-, N; Two (2-hydroxyethyl) the pentadecane acid amides of N-, N, two (2-hydroxyethyl) palmitic amides of N-, N, two (2-hydroxyethyl) the heptadecane acid amides of N-, N; Two (2-hydroxyethyl) kemanide Ss of N-, N, two (2-hydroxyethyl) the nonadecane acid amides of N-, N, two (2-hydroxyethyl) the eicosane acid amides of N-, N; Two (2-hydroxyethyl) the heneicosane acid amides of N-, N, two (2-hydroxyethyl) the docosane acid amides of N-, N, two (2-hydroxyethyl) the tricosane acid amides of N-, N; Two (2-hydroxyethyl) the tetracosane acid amides of N-, N, two (2-hydroxyethyl) the pentacosane acid amides of N-, N, two (2-hydroxyethyl) the hexacosane acid amides of N-, N; Two (2-hydroxyethyl) the heptacosane acid amides of N-, N; Two (2-hydroxyethyl) the octacosane acid amides of N-, N, two (2-hydroxyethyl) the nonacosane acid amides of N-, N, two (2-hydroxyethyl) the triacontane acid amides of N-
, especially preferably comprise N, two (2-hydroxyethyl) the nonane acid amides of N-, N, two (2-hydroxyethyl) the decane acid amides of N-, N; Two (2-hydroxyethyl) undecanoic amides of N-, N; Two (2-hydroxyethyl) the dodecyl acid amides of N-, N, two (2-hydroxyethyl) the tridecane acid amides of N-, N, two (2-hydroxyethyl) myristamide and the N of N-; The N of two (2-hydroxyethyl) the pentadecane acid amides of N-, two (2-hydroxyethyl) the fatty acid distribution of coconut oil acid amides of N-.
The sub-property compound (E) of supplying power
Of the present inventionly during with the manufacturing of catalyst component and addition polymer, the sub-property compound of power supply (E) is contacted with catalyst component with catalyzer or through prepolymerized addition polymerization through prepolymerized addition polymerization.As power supply sub-property compound (E); Be preferably the compound that contains nitrogen-atoms, phosphorus atom, Sauerstoffatom or sulphur atom; Can enumerate: oxygenatedchemicals, nitrogenous compound, P contained compound, sulfocompound, wherein preferred oxygenatedchemicals or nitrogenous compound.As oxygenatedchemicals, can enumerate: the amides of ester class, organic acid or the mineral acid of alkoxyl silicone class, ethers, ketone, aldehydes, carboxylic-acid, organic acid or mineral acid, anhydrides etc., wherein preferred alkoxyl silicone class or ethers.As nitrogenous compound, can enumerate: amine, nitrile, isocyanates etc., preferred amine.
As the alkoxyl silicone class, can preferably use general formula R
7 rSi (OR
8)
4-r(in the formula, R
7Represent alkyl, the Wasserstoffatoms of carbonatoms 1～20 or contain heteroatomic substituting group, R
8The alkyl of expression carbonatoms 1～20, r representes to satisfy the number of 0≤r＜4.Whole R
7With whole R
8Can be identical or different respectively) shown in alkoxy-silicon compound.
R
7Or R
8During for alkyl, can enumerate aryl such as cycloalkenyl groups such as naphthenic base such as branched-chain alkyl, cyclopentyl, cyclohexyl, cyclopentenyl, phenyl, tolyl such as straight chain shape alkyl, sec.-propyl, sec.-butyl, the tertiary butyl, tert-pentyl such as methyl, ethyl, propyl group, butyl, amyl group etc.R
7When containing heteroatomic substituting group, as heteroatoms, can enumerate: Sauerstoffatom, nitrogen-atoms, sulphur atom, phosphorus atom.Specifically can enumerate: dimethylamino, methylethyl amino, diethylamino, ethyl n-propyl are amino, di is amino, pyrryl, pyridyl, pyrrolidyl, piperidyl, perhydro indyl, hexahydroisoindoline base, perhydro quinolyl, perhydro isoquinolyl, perhydro carbazyl, perhydro acridyl, furyl, pyranyl, perhydro furyl, thienyl etc.
As the alkoxyl silicone class, preferred R
7And R
8For alkyl, more preferably r is for satisfying the number of 4＞r>=2.
As the concrete example of aforementioned alkoxyl silicone class, can enumerate: tetramethoxy-silicane, methyltrimethoxy silane, ethyl trimethoxy silane, n-propyl Trimethoxy silane, sec.-propyl Trimethoxy silane, normal-butyl Trimethoxy silane, isobutyl-Trimethoxy silane, sec.-butyl Trimethoxy silane, tert-butyl trimethoxy silane, n-pentyl Trimethoxy silane, tert-pentyl Trimethoxy silane, dimethyldimethoxysil,ne, diethylammonium dimethoxy silane, di-n-butyl dimethoxy silane, second, isobutyl dimethoxy silane, di-t-butyl dimethoxy silane, methylethyl dimethoxy silane, methyl n-propyl dimethoxy silane, methyl normal-butyl dimethoxy silane, methyl-isobutyl dimethoxy silane, tertiary butyl methyl dimethoxysilane, tertiary butyl ethyl dimethoxy silane, tertiary butyl n-propyl dimethoxy silane, tertiary butyl sec.-propyl dimethoxy silane, tertiary butyl normal-butyl dimethoxy silane, tertiary butyl isobutyl-dimethoxy silane, tert-pentyl methyl dimethoxysilane, tert-pentyl ethyl dimethoxy silane, tert-pentyl n-propyl dimethoxy silane, tert-pentyl normal-butyl dimethoxy silane, isobutyl-sec.-propyl dimethoxy silane, two cyclobutyl dimethoxy silane, cyclobutylmethyl dimethoxy silane, cyclobutyl ethyl dimethoxy silane, cyclobutyl sec.-propyl dimethoxy silane, cyclobutyl normal-butyl dimethoxy silane, cyclobutyl isobutyl-dimethoxy silane, cyclobutyl tertiary butyl dimethoxy silane, dicyclopentyl dimethoxyl silane, cyclopentyl-methyl dimethoxy silane, cyclopentyl n-propyl dimethoxy silane, cyclopentyl sec.-propyl dimethoxy silane, cyclopentyl normal-butyl dimethoxy silane, cyclopentyl isobutyl-dimethoxy silane, cyclopentyl tertiary butyl dimethoxy silane, dicyclohexyl dimethoxy silane, cyclohexyl methyl dimethoxy silane, cyclohexyl ethyl dimethoxy silane, cyclohexyl n-propyl dimethoxy silane, cyclohexyl sec.-propyl dimethoxy silane, cyclohexyl normal-butyl dimethoxy silane, cyclohexyl isobutyl-dimethoxy silane, cyclohexyl tertiary butyl dimethoxy silane, cyclohexyl ring amyl group dimethoxy silane, cyclohexyl phenyl dimethoxy silane, dimethoxydiphenylsilane, phenyl methyl dimethoxy silane, phenylethyl dimethoxy silane, phenyl n-propyl dimethoxy silane, propyloxy phenyl base dimethoxy silane, phenyl normal-butyl dimethoxy silane, phenyl isobutyl-dimethoxy silane, phenyl tertiary butyl dimethoxy silane, benzyl ring amyl group dimethoxy silane, 2-norbornane methyl dimethoxysilane, two (perhydro quinolyl) dimethoxy silane, two (perhydro isoquinolyl) dimethoxy silane, (perhydro quinolyl) (perhydro isoquinolyl) dimethoxy silane, (perhydro quinolyl) methyl dimethoxysilane, (perhydro isoquinolyl) methyl dimethoxysilane, (perhydro quinolyl) ethyl dimethoxy silane, (perhydro isoquinolyl) ethyl dimethoxy silane, (perhydro quinolyl) (n-propyl) dimethoxy silane, (perhydro isoquinolyl) (n-propyl) dimethoxy silane, ((perhydro quinolyl) (tertiary butyl) dimethoxy silane, (perhydro isoquinolyl) (tertiary butyl) dimethoxy silane, trimethylammonium methoxy silane, triethyl methoxy silane, three n-propyl methoxy silane, triisopropyl methoxy silane, three normal-butyl methoxy silane, triisobutyl methoxy silane, tri-tert methoxy silane etc.But also illustration the methoxyl group of these compounds is replaced into oxyethyl group, propoxy-, n-butoxy, isobutoxy, tert.-butoxy, phenoxy and compound.Preferred dialkyl dialkoxy silicane or trialkyl-single organoalkoxysilane, more preferably trialkyl-single organoalkoxysilane.
As the example of ethers, can enumerate: dialkyl ether, alkyl aryl ether, diaryl ether, diether compounds, ring-type ethers and ring-type two ethers.
As concrete example, can enumerate: dimethyl ether, Anaesthetie Ether, di ether, Di Iso Propyl Ether, di-n-butyl ether, diisobutyl ether, di-tert-butyl ether, dicyclohexyl ether, diphenyl ether, methyl ethyl ether, methyl n-propyl ether, methyl isopropyl ether, methyl n-butyl ether, methyl-isobutyl ether, MTBE, methylcyclohexyl ether, methyl phenyl ether, oxyethane, propylene oxide, trimethylene oxide, THF, 2,5-dimethyl-tetrahydrofuran, tetrahydropyrans, 1; 2-glycol dimethyl ether, 1,2-diethoxyethane, 1,2-two isobutoxy ethane, 2; 2-Propanal dimethyl acetal, 1,3-Propanal dimethyl acetal, 2,2-diisobutyl-1; 3-Propanal dimethyl acetal, 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal, 2, two (cyclohexyl methyl)-1 of 2-; 3-Propanal dimethyl acetal, 2-sec.-propyl-2-3,7-dimethyl-octyl group-1,3-Propanal dimethyl acetal, 2; 2-di-isopropyl-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-cyclohexyl methyl-1,3-Propanal dimethyl acetal, 2; 2-dicyclohexyl-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-isobutyl--1,3-Propanal dimethyl acetal, 2; 2-di-isopropyl-1,3-Propanal dimethyl acetal, 2,2-dipropyl-1; 3-Propanal dimethyl acetal, 2-sec.-propyl-2-cyclohexyl-1; 3-Propanal dimethyl acetal, 2-sec.-propyl-2-cyclopentyl-1,3-Propanal dimethyl acetal, 2,2-two cyclopentyl-1; 3-Propanal dimethyl acetal, 2-heptyl-2-amyl group-1; 3-Propanal dimethyl acetal, 1,2-dimethoxy benzene, 1,3-dimethoxy benzene, 1; 4-dimethoxy benzene, 1; 3-dioxolane, 1,4-two
alkane, 1,3-two
alkane etc.Preferred Anaesthetie Ether, di-n-butyl ether, methyl n-butyl ether, methyl phenyl ether, THF, 1; 3-two
alkane, 1; 4-two
alkane, 1; 3-dioxolane, more preferably Anaesthetie Ether, di-n-butyl ether or THF.
As the concrete example of carboxylic acid esters, can enumerate: list and multi-carboxylate, as their example, can enumerate representative examples of saturated aliphatic carboxylic ester, unsaturated aliphatic carboxylicesters, ester ring type carboxylicesters, aromatic carboxylic acid esters.As concrete example, can enumerate: methyl acetate, ETHYLE ACETATE, n-butyl acetate, isobutyl acetate, tert.-butyl acetate, acetate phenylester, methyl propionate, ethyl propionate, ethyl n-butyrate, Valeric acid ethylester, ethyl propenoate, TEB 3K, oil of Niobe, ethyl benzoate, the positive butyl ester of phenylformic acid, isobutyl benzoate, t-butyl perbenzoate, toluic acid methyl esters, toluic acid ethyl ester, p-Methoxybenzoic acid methyl ester, ethyl anisate, succsinic acid dimethyl esters, succsinic acid diethyl ester, succsinic acid di-n-butyl ester, propanedioic acid dimethyl esters, propanedioic acid diethyl ester, propanedioic acid di-n-butyl ester, toxilic acid dimethyl esters, toxilic acid dibutyl ester, methylene-succinic acid diethyl ester, methylene-succinic acid di-n-butyl ester, phthalic acid list ethyl ester, phthalic acid dimethyl esters, phthalic acid methylethyl ester, phthalic acid diethyl ester, phthalic acid di ester, phthalic acid diisopropyl ester, phthalic acid di-n-butyl ester, o-benzene butyl phthalate ester, phthalic acid di-t-butyl ester, phthalic acid diamyl ester, phthalic acid di-n-hexyl ester, phthalic acid diheptyl ester, phthalic acid di-n-octyl ester, phthalic acid two (2-ethylhexyl) ester, phthalic acid diiso decyl ester, dicyclohexyl phthalate, phthalic acid diphenyl, m-phthalic acid dimethyl esters, m-phthalic acid diethyl ester, m-phthalic acid di-n-butyl ester, m-phthalic acid diisobutyl ester, m-phthalic acid di-t-butyl ester, terephthalic acid dimethyl esters, terephthalic acid diethyl ester, terephthalic acid di-n-butyl ester, terephthalic acid diisobutyl ester, terephthalic acid di-t-butyl ester etc.Preferred methyl acetate, ETHYLE ACETATE, oil of Niobe, ethyl benzoate, phthalic acid dimethyl esters, phthalic acid diethyl ester, phthalic acid di-n-butyl ester, o-benzene butyl phthalate ester, terephthalic acid dimethyl esters or terephthalic acid diethyl ester, more preferably oil of Niobe, phthalic acid dimethyl esters, phthalic acid diethyl ester, o-benzene butyl phthalate ester or terephthalic acid dimethyl esters.
As the exemplary compounds of amine, can enumerate trialkylamine, can enumerate: Trimethylamine, triethylamine, tripropylamine, tri-n-butyl amine, triisobutyl amine, three hexyl amines, trioctylphosphine amine, tridodecylamine, triphenylamine.Preferred triethylamine or trioctylphosphine amine.
As power supply sub-property compound (E), preferably use alkoxyl silicone class, ethers or amine.And then, more preferably use amine.These sub-property compounds (E) of supplying power can only use a kind of, also can make up two or more uses.
The method of manufacture of addition polymer of the present invention comprises following operation.
(1) mixed polymerization forms the operation of mixture with solvent and organic cpds (D)
(2) in the presence of catalyzer, but with monomer prepolymerization in aforementioned mixture of addition polymerization, thereby operation obtained through prepolymerized addition polymerization catalyst component
(3) at this in the presence of prepolymerized addition polymerization catalyst component, but the monomer of addition polymerization carried out addition polymerization and make the operation of addition polymer
Use solvent as polymerization, for example can enumerate: halogenated hydrocarbon solvent such as aromatic hydrocarbon solvents such as aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane and octane, benzene and toluene and methylene dichloride.In addition, also can use monomer itself to use solvent, as this monomer, for example can enumerate: ethene, propylene, 1-butylene and 1-hexene as polymerization.
The present invention has mixed polymerization forms mixture with organic cpds (D) shown in solvent and the formula ［ 2 ］ operation.
Organic cpds (D) with respect to polymerization with the amount of solvent be preferably usually the scope of 0.1～1000mg/L, more preferably 1～100mg/L scope, further be preferably the scope of 1.5～40mg/L.
Polymerization can be carried out in polymerization reactor with solvent and mixing of organic cpds (D), also can after mixed polymerization in advance is with solvent and organic cpds (D), this mixture be added into polymerization reactor.In addition, organic cpds (D) also can mix after with solvent monomer being imported polymerization.
Preferable methods is: mixed polymerization forms mixture with solvent and organic cpds (D); Mixing cpd in this mixture (A), acvator (B), organic cpds as required (C) and form catalyzer; Then monomer is imported mixture, carry out the polymeric method through aforementioned catalyzer.
Mixed polymerization does not limit with the method for solvent and organic cpds (D) is special, for example can enumerate: with polymerization with solvent and the direct method of mixing of organic cpds (D); Earlier with organic cpds (D) and with polymerization with solvent phase with solvent, then with this mixture and polymerization method with solvent; Earlier with organic cpds (D) with polymerization with the different solvent of solvent, then with this mixture and polymerization method with solvent; Organic cpds (D) is added into polymerization with the method in the solvent with inert gas flow; Organic cpds (D) is added into polymerization with method in the solvent etc. with the monomer gas air-flow.
Mixed polymerization is preferably stirred with solvent polymerization during with solvent and organic cpds (D).
Temperature when polymerization is added with organic compounds (D) in solvent is not special to be limited, but common 0 ℃ to 150 ℃, preferred 5 ℃ to 100 ℃, more preferably 10 ℃ to 80 ℃ be preferred.
Mixed polymerization is with solvent and organic cpds (D) and the mixture that forms can promptly be used for polymerization after it just forms, and also can mixed polymerization behind the formation mixture, be used further to polymerization with solvent and organic cpds (D) after a while.In the latter's situation, from forming mixture, preferred 5 hours with interior, more preferably 3 hours with interior, further preferred 1 hour with interior this mixture is used for polymerization is preferred.
Catalyzer
Catalyzer among the present invention be make above-claimed cpd (A), acvator (B) and organo-aluminium compound as required (C) contact and.As the contact amount ratio of each composition, the contact amount of compound (A) is generally 0.1～1000 μ mol/g with respect to acvator (B), is preferably 1～500 μ mol/g, more preferably 10～300 μ mol/g.The contact amount of organo-aluminium compound (C) is generally 0.01～10000mmol/g with respect to compound (A), is preferably 0.1～1000mmol/g, more preferably 0.5～200mmol/g.
Make not special qualification of method that compound (A), acvator (B) and organo-aluminium compound (C) contact, for example can enumerate following＜13＞～＜15＞method.
＜13＞make above-mentioned each composition contact, and the gained contactant is dropped into the method for polymerization reactor.
＜14＞above-mentioned each composition is supplied to polymerization reactor respectively, in polymerization reactor, make the method for their contacts.
＜15＞before the input polymerization reactor, make the part contact of above-mentioned each composition and obtain preparatory contactant, the method that this preparatory contactant and remaining component are contacted in polymerization reactor.
As contact method, preferably above-mentioned＜14＞.Can compound (A) be dropped into polymerization reactor with powder or the slurry form that is suspended in the solvent, but the method that preferably compound (A) is dropped into powder.
In addition, to exist mixed polymerization with solvent and organic cpds (D) and the polymerization reactor of mixture in, drop into each composition, make each composition contact and contactant or in advance the method for contactant be preferred.
Make not special qualification of order that compound (A), acvator (B) and organo-aluminium compound (C) contact, for example can enumerate following＜16＞～＜21＞order.
＜16＞compound (A) is contacted with acvator (B), the gained contactant is contacted with organo-aluminium compound (C).
＜17＞compound (A) is contacted with organo-aluminium compound (C), the gained contactant is contacted with acvator (B).
＜18＞acvator (B) is contacted with organo-aluminium compound (C), the gained contactant is contacted with compound (A).
＜19＞compound (A) is contacted with organo-aluminium compound (C), the contactant contact that the gained contactant is got with acvator (B) is contacted with organo-aluminium compound (C).
＜20＞compound (A) is contacted with acvator (B), the contactant contact that the gained contactant is got with acvator (B) is contacted with organo-aluminium compound (C).
＜21＞compound (A) is contacted with organo-aluminium compound (C), the contactant contact that the gained contactant is got with compound (A) is contacted with acvator (B).As engagement sequence, preferably above-mentioned＜16＞.
Can use solvent when in addition, each composition being in contact with one another.Use solvent efficient to form active site well, so preferred.The solvent that uses during as contact is not so long as can make the solvent of the active site inactivation of generation get final product.In addition; More preferably the solvent of dissolved compound (A) specifically also can use halogenated hydrocarbon solvent, ethers, ester class, ketone isopolarity solvents such as aromatic hydrocarbon solvents, methylene dichloride such as aliphatic hydrocarbon solvents such as butane, pentane, hexane, octane and benzene,toluene,xylene.When using in the polymerization (for example, slurry polymerization, mass polymerization etc.) of formation particle, the preferred addition polymer that generates can dissolved solvent, specifically aliphatic hydrocarbon solvent.In addition, also can there be monomer during contact.
Temperature when contacting each composition can be set arbitrarily.Usually-50 ℃ to 100 ℃, preferred-30 ℃ to 80 ℃, more preferably-10 ℃ be preferred to 60 ℃.Can set arbitrarily duration of contact.Be generally and drop into (being 0 minute basically) continuously to 24 hours, preferred 1 minute to 12 hours, more preferably 3 minutes to 10 hours.
Preferably each composition is in contact with one another while stirring.
Use the prepolymerization method of catalyzer
The prepolymerization method of the use catalyzer among the present invention is meant and uses aforementioned catalyzer, but makes the monomer of addition polymerization carry out prepolymerization and obtain through the method for prepolymerized addition polymerization with catalyst component.Sometimes be also referred to as through the pre-polymerized catalyst composition with catalyst component through prepolymerized addition polymerization.
As the prepolymerization method that uses catalyzer, can enumerate the solution polymerization process that in solvent, makes monomer polymerization, slurry polymerization process (suspension polymerization) or will be as the mass polymerization of the monomer polymerization of liquid, preferred slurries polymerization or mass polymerization.
Prepolymerization can be carried out with intermittent type, continous way.And then, prepolymerization can be divided into the 2 different stages of reaction conditions with on carry out.The prepolymerization time suits to determine according to kind, the reaction unit of target olefin polymer usually, can adopt 1 minute～20 hours scope.Solvent and polymerization temperature and polymerization pressure are chosen as solvent and at least a portion monomer are kept with liquid phase, and monomer is contacted with catalyzer.
For the prepolymerization temperature ,-50 ℃ to 100 ℃ usually, preferred-30 ℃ to 80 ℃, more preferably-10 ℃ be preferred to 60 ℃.In addition, can in polymerization process, change temperature.In addition, the pressure during prepolymerization is generally 0.001MPa to 5MPa, is preferably 0.01MPa to 2MPa.
Prepolymerization can be carried out according to known method and condition.The preferred method of this method be with monomer, solvent and other aliment etc. be supplied to continuously or off and on as required polymerization reactor, and will generate through prepolymerized polymerization catalyst component from the polymerization reactor method of taking-up continuously or off and on.As this polymerization reactor, can use annular-pipe reactor, have the reactor drum of stirrer and the reactor drum that kind or the different a plurality of reactor drums that have stirrer of polymeric reaction condition are formed with series, parallel or their built up section.
In the prepolymerization, composition and monomer that catalyzer or be used to obtains this catalyzer can be supplied to polymerization reactor in any order through known method.As the method that they is supplied to polymerization reactor; For example can enumerate: to contain mixed polymerization with solvent and organic cpds (D) and the polymerization reactor of mixture in, (1) is supplied with catalyzer simultaneously or is used to obtain the composition and the monomer methods of this catalyzer; (2) supply with catalyzer or be used to obtain the composition and the monomer methods of this catalyzer in order.
But the monomer that uses in the prepolymerization can be selected arbitrarily from the monomer of addition polymerization.Can also use the monomer more than 2 kinds.As the monomer that uses in the prepolymerization, the alkene of preferred carbonatoms 2～20.As this alkene, for example can enumerate: ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene, 4-methyl-2-amylene and vinyl cyclohexane etc., optimal ethylene.
When using the monomer more than 2 kinds in the prepolymerization, as monomeric combination, for example can enumerate: ethene and propylene, ethene and 1-butylene, ethene and 1-hexene and combinations such as propylene and 1-butylene.
In the prepolymerization, can make the coexistence of hydrogen equimolecular quantity regulator to regulate the molecular weight of prepolymer.
Among the present invention and since polymerization with solvent in the presence of formation through prepolymerized addition polymerization catalyst component, so can with this be used for formal polymerization with polymerization with solvent through prepolymerized addition polymerization catalyst component.Also can be from polymerization with separating the solvent through the pre-polymerized catalyst composition; Carry out demonomerization, solvent through the pre-polymerized catalyst composition and heat up in a steamer, filter, wash and processing such as drying isolating, and obtain solid state through the pre-polymerized catalyst composition and use it for formal polymerization.
Is that the mode of common 0.1～1000g, preferred 0.5～500g, preferred especially 1～100g is implemented prepolymerization with the amount of polymers (it is right to be also referred to as pre-polymerization) that generates through prepolymerization with respect to composition (B) 1g.
Formal polymerization
Among the present invention, use through prepolymerized addition polymerization to be called formal polymerization with the addition polymerization of catalyst component.During formal polymerization, can gained directly use catalyzer as addition polymerization through the pre-polymerized catalyst composition, also can the contactant through pre-polymerized catalyst composition and organo-aluminium compound be used as addition polymerization and use catalyzer.From the viewpoint of polymerization activity aspect excellence, the preferred latter.As the organo-aluminium compound of latter's situation, can use as the illustrative organo-aluminium compound of aforesaid compound (C).When so using organo-aluminium compound, its usage quantity with respect to compound (A) be generally 1～10000mol/mol, be preferably 10～5000mol/mol, 30～1000mmol/g more preferably.
Make through the pre-polymerized catalyst composition and contact with organo-aluminium compound (C) when using; This can drop into polymerization reactor in any order through pre-polymerized catalyst composition and this organo-aluminium compound (C) and use, and they is contacted in advance drop into polymerization reactor again and use.
Be supplied to Preparation of Catalyst with the not special qualification of the method for reactor drum or formal polymeric polymerization reactor with of the present invention through pre-polymerized catalyst composition and organo-aluminium compound (C).As this method; For example can enumerate: the method that will supply with solid state through pre-polymerized catalyst composition and organo-aluminium compound (C), and so that be dissolved in the solution state fully removed in the hydrocarbon solvent of composition that moisture, oxygen etc. make the catalyst component inactivation or to make it to suspend or method that the state of slurryization is supplied with etc. through pre-polymerized catalyst composition and organo-aluminium compound (C).Hydrocarbon solvent as this moment; For example can enumerate: halogenated hydrocarbon solvent such as aromatic hydrocarbon solvents such as aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane and octane, benzene and toluene and methylene dichloride; Wherein, Aliphatic hydrocarbon solvent or aromatic hydrocarbon solvents, more preferably aliphatic hydrocarbon solvent.
Polymerization method in the formal polymerization is not special to be limited.As this method, for example can enumerate: the polymeric gaseous polymerization is carried out to gasiform monomer in (1); (2) in solvent with the solution polymerization process or the slurry polymerization process (suspension polymerization) of monomer polymerization; (3) will be as the mass polymerization of the monomer polymerization of liquid.Formal polymerization can be carried out with intermittent type, continous way.And then, formal polymerization can be divided into the 2 different stages of reaction conditions with on carry out.Formal polymeric polymerization time is decided by the kind of target addition polymer, the polymerization reactor of use usually, is generally 1 minute～20 hours.
When formally being polymerized to solution polymerization, slurry polymerization or mass polymerization, this polymerization can be carried out according to known method and condition.The preferred method of this polymerization method is that monomer, thinner and other aliment etc. are supplied to polymerization reactor and with the addition polymer that generates from polymerization reactor continuously or the method for taking out off and on as required continuously or off and on.As this polymerization reactor, for example can enumerate annular-pipe reactor, have the reactor drum of stirrer and the reactor drum that kind or the different a plurality of reactor drums that have stirrer of polymeric reaction condition are formed with series, parallel or their built up section.
When formally being polymerized to vapour phase polymerization, this vapour phase polymerization can be carried out according to known method and condition.The reactor drum that this vapour phase polymerization is used is the fluidized bed type reactive tank, is preferably the fluidized bed type reactive tank with expansion section.This reactor drum can have agitating vane in reactive tank.
As the method that will be supplied to polymerization reactor, for example can enumerate: method of usually supplying with the state of no moisture with rare gas elementes such as nitrogen and argon, hydrogen or ethene or the method that will supply with the slurry that is dissolved in solution or dilution in the solvent through the pre-polymerized catalyst composition through the pre-polymerized catalyst composition.
When formally being polymerized to vapour phase polymerization, the polymerization temperature of this vapour phase polymerization is not as long as limit less than the melt temperature of the addition polymer of manufacturing is then special, but is preferably 0 ℃～150 ℃, is in particular preferred 30 ℃～100 ℃.For the melt fluidity of the addition polymer of regulating manufacturing, can add hydrogen as molecular weight regulator.In addition, when gasiform monomer was carried out polymerization, rare gas element can also coexist in the gas.
But the monomer of addition polymerization
As the monomer in the method for manufacture of addition polymer of the present invention, for example can enumerate: the alkene of carbonatoms 2～20, diolefine, cyclic olefin, alkenyl aroma family hydrocarbon and polar monomer.Can also use the monomer more than 2 kinds.
As this monomer, for example can enumerate: alkene such as ethene, propylene, 1-butylene, 1-amylene, 4-methyl-1-pentene, 5-methyl isophthalic acid-hexene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and vinyl cyclohexane; 1,5-hexadiene, 1,4-hexadiene, 1,4-pentadiene, 1; 7-octadiene, 1,8-nonadiene, 1,9-decadiene, 4-methyl isophthalic acid, 4-hexadiene, 5-methyl isophthalic acid; 4-hexadiene, 7-methyl isophthalic acid, 6-octadiene, 5-ethylidene-2-norbornene, Dicyclopentadiene (DCPD), 5-vinyl-2-norbornylene, norbornadiene, 5-methylene-2-norbornene, 1,5-cyclooctadiene, 5; 8-endo-methylene group hexahydro naphthalene, 1,3-butadiene, isoprene, 1,3-hexadiene, 1; 3-octadiene, 1, diolefine such as 3-cyclooctadiene and 1; Norbornylene; 5-methyl-2-norbornylene; 5-ethyl-2-norbornylene; 5-butyl-2-norbornylene; 5-phenyl-2-norbornylene; 5-benzyl-2-norbornylene; Tetracyclododecane; Tricyclo decene; Three ring undecylenes; Five rings 15 carbenes; The five rings cetene; 8-methyl tetracyclododecane; 8-ethyl tetracyclododecane; 5-ethanoyl-2-norbornylene; 5-acetoxyl group-2-norbornylene; 5-methoxycarbonyl-2-norbornylene; 5-ethoxy carbonyl-2-norbornylene; 5-methyl-5-methoxycarbonyl-2-norbornylene; 5-cyanic acid-2-norbornylene; 8-methoxycarbonyl tetracyclododecane; 8-methyl-8-tetracyclododecane; With cyclic olefins such as 8-cyanic acid tetracyclododecane; Vinylbenzene, alkenyl benzene are (for example; 2-phenyl propylene, 2-phenyl butylene and 3-phenyl propylene), ring-alkylated styrenes (for example, p-methylstyrene, a vinyl toluene, o-methyl styrene, to ethyl styrene, an ethyl styrene, adjacent ethyl styrene, alpha-methyl styrene, 2,4-dimethyl styrene, 2; 5-dimethyl styrene, 3; 4-dimethyl styrene, 3,5-dimethyl styrene, 3-methyl-5-ethyl styrene, 1, to t-butyl styrene with to sec.-butylbenzene ethene) and two alkenyl benzene (for example; Vinylstyrene), thiazolinyl naphthalene alkenyl aroma family hydrocarbon such as (for example, 1-vinyl naphthalenes); And α; Beta-unsaturated carboxylic acid (for example; Vinylformic acid, methylacrylic acid, fumaric acid, maleic anhydride, methylene-succinic acid, itaconic anhydride and dicyclo (2; 2; 1)-5-heptene-2; The 3-dioctyl phthalate), this α, metal-salt, the α of metals such as the sodium of beta-unsaturated carboxylic acid, potassium, lithium, zinc, magnesium and calcium, the beta-unsaturated carboxylic acid ester (for example; Methyl acrylate, ethyl propenoate, vinylformic acid n-propyl, isopropyl acrylate, tert-butyl acrylate, 2-EHA, TEB 3K, Jia Jibingxisuanyizhi, n propyl methacrylate, isopropyl methacrylate, n-BMA and Propenoic acid, 2-methyl, isobutyl ester), unsaturated dicarboxylic acid (for example; Toxilic acid and methylene-succinic acid), vinyl ester (for example, vinyl-acetic ester, vinyl propionate base ester, caproic acid vinyl ester, capric acid vinyl ester, LAURIC ACID 99 MIN vinyl ester, vinyl stearate base ester and trifluoroacetic acid vinyl ester) and unsaturated carboxylic acid glycidyl ester (for example, glycidyl acrylate, SY-Monomer G and methylene-succinic acid list glycidyl ester) isopolarity monomer.
As this monomer, the alkene of preferred carbonatoms 2～20.As this alkene, for example can enumerate: ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene, 4-methyl-2-amylene and vinyl cyclohexane etc.
When using more than 2 kinds monomer, preferably use ethene and terminal olefin.As the monomeric combination of using, the combination of optimal ethylene and propylene, ethene and 1-butylene, ethene and 1-hexene, ethene and 1-octene, ethene and 1-butylene and 1-hexene, ethene and 1-butylene and 1-octene, ethene and 1-hexene and 1-octene, propylene and 1-butylene, propylene and 1-hexene, propylene and 1-octene.
Be preferably the multipolymer of ethene and terminal olefin especially by the addition polymer of method of manufacture gained of the present invention, wherein, preferably have the ethene of Vilaterm crystalline texture and the multipolymer of terminal olefin.As this terminal olefin, for example the terminal olefin of preferred carbonatoms 3～8 for example can be enumerated: 1-butylene, 1-hexene and 1-octene.
[embodiment]
Below, through embodiment and comparative example the present invention is more specified, but the present invention does not receive their qualification.The character of the olefin polymer among the embodiment is measured through following method.
(1) ultimate analysis
Zn: after sample dropped into aqueous sulfuric acid (1M), the aqueous sulfuric acid that contains sample is applied UW, metal ingredient is extracted into the aqueous sulfuric acid from sample.For the liquid portion of the aqueous sulfuric acid that contains metal ingredient, Zn is quantitative through the ICP luminescence analysis;
F: sample is burnt in the flask of filling aerobic, the combustion gases that produce are absorbed to aqueous sodium hydroxide solution (10%), F is quantitative to this aqueous solution of gained with the ion electrode method.
(4) through the accumulating weight mark of prepolymerized addition polymerization with the particle of particle diameter below 60 μ m of catalyst component
Use system laser diffraction formula particle size distribution device HELOS&RODOS system of SYMPATEC society; Through following condition determination; Make through prepolymerized addition polymerization and disperse with dryness with catalyst component; Measure its size-grade distribution, with particle diameter calculating according to volume with the amount of catalyst component below 60 μ m through prepolymerized addition polymerization.
(condition determination)
Scope: R4 1.8～350 μ m
Trigger condition: with reference to 2 seconds time length
: time base 100m second
: beginning passage 15 >=0.5%
: finish 2s, passage 15≤0.5%, 10s real time
Dispersion condition: RODOS (dry type airflow dispersal unit) direct-throwing
: feeder VIBRI
: carry 50%
: syringe 4mm
: dispersion pressure 1.5bar.
［ embodiment 1 ］
(1) manufacturing of acvator (B)
To make the particle in this specification sheets through modification with the embodiment 1 (1) of TOHKEMY 2009-79180 communique and the identical method of preparation of (2) middle composition (A).The result of ultimate analysis is: Zn=11wt%, F=6.4wt%.
(2) prepolymerization
Behind the drying under reduced pressure; To vacuumize with the autoclave of the band stirrer of 3 liters of nitrogen metathetical internal volumes; Adding butane 480g and prepared at concentrations is the N of 10mg/ml, two (2-hydroxyethyl) fatty acid distribution of coconut oil acid amides (ケ ミ ス タ ッ ト 2500, Sanyo change into industrial society system) the hexane solution 5.0ml (D) of N-.Then, ethylenebis (indenyl) zirconium diphenyl oxide compound (A) 195mg (366 μ mol) is added autoclave, after 1 hour, be cooled to 30 ℃ 50 ℃ of stirrings.Then, add ethene 1g, adds in above-mentioned (1) gained, and then to add prepared at concentrations be the hexane solution 3.5ml (3.5mmol) of the triisobutyl aluminium (C) of 1.0mmol/ml, begin prepolymerization through particle (B) 7.1g of modification.Divide with 0.13g/ at first and supply with ethene, carry out prepolymerization in 30 minutes at 30 ℃ simultaneously.Then, be replaced by ethene/hydrogen mixed gas (hydrogen concentration: 0.182mol%), divide on one side with 0.81g/ and to supply with, on one side be warming up to 50 ℃ with 30 minutes, continuation is carried out prepolymerization in 2 hours at 50 ℃.Remove monomer and butane, reclaim and use catalyst component through prepolymerized addition polymerization.Yield is 107.0g, is 15.1g/g with respect to the polymerization degree through the particle (B) of modification.Measure this size-grade distribution through the pre-polymerized catalyst composition, the result should the amount of the contained particle of particle diameter below 60 μ m be 1.7% in the pre-polymerized catalyst composition.
(3) formal polymerization
Behind the drying under reduced pressure, will vacuumize in the autoclave with the band stirrer of 5 liters of argon metathetical internal volumes, hydrogen will be added 0.037MPa with partial pressure gauges, add 154g hexene-1 and 1046g butane, be warming up to 70 ℃.Then, adding ethene, to make its dividing potential drop be that 1.6MPa makes in the system stable.Carry out gas chromatographic analysis, the gas composition in the system is hydrogen=1.95mol% as a result.To wherein adding the hexane solution 2.0ml that prepared at concentrations is the triisobutyl aluminium of 1mmol/ml.Then, adding prepared at concentrations is the toluene solution 1.0ml of the triethylamine of 0.1mmol/ml.And then, add above-mentioned (1) middle gained and use catalyst component 309.1mg through prepolymerized addition polymerization.Stagnation pressure is kept the constant mode supply with ethene/hydrogen mixed gas (hydrogen 0.293mol%), carry out polymerization in 3 hours at 70 ℃ simultaneously.The result obtains olefin polymer.
［ comparative example 1 ］
(1) prepolymerization
Except adding in ethylenebis (indenyl) zirconium diphenyl oxide compound (A) 198mg (372 μ mol), the foregoing description 1 (1) gained through particle (B) 7.0g of modification; And be not added with outside the organic compounds (D), likewise implement prepolymerization with embodiment 1 (2).Yield is 130.3g, is 18.6g/g with respect to the polymerization degree through the particle (B) of modification.Mensuration is through the size-grade distribution of pre-polymerized catalyst composition, and the result should the amount of the contained particle of particle diameter below 60 μ m be 11.0% in the pre-polymerized catalyst composition.
Claims (8)
1. method, but it is that it has following operation with the prepolymerized method of the monomer of addition polymerization:
(1) mixed polymerization forms the operation of mixture with the organic cpds (D) shown in solvent and the formula ［ 2 ］
(2) compound (A) in the transistion metal compound dimer that makes transistion metal compound shown in the formula of being selected from ［ 1 ］ and mu-oxo type thereof contact with acvator (B) and the catalyzer that forms in the presence of, with aforementioned monomer prepolymerized operation in aforementioned mixture
L
1 aM
1X
1 b ［1］
M
1Transition metal atoms for IVB family; L
1For group or contain heteroatomic group with cyclopentadiene shape anion frame; X
1Be halogen atom,-oxyl or alkyl, wherein, get rid of group with cyclopentadiene shape anion frame; A is for satisfying the number of 0＜a≤3; B is for satisfying the number of 0＜b≤3; A is greater than 1 o'clock, 1 L
1Can with other L
1Directly perhaps link each other through the group that contains carbon atom, Siliciumatom, nitrogen-atoms, Sauerstoffatom, sulphur atom or phosphorus atom;
R
1C（＝O）NR
2 2 ［2］
R
1For having the alkyl of substituent carbonatoms 1～30; R
2For having the alkyl of substituent carbonatoms 1～30; Two R
2Can be identical or different each other.
2. method, but it is that it has following operation with the prepolymerized method of the monomer of addition polymerization:
(1) mixed polymerization forms the operation of mixture with the organic cpds (D) shown in solvent and the formula ［ 2 ］
(2) compound (A) in the transistion metal compound dimer that makes transistion metal compound shown in the formula of being selected from ［ 1 ］ and mu-oxo type thereof, acvator (B) contact with organo-aluminium compound (C) and the catalyzer that forms in the presence of, with aforementioned monomer prepolymerized operation in aforementioned mixture
L
1 aM
1X
1 b ［1］
M
1Transition metal atoms for IVB family; L
1For group or contain heteroatomic group with cyclopentadiene shape anion frame; X
1Be halogen atom,-oxyl or alkyl, wherein, get rid of group with cyclopentadiene shape anion frame; A is for satisfying the number of 0＜a≤3; B is for satisfying the number of 0＜b≤3; A is greater than 1 o'clock, 1 L
1Can with other L
1Directly perhaps link each other through the group that contains carbon atom, Siliciumatom, nitrogen-atoms, Sauerstoffatom, sulphur atom or phosphorus atom;
R
1C（＝O）NR
2 2 ［2］
R
1For having the alkyl of substituent carbonatoms 1～30; R
2For having the alkyl of substituent carbonatoms 1～30; Two R
2Can be identical or different each other.
3. claim 1 or 2 described prepolymerization methods, wherein, acvator (B) be following (a), following (b), following (c) are contacted with following (d) and the particle through modification:
(a): the compound shown in the formula ［ 3 ］
M
2L
2 2? ［3］
(b): the compound shown in the formula ［ 4 ］
R
3 t-1TH ［4］
(c): the compound shown in the formula ［ 5 ］
R
4 u-2T’H
2? ［5］
(d): inorganic oxide particle or organic polymer particle
M
2Be IIB family element; L
2Be Wasserstoffatoms, halogen atom or alkyl, 2 L
2Can be identical or different each other; R
3For electrophilic property group or contain the group of electrophilic property group; T-1 is greater than 1 o'clock, a plurality of R
3Can be identical or different each other; R
4Be alkyl or halo alkyl; T is VA family element or VIA family element; T is the number that is equivalent to the valency of T; T ' is VA family element or VIA family element; U is the number that is equivalent to the valency of T '.
4. each described prepolymerization method in the claim 1～3, it is the method for in slurry, carrying out.
5. what got by each described method in the claim 1～4 uses catalyst component through prepolymerized addition polymerization.
6. method, it is the method for manufacture of addition polymer, wherein, claim 5 described through prepolymerized addition polymerization with in the presence of the catalyst component, but with the monomer polymerization of addition polymerization.
7. method, it is the method for manufacture of addition polymer, wherein, claim 5 described through prepolymerized addition polymerization with the mixture of catalyst component and organo-aluminium compound (C) in the presence of, but with the monomer polymerization of addition polymerization.
8. the described method of claim 6 or claim 7, wherein, but the monomer of addition polymerization is ethene and terminal olefin.
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|---|---|
| JP (1) | JP2012193348A (en) |
| CN (1) | CN102653570A (en) |
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2012
- 2012-02-23 JP JP2012037246A patent/JP2012193348A/en active Pending
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