CN101490069A - Rare earth metal complex, polymerization catalyst and method for producing polymer - Google Patents

Rare earth metal complex, polymerization catalyst and method for producing polymer Download PDF

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CN101490069A
CN101490069A CNA2007800258064A CN200780025806A CN101490069A CN 101490069 A CN101490069 A CN 101490069A CN A2007800258064 A CNA2007800258064 A CN A2007800258064A CN 200780025806 A CN200780025806 A CN 200780025806A CN 101490069 A CN101490069 A CN 101490069A
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千田太一
花冈秀典
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Sumitomo Chemical Co Ltd
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Abstract

Disclosed is a rare earth metal complex represented by the following formula (1). (In the formula (1), A represents a group 14 element of the periodic table; Cp represent a substituted or unsubstituted group having a cyclopentadienyl type anion skeleton; Ln represents a group 3 metal atom or a lanthanoid metal atom; R<1>-R<6> may be the same as or different from one another and represent a hydrogen atom, a halogen atom, an alkyl group having 1-20 carbon atoms, an aryl group having 6-20 carbon atoms, an aralkyl group having 7-20 carbon atoms, a silyl group substituted with a hydrocarbon group having 1-20 carbon atoms, an alkoxy group having 1-20 carbon atoms or the like; R<7> represents an alkyl group having 1-20 carbon atoms, an aryl group having 6-20 carbon atoms or an aralkyl group having 7-20 carbon atoms; X represents a monoanionic ligand; Y represents a neutral ligand; m represents an integer of 1-3; and n represents an integer of 0-3.) For example, this rare earth metal complex is useful as a catalyst for olefin polymerization reactions. A polar monomer such as a lactone can be polymerized by using this rare earth metal complex as a catalyst.

Description

The preparation method of rare earth metal complex, catalyst for polymerization and polymkeric substance
Technical field
The present invention relates to rare earth metal complex and its preparation method, contain the preparation method of the polar monomer polymkeric substance of the alkene of this rare earth metal complex or lactone catalyst for polymerization and alkene or lactone etc.
Background technology
Known metallocene complex with a cyclopentadiene part is referred to as the semi-metallocene title complex, it is the compound that can be used as various olefin polymerization catalyst components, according to the difference of the kind of its central metal, its characteristic (for the catalytic activity of polyreaction) also has very big difference.Known wherein contain central metal be the 3rd family's metal or lanthanide series metal (below, the 3rd family's metal and lanthanide series metal are collectively referred to as rare earth metal) the polymerizing catalyst composition of semi-metallocene title complex can be used for the polymerization of ethene or alpha-olefin or the polymerization or the copolymerization (for example, with reference to WO2006/004068) of monomeric polymerization of atomatic olefins such as copolymerization, vinylbenzene or cyclic olefin monomers such as copolymerization, norbornylene.In addition, the semi-metallocene title complex that known this central metal is a rare earth metal also can be used for the polymerization of cyclohexene oxide or the copolymerization of cyclohexene oxide and carbonic acid gas (for example, with reference to Macromolecules 2005,38,4089).Known central metal be the polymerization of the block copolymerization that can be used for syndiotactic polymerization, ethene and the methacrylic ester of methacrylic ester of the semi-metallocene title complex of lanthanum, isocyanides and vinyl cyanide polymerization (for example, with reference to J.Polym.Sci.:Part A:Polym.Chem.2001,39,1382).Like this, central metal is that the semi-metallocene title complex of rare earth metal is to expect to be used for multi-purpose metal complexes.On the other hand, known conduct has cyclopentadiene derivant and the phenol derivatives metal complexes with the crosslinked part of the 14th family's atom, the 4th group 4 transition metal complexes can be as catalyst for olefines polymerizing (for example, open flat 9-87313 communique with reference to the spy), but do not have the example of rare earth metal complex to report.
In addition, with the polymkeric substance that the industrial 6-caprolactone that can prepare at a low price is the lactone compound of representative, be the material modified compound that can be used as urethane, coating resin, plastics.In polymkeric substance, especially the high-molecular weight lactone polymer is to be subjected to remarkable compound as the Biodegradable polymkeric substance.The preparation method of the high-molecular weight polymer of known lactone has alkoxide with rare earth class as catalyzer and with the method for lactone ring opening polymerization (for example, with reference to WO91/05001), be catalyzer and as the rare earth class title complex of part perhaps with the method (for example, opening flat 5-247184 communique) of lactone ring opening polymerization with reference to the spy to have cyclopentadiene.Afterwards for of the ring-opening polymerization of rare earth class title complex, begin to have trial to obtain the report (for example, with reference to Macromolecules 1999,29,1798) of the polymkeric substance of narrow molecular weight distribution with high-level efficiency more as the lactone of catalyzer.
Summary of the invention
The 1st purpose of the present invention provides novel rare earth metal complex and its preparation method that can be used as alkene or lactone isopolarity monomer polymerization usefulness catalyst component.
The 2nd purpose of the present invention provides the preparation method of the polymkeric substance or the multipolymer of the alkene that has used the catalyst component that contains this rare earth metal complex.
The 3rd purpose of the present invention provides the preparation method of the polar monomer polymkeric substance that has used the catalyst component that contains this rare earth metal complex, wherein the preparation method of the high-molecular weight polymer of the lactone that especially efficient is high.
According to the 1st scheme, the invention provides rare earth metal complex as the formula (1),
Formula (1):
Figure A200780025806D00061
(in the formula, A represents the 14th family's element of the periodic table of elements,
Cp represents to have the group that replaces or do not have the cyclopentadienyl type anion frame of replacement, and Ln represents the 3rd family's atoms metal or lanthanide series metal atom,
R 1, R 2, R 3, R 4, R 5And R 6Identical or different, expression hydrogen atom, halogen atom, carbonatoms are that 1～20 alkyl, carbonatoms are that 6～20 aryl, carbonatoms are 7～20 aralkyl, are that silyl, carbonatoms that 1～20 alkyl replaces are that 1～20 alkoxyl group, carbonatoms are 6～20 aryloxy, are that 7～20 aralkoxy or carbonatoms are the amino of 1～20 alkyl replacement with carbonatoms with carbonatoms
R 7The expression carbonatoms is that 1～20 alkyl, carbonatoms are that 6～20 aryl, carbonatoms are 7～20 aralkyl.
Wherein, at R 1～R 7In, alkyl, aryl, aralkyl, alkoxyl group, aryloxy, aralkoxy or alkyl also can replace with halogen atom,
R 1With R 2Also can in conjunction with and form ring,
R 3, R 4, R 5And R 6In abutting connection with group also can distinguish at random in conjunction with and form ring.
M X is identical or different, expression single anion part.
N Y is identical or different, the expression neutral ligand.
M represents 1～3 integer.
N represents 0～3 integer.)。
According to the 2nd scheme, the invention provides the preparation method of the rare earth metal complex shown in following formula (1), it is characterized in that, make the replacement shown in the formula (2) or do not have the cyclopentadiene compound of replacement and the rare earth metal compound shown in the formula (3) reacts and prepares.
Formula (2):
Figure A200780025806D00071
(in the formula, A, Cp, R 1, R 2, R 3, R 4, R 5, R 6And R 7Represent the meaning same as described above.)
Formula (3):
Figure A200780025806D00072
(in the formula, Ln, X, Y, m and n represent the meaning same as described above.R 8Represent the alkyl that also available silyl replaces, described silyl carbonatoms is 1～20 alkyl replacement, perhaps represents the also aralkyl of available amino end replacement, and described amino is 1～20 alkyl replacement with carbonatoms.)
According to the 3rd scheme, the invention provides and contain the catalyst for olefines polymerizing composition that the rare earth metal complex shown in the following formula (1) forms.
According to the 4th scheme, the invention provides make above-mentioned catalyst for olefines polymerizing composition and be selected from that at least a kind the compound of following aluminum compound (A1)～(A3) with following boron compound (B1)～(B3) contacts and catalyst for olefines polymerizing,
Aluminum compound (A):
(A1): with formula (E 1) aAlZ (3-a)The organo-aluminium compound of expression;
(A2): have with formula { Al (E 2)-O-} bThe ring-type aikyiaiurnirsoxan beta (ア Le ミ ノ キ サ Application) of the structure of expression;
(A3): have the formula of using E 3{ Al (E 3)-O-} cAl (E 3) 2The line style aikyiaiurnirsoxan beta of the structure of expression
(in the formula, a represents to satisfy the numerical value of 0＜a≤3, and b represents the integer more than 2, and c represents the integer more than 1.E 1, E 2And E 3Represent that respectively carbonatoms is 1～20 alkyl, a plurality of E 1, a plurality of E 2With a plurality of E 3Can be respectively identical, also can be different.Z represents hydrogen atom or halogen atom, and a plurality of Z can be identical mutually, also can be different.)
Boron compound (B):
(B1): use formula BQ 1Q 2Q 3The boron compound of expression;
(B2): use formula G +(BQ 1Q 2Q 3Q 4) -The boron compound of expression;
(B3): with formula (L 1-H) +(BQ 1Q 2Q 3Q 4) -The boron compound of expression
(in the formula, B represents the boron atom of the valence state of 3 valencys, Q 1, Q 2, Q 3And Q 4Represent halogen atom, alkyl, halogenation alkyl respectively independently, replace silyl, alkoxyl group or 2 substituted-aminos, G +Represent inorganic or organic positively charged ion, L 1The expression neutral Lewis base.)。
According to the 5th scheme, the invention provides and contain in the presence of above-mentioned catalyst for olefines polymerizing, alkene is carried out the preparation method of polymeric olefin polymer.
According to the 6th scheme, the invention provides to contain and make polar monomer contact the preparation method who carries out polymeric polar monomer polymkeric substance with the rare earth metal complex shown in the following formula (1).
According to the 7th scheme, the invention provides and contain the preparation method who lactone is contacted with the rare earth metal complex shown in the following formula (1) and carry out the lactone polymkeric substance of ring-opening polymerization.
According to the 8th scheme, the invention provides and contain the preparation method who alkylene oxides is contacted with the rare earth metal complex shown in the following formula (1) and carry out the alkylene oxides polymkeric substance of ring-opening polymerization.
According to the 9th scheme, the invention provides and contain the preparation method who acrylate or methacrylic ester is contacted with the rare earth metal complex shown in the following formula (1) and carry out polymeric acrylic ester polymer or methacrylate polymers.
Novel rare earth metal complex of the present invention for example can be used as the catalyzer of the polyreaction of alkene.In addition, the rare earth metal complex of the application of the invention can carry out the polymerization of polar monomer as catalyzer, for example can be with short time efficient production high-molecular weight lactone polymer under lower temperature.
Embodiment
The rare earth metal complex shown in the following formula (1) (below, abbreviate rare earth metal complex (1) as) in, the example of the group of representing with Cp with cyclopentadienyl type anion frame can be enumerated cyclopentadienyl, indenyl, the fluorenyl that replaces or do not have replacement.
Object lesson with group of cyclopentadienyl type anion frame can be enumerated cyclopentadienyl, methyl cyclopentadienyl, the dimethyl cyclopentadienyl, the trimethylammonium cyclopentadienyl, the tetramethyl-ring pentadienyl, the ethyl cyclopentadienyl, the n-propyl cyclopentadienyl, the sec.-propyl cyclopentadienyl, n-butyl cyclopentadienyl, the sec-butyl cyclopentadienyl, tertiary butyl cyclopentadienyl, tetrahydro indenyl, octahydrofluorenyl, the benzyl ring pentadienyl, the trimethyl silyl cyclopentadienyl, the replacement of t-butyldimethylsilyl cyclopentadienyl etc. or do not have the cyclopentadienyl of replacement; The replacement of indenyl, methyl indenyl, dimethyl indenyl, ethyl-indenyl, n-propyl indenyl, sec.-propyl indenyl, normal-butyl indenyl, sec-butyl indenyl, tertiary butyl indenyl, phenyl indenyl etc. or do not have the indenyl of replacement; Fluorenyl, the 2-methyl amyl, 2,7-dimethyl fluorenyl, 2-ethyl fluorenyl, 2,7-diethyl fluorenyl, 2-n-propyl fluorenyl, 2,7-di fluorenyl, 2-sec.-propyl fluorenyl, 2,7-di-isopropyl fluorenyl, 2-normal-butyl fluorenyl, 2-sec-butyl fluorenyl, 2-tertiary butyl fluorenyl, 2,7-di-n-butyl fluorenyl, 2,7-two sec-butyl fluorenyls, 2,7-di-t-butyl fluorenyl, 3,6-di-t-butyl fluorenyl, 2-phenyl fluorenyl, 2,7-phenylbenzene fluorenyl, the fluorenyl of the replacement of 2-aminomethyl phenyl fluorenyl etc. is preferably enumerated cyclopentadienyl, methyl cyclopentadienyl, the dimethyl cyclopentadienyl, the trimethylammonium cyclopentadienyl, the tetramethyl-ring pentadienyl, tertiary butyl cyclopentadienyl etc.
The replacement shown in rare earth metal complex (1) and the formula (2) or do not have the substituted-cyclopentadienyl compound (below, abbreviate cyclopentadiene compound (2) as.) in, the example of the 14th family's element of the periodic table of elements of representing with A can be enumerated carbon atom, Siliciumatom, germanium atom etc., preferably enumerates carbon atom, Siliciumatom.
In substituent R 1, R 2, R 3, R 4, R 5And R 6In, halogen atom can be enumerated fluorine atom, chlorine atom, bromine atoms, iodine atom etc., preferably enumerates the chlorine atom.
In substituent R 1, R 2, R 3, R 4, R 5, R 6And R 7In, carbonatoms is that the object lesson of 1～20 alkyl can be enumerated methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, n-pentyl, neo-pentyl, amyl group (ア ミ Le base), n-hexyl, heptyl, n-octyl, n-nonyl, positive decyl, dodecyl, n-tridecane base, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and NSC 62789 base, preferably enumerates methyl, ethyl, sec.-propyl, the tertiary butyl, amyl group etc.
In substituent R 1, R 2, R 3, R 4, R 5, R 6And R 7In, the carbonatoms that halogen replaces is that the object lesson of 1～20 alkyl can be enumerated these alkyl and replaces the group that forms with halogen atoms such as fluorine atom, chlorine atom, bromine atoms or iodine atoms.
In substituent R 1, R 2, R 3, R 4, R 5, R 6And R 7In, carbonatoms is that the object lesson of 6～20 aryl can be enumerated phenyl, the 2-tolyl, the 3-tolyl, the 4-tolyl, 2, the 3-xylyl, 2, the 4-xylyl, 2, the 5-xylyl, 2, the 6-xylyl, 3, the 4-xylyl, 3, the 5-xylyl, 2,3, the 4-trimethylphenyl, 2,2,3, the 6-trimethylphenyl, 2,4, the 6-trimethylphenyl, 3,4, the 5-trimethylphenyl, 2,3,4, the 5-tetramethylphenyl, 2,3,4, the 6-tetramethylphenyl, 2,3,5, the 6-tetramethylphenyl, pentamethylbenzene, ethylphenyl, the n-propyl phenyl, isopropyl phenyl, n-butylphenyl, secondary butyl phenenyl, tert-butyl-phenyl, the n-pentyl phenyl, the neo-pentyl phenyl, the n-hexyl phenyl, the n-octyl phenyl, positive decyl phenyl, the dodecyl phenyl, n-tetradecane base phenyl, naphthyl, anthryls etc. are preferably enumerated phenyl.
In substituent R 1, R 2, R 3, R 4, R 5, R 6And R 7In, the carbonatoms that halogen replaces is that the object lesson of 6～20 aryl can be enumerated, these aryl replace the group that forms with halogen atoms such as fluorine atom, chlorine atom, bromine atoms or iodine atoms.
In substituent R 1, R 2, R 3, R 4, R 5, R 6And R 7In, carbonatoms is that the object lesson of 7～20 aralkyl 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, (4, the 6-3,5-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, (n-pentyl phenyl) methyl, (neo-pentyl phenyl) methyl, (n-hexyl phenyl) methyl, (n-octyl phenyl) methyl, (positive decyl phenyl) methyl, (positive decyl) methyl, naphthyl methyl, anthryl methyl etc. are preferably enumerated benzyl.
In substituent R 1, R 2, R 3, R 4, R 5, R 6And R 7In, the carbonatoms that halogen replaces is that the object lesson of 7～20 aralkyl can be enumerated, these aralkyl replace the group that forms with halogen atoms such as fluorine atom, chlorine atom, bromine atoms or iodine atoms.
In substituent R 1, R 2, R 3, R 4, R 5And R 6In, the example of the alkyl in the silyl that replaces with alkyl can be enumerated the aryl etc. that carbonatomss such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, isobutyl-, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, positive decyl are 1～10 alkyl, phenyl etc.With this carbonatoms is that the object lesson of the silyl that replaces of 1～20 alkyl can be enumerated the methyl-silicane base, the ethyl silicane base, the carbonatoms of phenyl silyl etc. is a replacement silyl of 1～20, dimetylsilyl, the diethylsilane base, usefulness carbonatomss such as diphenylmethyl silylation be 1～20 alkyl replace form two replace silyls, trimethyl silyl, triethylsilyl, three n-propyl silyls, the triisopropyl silyl, three normal-butyl silyls, three sec-butyl silyls, the tri-tert silyl, tri-iso-butylsilyl, t-butyldimethylsilyl, three n-pentyl silyls, three n-hexyl silyls, the thricyclohexyl silyl, triphenyl silyl etc. with carbonatoms be 1～20 alkyl replace form three replace silyls etc., preferably enumerate trimethyl silyl, t-butyldimethylsilyl, the triphenyl silyl.
Except above-mentioned alkyl, the example that constitutes the alkyl that replaces silyl can also be enumerated the alkyl that replaces with halogen atoms such as fluorine atom, chlorine atom, bromine atoms, iodine atoms.
In substituent R 1, R 2, R 3, R4, R 5And R 6In, carbonatoms is that the object lesson of 1～20 alkoxyl group can be enumerated methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, tert.-butoxy, n-pentyloxy, neopentyl oxygen, positive hexyloxy, n-octyloxy, positive ninth of the ten Heavenly Stems the oxygen base, n-decyloxy, n-dodecane oxygen base, n-undecane oxygen base, n-dodecane oxygen base, n-tridecane oxygen base, tetradecyloxyaniline, pentadecane oxygen base, n-Hexadecane oxygen base, heptadecane oxygen base, octadecane oxygen base, nonadecane oxygen base, with NSC 62789 oxygen base etc., preferably enumerate methoxyl group, oxyethyl group, tert.-butoxy.
The carbonatoms that halogen replaces is that the object lesson of 1～20 alkoxyl group can be enumerated, and these alkoxyl groups replace the group that forms with halogen atoms such as fluorine atom, chlorine atom, bromine atoms or iodine atoms.
In substituent R 1, R 2, R 3, R 4, R 5And R 6In, carbonatoms is that the object lesson of 6～20 aryloxy can be enumerated phenoxy group, the 2-methylphenoxy, the 3-methylphenoxy, the 4-methylphenoxy, 2, the 3-dimethyl phenoxy, 2, the 4-dimethyl phenoxy, 2, the 5-dimethyl phenoxy, 2, the 6-dimethyl phenoxy, 3, the 4-dimethyl phenoxy, 3, the 5-dimethyl phenoxy, 2,3,4-trimethylammonium phenoxy group, 2,3,5-trimethylammonium phenoxy group, 2,3,6-trimethylammonium phenoxy group, 2,4,5-trimethylammonium phenoxy group, 2,4,6-trimethylammonium phenoxy group, 3,4,5-trimethylammonium phenoxy group, 2,3,4,5-tetramethyl-phenoxy group, 2,3,4,6-tetramethyl-phenoxy group, 2,3,5,6-tetramethyl-phenoxy group, the pentamethyl-phenoxy group, the ethyl phenoxy group, the n-propyl phenoxy group, the sec.-propyl phenoxy group, the normal-butyl phenoxy group, the sec-butyl phenoxy group, tertiary butyl phenoxy group, the n-hexyl phenoxy group, the n-octyl phenoxy group, positive decyl phenoxy group, the n-tetradecane phenoxyl, naphthyloxy, the carbonatoms of anthracene oxygen base etc. is 6～20 a aryloxy etc.The carbonatoms that replaces of halogen is that the object lesson of 6～20 aryloxy can be enumerated in addition, and above-mentioned carbonatoms is that 6～20 aryloxy replaces the group that forms with halogen atoms such as fluorine atom, chlorine atom, bromine atoms, iodine atoms.
In substituent R 1, R 2, R 3, R 4, R 5And R 6In, carbonatoms is that the object lesson of 7～20 aralkoxy can be enumerated benzyloxy, (2-aminomethyl phenyl) methoxyl group, (3-aminomethyl phenyl) methoxyl group, (4-aminomethyl phenyl) methoxyl group, (2, the 3-3,5-dimethylphenyl) methoxyl group, (2, the 4-3,5-dimethylphenyl) methoxyl group, (2, the 5-3,5-dimethylphenyl) methoxyl group, (2, the 6-3,5-dimethylphenyl) methoxyl group, (3, the 4-3,5-dimethylphenyl) methoxyl group, (3, the 5-3,5-dimethylphenyl) methoxyl group, (2,3, the 4-trimethylphenyl) methoxyl group, (2,3, the 5-trimethylphenyl) methoxyl group, (2,3, the 6-trimethylphenyl) methoxyl group, (2,4, the 5-trimethylphenyl) methoxyl group, (2,4, the 6-trimethylphenyl) methoxyl group, (3,4, the 5-trimethylphenyl) methoxyl group, (2,3,4, the 5-tetramethylphenyl) methoxyl group, (2,3,4, the 6-tetramethylphenyl) methoxyl group, (2,3,5, the 6-tetramethylphenyl) methoxyl group, (pentamethyl-phenyl) methoxyl group, (ethylphenyl) methoxyl group, (n-propyl phenyl) methoxyl group, (isopropyl phenyl) methoxyl group, (n-butylphenyl) methoxyl group, (secondary butyl phenenyl) methoxyl group, (tert-butyl-phenyl) methoxyl group, (n-hexyl phenyl) methoxyl group, (n-octyl phenyl) methoxyl group, (positive decyl phenyl) methoxyl group, the naphthyl methoxyl group, anthryl methoxyl groups etc. are preferably enumerated benzyloxy.
The carbonatoms that halogen replaces is that the object lesson of 7～20 aralkoxy can be enumerated, and these aralkoxies replace the group that forms with halogen atoms such as fluorine atom, chlorine atom, bromine atoms, iodine atoms.
In substituent R 1, R 2, R 3, R 4, R 5And R 6In, so-called is the amino of 1～20 alkyl replacement with carbonatoms, be meant with 2 alkyl and replace the amino that forms, here can to enumerate carbonatomss such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, isobutyl-, n-pentyl, n-hexyl, cyclohexyl be aryl of 1～20 alkyl, phenyl etc. etc. to the example of alkyl, and these substituting groups also can mutually combine and form ring.Above-mentioned is that the example of the amino that replaces of 1～20 alkyl can be enumerated dimethylamino with carbonatoms, diethylin, two n-propylamine bases, diisopropylaminoethyl, two n-butyl amine bases, di-secondary fourth amino, two uncle's fourth amino, two isobutyl amino, tertiary butyl isopropylamino, two is just own amino, two is positive hot amino, two positive last of the ten Heavenly stems amino, diphenyl amino, two (trimethyl silyl) amino, two (t-butyldimethylsilyl) amino, pyrryl, pyrrolidyl, piperidyl, carbazyl, indolinyl, dihydro-iso indolyls etc. are preferably enumerated dimethylamino, diethylin, pyrrolidyl, piperidyl etc.
And then, as the alkyl that constitutes these substituted-aminos, except above-mentioned alkyl, can also enumerate the alkyl that forms with the replacement of halogen atoms such as fluorine atom, chlorine atom, bromine atoms, iodine atom.
R 1With R 2Also can in conjunction with and form ring, R 3, R 4, R 5And R 6In 2 substituting groups of adjacency also can be arbitrarily in conjunction with and form and encircle.
As R 1With R 2In conjunction with and the ring that forms, and R 3, R 4, R 5And R 6In adjacency 2 substituting groups in conjunction with and the example of the ring that forms, can enumerate with carbonatoms be 1～20 alkyl replacement, saturated or undersaturated hydrocarbon ring etc.Its object lesson can be enumerated cyclopropane ring, tetramethylene ring, pentamethylene ring, cyclohexane ring, suberane ring, cyclooctane ring, phenyl ring, naphthalene nucleus, anthracene nucleus etc.
The example of rare earth metal complex of the present invention (1) can be enumerated following title complex.
[1-(dimethyl { the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl } silyl)-2,3,4,5-tetramethyl-ring pentadienyl] two (neighbour-N, N-dimethylamino benzyl) scandium, [1-(diethyl { the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl } silyl)-2,3,4,5-tetramethyl-ring pentadienyl] two (neighbour-N, N-dimethylamino benzyl) scandium, [1-(dimethyl { the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl } silyl) cyclopentadienyl] two (neighbour-N, N-dimethylamino benzyl) scandium, [1-(diethyl { the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl } silyl) cyclopentadienyl] two (neighbour-N, N-dimethylamino benzyl) scandium, [1-(dimethyl { the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl } silyl)-2,4-dimethyl cyclopentadienyl] two (neighbour-N, N-dimethylamino benzyl) scandium, [1-(diethyl { the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl } silyl)-2,4-dimethyl cyclopentadienyl] two (neighbour-N, N-dimethylamino benzyl) scandium, [1-(dimethyl { the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl } silyl)-2,3,5-trimethylammonium cyclopentadienyl] two (neighbour-N, N-dimethylamino benzyl) scandium, [1-(diethyl { the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl } silyl)-2,3,5-trimethylammonium cyclopentadienyl] two (neighbour-N, N-dimethylamino benzyl) scandium;
[1-(dimethyl { the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl } silyl)-2,3,4,5-tetramethyl-ring pentadienyl] two (trimethyl silyl methyl) scandium, [1-(diethyl { the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl } silyl)-2,3,4,5-tetramethyl-ring pentadienyl] two (trimethyl silyl methyl) scandium, [1-(dimethyl { the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl } silyl) cyclopentadienyl] two (trimethyl silyl methyl) scandium, [1-(diethyl { the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl } silyl) cyclopentadienyl] two (trimethyl silyl methyl) scandium, [1-(dimethyl { the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl } silyl)-2,4-dimethyl cyclopentadienyl] two (trimethyl silyl methyl) scandium, [1-(diethyl { the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl } silyl)-2,4-dimethyl cyclopentadienyl] two (trimethyl silyl methyl) scandium, [1-(dimethyl { the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl } silyl)-2,3,5-trimethylammonium cyclopentadienyl] two (trimethyl silyl methyl) scandium, [1-(diethyl { the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl } silyl)-2,3,5-trimethylammonium cyclopentadienyl] two (trimethyl silyl methyl) scandium;
[1-(dimethyl { the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl } silyl)-2,3,4,5-tetramethyl-ring pentadienyl] two (neighbour-N, N-dimethylamino benzyl) lutetium, [1-(diethyl { the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl } silyl)-2,3,4,5-tetramethyl-ring pentadienyl] two (neighbour-N, N-dimethylamino benzyl) lutetium, [1-(dimethyl { the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl } silyl) cyclopentadienyl] two (neighbour-N, N-dimethylamino benzyl) lutetium, [1-(diethyl { the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl } silyl) cyclopentadienyl] two (neighbour-N, N-dimethylamino benzyl) lutetium, [1-(dimethyl { the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl } silyl)-2,4-dimethyl cyclopentadienyl] two (neighbour-N, N-dimethylamino benzyl) lutetium, [1-(diethyl { the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl } silyl)-2,4-dimethyl cyclopentadienyl] two (neighbour-N, N-dimethylamino benzyl) lutetium, [1-(dimethyl { the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl } silyl)-2,3,5-trimethylammonium cyclopentadienyl] two (neighbour-N, N-dimethylamino benzyl) lutetium, [1-(diethyl { the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl } silyl)-2,3,5-trimethylammonium cyclopentadienyl] two (neighbour-N, N-dimethylamino benzyl) lutetium;
[1-(dimethyl { the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl } silyl)-2,3,4,5-tetramethyl-ring pentadienyl] two (trimethyl silyl methyl) lutetium, [1-(diethyl { the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl } silyl)-2,3,4,5-tetramethyl-ring pentadienyl] two (trimethyl silyl methyl) lutetium, [1-(dimethyl { the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl } silyl) cyclopentadienyl] two (trimethyl silyl methyl) lutetium, [1-(diethyl { the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl } silyl) cyclopentadienyl] two (trimethyl silyl methyl) lutetium, [1-(dimethyl { the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl } silyl)-2,4-dimethyl cyclopentadienyl] two (trimethyl silyl methyl) lutetium, [1-(diethyl { the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl } silyl)-2,4-dimethyl cyclopentadienyl] two (trimethyl silyl methyl) lutetium, [1-(dimethyl { the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl } silyl)-2,3,5-trimethylammonium cyclopentadienyl] two (trimethyl silyl methyl) lutetium, [1-(diethyl { the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl } silyl)-2,3,5-trimethylammonium cyclopentadienyl] two (trimethyl silyl methyl) lutetium;
[1-{1-(the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl)-1-methylethyl } cyclopentadienyl] two (neighbour-N, N-dimethylamino benzyl) yttrium, [1-{1-(the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl)-1-ethyl propyl } cyclopentadienyl] two (neighbour-N, N-dimethylamino benzyl) yttrium, [1-{1-(the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl)-1-methylethyl }-the 3-methyl cyclopentadienyl] two (neighbour-N, N-dimethylamino benzyl) yttrium, [1-{1-(the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl)-1-ethyl propyl }-the 3-methyl cyclopentadienyl] two (neighbour-N, N-dimethylamino benzyl) yttrium, [1-{1-(the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl)-1-methylethyl }-3-tertiary butyl cyclopentadienyl] two (neighbour-N, N-dimethylamino benzyl) yttrium, [1-{1-(the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl)-1-ethyl propyl }-3-tertiary butyl cyclopentadienyl] two (neighbour-N, N-dimethylamino benzyl) yttrium;
[1-{1-(the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl)-1-methylethyl } cyclopentadienyl] two (trimethyl silyl methyl) yttrium, [1-{1-(the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl)-1-ethyl propyl } cyclopentadienyl] two (trimethyl silyl methyl) yttrium, [1-{1-(the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl)-1-methylethyl }-the 3-methyl cyclopentadienyl] two (trimethyl silyl methyl) yttrium, [1-{1-(the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl)-1-ethyl propyl }-the 3-methyl cyclopentadienyl] two (trimethyl silyl methyl) yttrium, [1-{1-(the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl)-1-methylethyl }-3-tertiary butyl cyclopentadienyl] two (trimethyl silyl methyl) yttrium, [1-{1-(the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl)-1-ethyl propyl }-3-tertiary butyl cyclopentadienyl] two (trimethyl silyl methyl) yttrium;
And then also can be to replace the compound that scandium, lutetium or the yttrium of above-claimed cpd form with lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium or ytterbium.
Rare earth metal complex (1) can by make the rare earth metal compound shown in cyclopentadiene compound (2) and the formula (3) (below, abbreviate rare earth metal compound (3) as.) reaction prepare.
Substituent R 8In alkyl also can replace with silyl, described silyl carbonatoms is 1～20 alkyl replacement, it as above-mentioned carbonatoms the example of 1～20 alkyl, can enumerate methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, n-pentyl, neo-pentyl, amyl group, n-hexyl, heptyl, n-octyl, n-nonyl, positive decyl, dodecyl, the n-tridecane base, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, with the NSC 62789 base, preferably enumerate methyl, ethyl, sec.-propyl, the tertiary butyl, amyl group etc.
As substituent R 8In the example of the alkyl that replaces of available silyl, described silyl carbonatoms is 1～20 alkyl replacement, can enumerate trimethyl silyl methyl, triethylsilyl methyl, triisopropyl silyl methyl, three normal-butyl silyl methyl, t-butyldimethylsilyl methyl etc., preferably enumerate the trimethyl silyl methyl.
Substituent R 8In aralkyl can replace with amino, described amino is 1～20 alkyl replacement with carbonatoms, it as above-mentioned carbonatoms the example of 1～20 alkyl, can enumerate methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, n-pentyl, neo-pentyl, amyl group, n-hexyl, heptyl, n-octyl, n-nonyl, positive decyl, dodecyl, the n-tridecane base, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, with the NSC 62789 base, preferably enumerate methyl, ethyl, sec.-propyl, the tertiary butyl, amyl group etc.
As substituent R 8In the example with the amino aralkyl that replaces, described amino be 1～20 alkyl replacement with carbonatoms, can enumerate neighbour-N, N-dimethylamino benzyl, neighbour-N, N-diethylamino benzyls etc. are preferably enumerated neighbour-N, N-dimethylamino benzyl.
Cyclopentadiene compound (2) for example can prepare with technique known (for example opening flat 9-87313 number with reference to the spy).
The example of above-mentioned cyclopentadiene compound (2) can be enumerated following compound:
(2-p-methoxy-phenyl) (cyclopentadienyl) diethylsilane, (2-methoxyl group-3-aminomethyl phenyl) (cyclopentadienyl) diethylsilane, (2-methoxyl group-3, the 5-3,5-dimethylphenyl) (cyclopentadienyl) diethylsilane, (2-methoxyl group-3-tert-butyl-phenyl) (cyclopentadienyl) diethylsilane, (the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl) (cyclopentadienyl) diethylsilane, (2-methoxyl group-3, the 5-di-tert-butyl-phenyl) (cyclopentadienyl) diethylsilane, (2-methoxyl group-5-methyl-3-phenyl) (cyclopentadienyl) diethylsilane, (2-methoxyl group-5-methyl-3-trimethyl silyl phenyl) (cyclopentadienyl) diethylsilane, (2-methoxyl group-3-t-butyldimethylsilyl-5-aminomethyl phenyl) (cyclopentadienyl) diethylsilane, (2-methoxyl group-3,5-diamyl phenyl) (cyclopentadienyl) diethylsilane, (the 2-methoxyl group-3-tertiary butyl-5-p-methoxy-phenyl) (cyclopentadienyl) diethylsilane, (the 2-methoxyl group-5-tertiary butyl-3-chloro-phenyl-) (cyclopentadienyl) diethylsilane, (1-methoxynaphthalene-2-yl) (cyclopentadienyl) diethylsilane, (the 2-methoxyl group-3-tertiary butyl-5-p-methoxy-phenyl) (cyclopentadienyl) diethylsilane
(2-p-methoxy-phenyl) (2,3,4,5-tetramethyl-ring pentadienyl) diethylsilane, (2-methoxyl group-3-aminomethyl phenyl) (2,3,4,5-tetramethyl-ring pentadienyl) diethylsilane, (2-methoxyl group-3, the 5-3,5-dimethylphenyl) (2,3,4,5-tetramethyl-ring pentadienyl) diethylsilane, (2-methoxyl group-3-tert-butyl-phenyl) (2,3,4,5-tetramethyl-ring pentadienyl) diethylsilane, (the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl) (2,3,4,5-tetramethyl-ring pentadienyl) diethylsilane, (2-methoxyl group-3,5-di-tert-butyl-phenyl) (2,3,4,5-tetramethyl-ring pentadienyl) diethylsilane, (2-methoxyl group-5-methyl-3-phenyl) (2,3,4,5-tetramethyl-ring pentadienyl) diethylsilane, (2-methoxyl group-5-methyl-3-trimethyl silyl phenyl) (2,3,4,5-tetramethyl-ring pentadienyl) diethylsilane, (2-methoxyl group-3-t-butyldimethylsilyl-5-aminomethyl phenyl) (2,3,4,5-tetramethyl-ring pentadienyl) diethylsilane, (2-methoxyl group-3,5-diamyl phenyl) (2,3,4,5-tetramethyl-ring pentadienyl) diethylsilane, (the 2-methoxyl group-3-tertiary butyl-5-p-methoxy-phenyl) (2,3,4,5-tetramethyl-ring pentadienyl) diethylsilane, (the 2-methoxyl group-5-tertiary butyl-3-chloro-phenyl-) (2,3,4,5-tetramethyl-ring pentadienyl) diethylsilane, (1-methoxynaphthalene-2-yl) (2,3,4,5-tetramethyl-ring pentadienyl) diethylsilane, (the 2-methoxyl group-3-tertiary butyl-5-p-methoxy-phenyl) (2,3,4,5-tetramethyl-ring pentadienyl) diethylsilane etc.;
Also can be the compound that the diethylsilane of above-claimed cpd is transformed to dimethylsilane, diphenyl silane, ethyl-methyl silane, aminomethyl phenyl silane, dimethylmethane, diethyl methane,
2-[1-(cyclopentadienyl)-1-methylethyl]-the 1-anisole, 2-[1-(cyclopentadienyl)-1-methylethyl]-1-methoxyl group-4, the 6-dimethyl benzene, the 6-tertiary butyl-2-[1-(cyclopentadienyl)-1-methylethyl]-1-methoxyl group-4-methylbenzene, 6-[1-(cyclopentadienyl)-1-methylethyl]-1-methoxyl group-2-phenyl benzene, 1-t-butyldimethylsilyl-3-[1-(cyclopentadienyl)-1-methylethyl]-2-methoxyl group-5-methylbenzene, 3-[1-(cyclopentadienyl)-1-methylethyl]-2-methoxyl group-5-methyl isophthalic acid-trimethyl silyl benzene, the 6-tertiary butyl-2-[1-(cyclopentadienyl)-1-methylethyl]-1, the 4-dimethoxy benzene, the 5-tertiary butyl-1-chloro-3-[1-(cyclopentadienyl)-1-methylethyl]-the 4-anisole, the 6-tertiary butyl-2-[1-(cyclopentadienyl)-1-methylethyl]-the 1-anisole;
1-methoxyl group-2-[1-(4-methyl cyclopentadienyl)-1-methylethyl] benzene, 1-methoxyl group-4,6-dimethyl-2-[1-(4-methyl cyclopentadienyl)-1-methylethyl] benzene, the 6-tertiary butyl-1-methoxyl group-4-methyl-2-[1-(4-methyl cyclopentadienyl)-1-methylethyl] benzene, 1-methoxyl group-6-[1-(4-methyl cyclopentadienyl)-1-methylethyl]-2-phenyl benzene, 1-t-butyldimethylsilyl-2-methoxyl group-5-methyl-3-[1-(4-methyl cyclopentadienyl)-1-methylethyl] benzene, 2-methoxyl group-5-methyl-3-[1-(4-methyl cyclopentadienyl)-1-methylethyl]-1-trimethyl silyl benzene, the 6-tertiary butyl-1,4-dimethoxy-2-[1-(4-methyl cyclopentadienyl)-1-methylethyl] benzene, the 5-tertiary butyl-1-chloro-4-methoxyl group-3-[1-(4-methyl cyclopentadienyl)-1-methylethyl] benzene, the 6-tertiary butyl-1-methoxyl group-2-[1-(4-methyl cyclopentadienyl)-1-methylethyl] benzene, 2-[1-(4-tertiary butyl cyclopentadienyl)-1-methylethyl]-the 1-anisole, 2-[1-(4-tertiary butyl cyclopentadienyl)-1-methylethyl]-1-methoxyl group-4, the 6-dimethyl benzene, the 6-tertiary butyl-2-[1-(4-tertiary butyl cyclopentadienyl)-1-methylethyl]-1-methoxyl group-4-methylbenzene, 6-[1-(4-tertiary butyl cyclopentadienyl)-1-methylethyl]-1-methoxyl group-2-phenyl benzene, 1-t-butyldimethylsilyl-3-[1-(4-tertiary butyl cyclopentadienyl)-1-methylethyl]-2-methoxyl group-5-methylbenzene, 3-[1-(4-tertiary butyl cyclopentadienyl)-1-methylethyl]-2-methoxyl group-5-methyl isophthalic acid-trimethyl silyl benzene, the 6-tertiary butyl-2-[1-(4-tertiary butyl cyclopentadienyl)-1-methylethyl]-1, the 4-dimethoxy benzene, the 5-tertiary butyl-1-chloro-3-[1-(4-tertiary butyl cyclopentadienyl)-1-methylethyl]-the 4-anisole, the 6-tertiary butyl-2-[1-(4-tertiary butyl cyclopentadienyl)-1-methylethyl]-the 1-anisole etc.;
It also can be the compound that the methoxyl group of above-claimed cpd is transformed into oxyethyl group, isopropoxy, phenoxy group, benzyloxy.
In rare earth metal complex (1) and rare earth metal compound (3), the example of the single anion part of representing with substituent X can be enumerated hydrogen atom, halogen atom, methyl, ethyl, normal-butyl, neo-pentyl, phenyl, inferior neo-pentyl (ネ オ ペ Application チ リ デ Application base), methoxyl group, tert.-butoxy, phenoxy group, benzyl, amide group, phosphino-, the trimethyl silyl methyl, two (trimethyl silyl) methyl, two (trimethyl silyl) amide group, neighbour-dimethylamino benzyl preferably enumerates methyl, the trimethyl silyl methyl, neighbour-dimethylamino benzyl.
When m was 2, two X can mutually combine, and perhaps also can form two anionic property parts together.
In rare earth metal complex (1) and rare earth metal compound (3), the example of the neutral ligand of representing with substituting group Y can be enumerated olefines, aromatic substance class, ethers, thioether class, amine, nitrile, phosphine class or phosphinoxides etc., preferably enumerates ethers or amine.
Specifically can enumerate ethene with the neutral ligand that Y represents, propylene, 1-butylene, cyclooctadiene, vinylbenzene, benzene, toluene, naphthalene, anthracene, Anaesthetie Ether, tetrahydrofuran (THF), 1, the 2-glycol dimethyl ether, dimethyl thioether, thiophene, tetramethylene sulfide, Trimethylamine, triethylamine, ethyl diisopropyl amine, N, accelerine, N, N, N ', N '-Tetramethyl Ethylene Diamine, pyridine, N, the N-dimethyl aminopyridine, acetonitrile, trimethyl-phosphine, triethyl phosphine, tri-butyl phosphine, tricyclohexyl phosphine, triphenylphosphine, the trimethyl-phosphine oxide compound, triphenylphosphine oxidation thing etc., preferably enumerate tetrahydrofuran (THF), Anaesthetie Ether, N, accelerine, trimethyl-phosphine etc.
X and Y also can in conjunction with and form polydentate ligand.
Polydentate ligand specifically can be enumerated neighbour-N, N-dimethylamino benzyl.
M represents 1～3 integer, and is preferred 1～2, more preferably 2.N represents 0～3 integer, and is preferred 0～2, more preferably 0 or 2.
Above-mentioned rare earth metal compound (3) can come synthetic according to known method (for example, J.Am.Chem.Soc., 1978,100,8068 or J.Chem.Soc., Chem.Comm., 1973,126).
The example of above-mentioned rare earth metal compound (3) can be enumerated three (trimethyl silyl methyl) scandium, three (neighbour-N, N-dimethylamino benzyl) scandium etc., also can be Anaesthetie Ether, tetrahydrofuran (THF), Trimethylamine, triethylamine, the N of these compounds in addition, accelerine, N, N, N ', the affixture of N '-Tetramethyl Ethylene Diamine.Also can enumerate equally in addition scandium is changed to the compound that yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium form.More preferably enumerate three (neighbour-N, N-dimethylamino benzyl) scandium, three (neighbour-N, N-dimethylamino benzyl) yttrium, three (neighbour-N, N-dimethylamino benzyl) lutetium.
Cyclopentadiene compound (2) can add rare earth metal compound (3) and carry out by add cyclopentadiene compound (2) in solvent after usually with the reaction of rare earth metal compound (3).
The usage quantity of rare earth metal compound (3) is generally 0.5～3 mole with respect to per 1 mole of cyclopentadiene compound (2), preferred 0.7～1.5 mole.
Temperature of reaction is the temperature from-100 ℃ to solvent boiling point normally, is preferably-80 ℃～60 ℃ scope.
Reaction is being to carry out in the inert solvent for reaction usually.The example of above-mentioned solvent can be enumerated aromatic hydrocarbon series solvents such as benzene, toluene; Aliphatic hydrocarbon such as hexane, heptane series solvent; Anaesthetie Ether, tetrahydrofuran (THF), 1, ether series solvents such as 4-diox; Acid amides such as hexamethylphosphoramide, dimethyl formamide series solvent; Acetonitrile, propionitrile, acetone, diethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone isopolarity solvent; The non-protonic solvent that halogen series solvents such as methylene dichloride, ethylene dichloride, chlorobenzene, dichlorobenzene are such etc.Above-mentioned solvent can be distinguished use separately, perhaps will mix more than 2 kinds and use, and its usage quantity is generally 1～200 weight part, preferred 3～50 weight parts with respect to per 1 weight part cyclopentadiene compound (2).
After reaction finishes, reaction mixture by gained utilizes usual method can obtain purpose rare earth metal complex (1), described usual method for example is after the precipitation that will generate filters, and concentrated filtrate and rare earth metal complex (1) is separated out is then with the method for its leaching etc.
(catalyst for olefines polymerizing)
Catalyst for olefines polymerizing of the present invention is with the catalyst for olefines polymerizing of rare earth metal complex (1) as the catalyst for olefines polymerizing composition, and it makes rare earth metal complex (1) contact and get with other co-catalyst composition.As this catalyst for olefines polymerizing, can enumerate making rare earth metal complex (1) and being selected from the catalyst for olefines polymerizing that at least a kind the compound of following aluminum compound (A1)～(A3) with following boron compound (B1)～(B3) contacts and get;
Aluminum compound (A):
(A1): with formula (E 1) aAlZ (3-a)The organo-aluminium compound of expression;
(A2): have with formula { Al (E 2)-O-} bThe ring-type aikyiaiurnirsoxan beta of the structure of expression;
(A3): have the formula of using E 3{ Al (E 3)-O-} cAl (E 3) 2The line style aikyiaiurnirsoxan beta of the structure of expression
(in the formula, a represents to satisfy the numerical value of 0＜a ≦ 3, and b represents the integer more than 2, and c represents the integer more than 1.E 1, E 2And E 3Represent that respectively carbonatoms is 1～20 alkyl, a plurality of E 1, a plurality of E 2With a plurality of E 3Can be respectively identical, also can be different.Z represents hydrogen atom or halogen atom, and a plurality of Z can be identical mutually, also can be different.)
Boron compound (B):
(B1): use formula BQ 1Q 2Q 3The boron compound of expression;
(B2): use formula G +(BQ 1Q 2Q 3Q 4) -The boron compound of expression;
(B3): with formula (L 1-H) +(BQ 1Q 2Q 3Q 4) -The boron compound of expression
(in the formula, B represents the boron atom of the valence state of 3 valencys, Q 1, Q 2, Q 3And Q 4Represent halogen atom, alkyl, halogenation alkyl respectively independently, replace silyl, alkoxyl group or 2 substituted-aminos, G +Represent inorganic or organic positively charged ion, L 1The expression neutral Lewis base.)。
With formula (E 1) aAlZ (3-a)The example of the organo-aluminium compound (A1) of expression can be enumerated trialkylaluminiums such as trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, three hexyl aluminium; Chlorination aluminum dialkyls such as chlorodimethylalumiu, diethylaluminum chloride, chlorination dipropyl aluminium, di-isobutyl aluminum chloride, chlorination dihexyl aluminium; Dichloride aluminum alkylss such as methylaluminium dichloride, ethylaluminium dichloride, dichloride propyl group aluminium, aluminium isobutyl dichloride, dichloride hexyl aluminium; Hydrogenation aluminum dialkyls such as hydrogenation dimethyl aluminium, diethyl aluminium hydride, hydrogenation dipropyl aluminium, diisobutylaluminium hydride, hydrogenation dihexyl aluminium etc.Preferred trialkylaluminium, more preferably triethyl aluminum or triisobutyl aluminium.
As having with formula { Al (E 2)-O-} bThe expression structure ring-type aikyiaiurnirsoxan beta (A2) or have the formula of using E 3{ Al (E 3)-O-} cAl (E 3) 2E in the line style aikyiaiurnirsoxan beta (A3) of the structure of expression 2And E 3Example, can enumerate alkyl such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, n-pentyl, neo-pentyl.B is the integer more than 2, and c is the integer more than 1.Preferred E 2And E 3Be methyl or isobutyl-independently respectively, b is 2～40, and c is 1～40.
Above-mentioned aikyiaiurnirsoxan beta can be made of various preparation methods.The preparation method does not limit especially, makes getting final product according to known method.The solution that dissolving trialkylaluminium (for example trimethyl aluminium etc.) is formed contacts with water to be made.In addition, can enumerate and make trialkylaluminium (for example trimethyl aluminium etc.) contact method of making etc. with the metal-salt that contains crystal water (for example copper sulfate hydrate etc.).
Using formula BQ 1Q 2Q 3In the boron compound (B1) of expression, B is the boron atom of the valence state of 3 valencys.Q 1～Q 3Preferred halogen atom, the carbonatoms represented independently respectively is that 1～20 alkyl, carbonatoms are that 1～20 halogenation alkyl, carbonatoms are that 1～20 replacement silyl, carbonatoms are that 1～20 alkoxyl group or carbonatoms are 2～20 2 substituted-aminos, and more preferably halogen atom, carbonatoms are that 1～20 alkyl or carbonatoms are 1～20 halogenation alkyl.
Use formula BQ 1Q 2Q 3The example of the boron compound (B1) of expression can be enumerated three (pentafluorophenyl group) borine, three (2,3,5,6-tetrafluoro phenyl) borine, three (2,3,4,5-tetrafluoro phenyl) borine, three (3,4, the 5-trifluorophenyl) borine, three (2,3,4-trifluorophenyl) borine, two (pentafluorophenyl group) borines of phenyl etc., preferred three (pentafluorophenyl group) borine.
Using formula G +(BQ 1Q 2Q 3Q 4) -In the boron compound (B2) of expression, G +Be inorganic or organic positively charged ion, B is the boron atom of the valence state of 3 valencys, Q 1～Q 4With the Q in above-mentioned (B1) 1～Q 3Equally.
Using G +(BQ 1Q 2Q 3Q 4) -In the boron compound (B2) of expression, for G as inorganic cation +, for example can enumerate ferrocene cation, alkyl replaces ferrocene cation, silver-colored positively charged ion etc., for as organic cations G +, can enumerate for example trityl group positively charged ion etc.In addition, (BQ 1Q 2Q 3Q 4) -Example can enumerate four (pentafluorophenyl group) borate, four (2,3,5,6-tetrafluoro phenyl) borate, four (2,3,4,5-tetrafluoro phenyl) borate, four (3,4, the 5-trifluorophenyl) borate, four (2,2,4-trifluorophenyl) borate, two (pentafluorophenyl group) borate, four [3,5-two (trifluoromethyl) phenyl] borates of phenyl etc.
Use formula G +(BQ 1Q 2Q 3Q 4) -The example of the boron compound (B2) of expression can be enumerated ferrocene four (pentafluorophenyl group) borate, 1,1 '-dimethyl ferrocene four (pentafluorophenyl group) borate, silver four (pentafluorophenyl group) borate, trityl group four (pentafluorophenyl group) borate, trityl group four [(3,5-two (trifluoromethyl) phenyl] borate etc., preferred trityl group four (pentafluorophenyl group) borate.
Using formula (L 1-H) +(BQ 1Q 2Q 3Q 4) -In the boron compound (B3) of expression, L 1Be neutral Lewis base, (L 1-H) +Be Bronsted acid, B is the boron atom of the valence state of 3 valencys, Q 1～Q 4With the Q in above-mentioned (B1) 1～Q 3Equally.
Using formula (L 1-H) +(BQ 1Q 2Q 3Q 4) -In the boron compound (B3) of expression, (L 1-H) +For example can enumerating, trialkyl replaces ammonium, N, N-dialkyl aniline, dialkyl ammonium, San Fang Ji Phosphonium etc., (BQ 1Q 2Q 3Q 4) -Can enumerate and above-mentioned same compound.
As using formula (L 1-H) +(BQ 1Q 2Q 3Q 4) -The example of the boron compound (B3) of expression, can enumerate triethyl ammonium four (pentafluorophenyl group) borate, tripropyl ammonium four (pentafluorophenyl group) borate, three normal-butyl ammonium four (pentafluorophenyl group) borates, three normal-butyl ammoniums four [3,5-two (trifluoromethyl) phenyl] borate, N, accelerine four (pentafluorophenyl group) borate, N, N-Diethyl Aniline four (pentafluorophenyl group) borate, N, N-2,4,6-pentamethylaminobenzene four (pentafluorophenyl group) borate, N, accelerine four [3,5-two (trifluoromethyl) phenyl] borate, di-isopropyl ammonium four (pentafluorophenyl group) borate, dicyclohexyl ammonium four (pentafluorophenyl group) borate, triphenyl phosphonium four (pentafluorophenyl group) borate, three (aminomethyl phenyl) Phosphonium four (pentafluorophenyl group) borates, three (3,5-dimethylphenyl) Phosphonium four (pentafluorophenyl group) borates etc., preferred three normal-butyl ammonium four (pentafluorophenyl group) borate or N, accelerine four (pentafluorophenyl group) borate.
Compound (B) can use usually uses formula BQ 1Q 2Q 3The boron compound (B1) of expression is used formula G +(BQ 1Q 2Q 3Q 4) -The boron compound (B2) of expression or with formula (L 1-H) +(BQ 1Q 2Q 3Q 4) -Any one of the boron compound (B3) of expression.
For the method that in the preparation of catalyst for olefines polymerizing, makes each catalyst component contact, also can make 2 kinds of catalyst component contacts arbitrarily in advance, another kind of catalyst component is in contact with it.In addition, each catalyst component also can contact in polymerizing reactor, each catalyst component can be joined respectively in the polymerizing reactor in any order, also can add the composition that the contact of the catalyst component more than 2 kinds is arbitrarily formed.
As the usage quantity of each catalyst component, the mol ratio of compound (A) (conversion of aluminium atom)/rare earth metal complex (1) is generally 0.1:1～10000:1, preferred 5:1～2000:1.When using organo-aluminium compound (Al) as compound (A), the mol ratio of compound (A)/rare earth metal complex (1) is 0.3:1～500:1 more preferably, and then preferred 0.5:1～100:1.In addition, the mol ratio of compound (B)/rare earth metal complex (1) is generally 0.01:1～100:1, preferred 0.5:1～10:1.
Concentration when using each catalyst component with solution state, the concentration of rare earth metal complex (1) be generally 0.0001～5 mmole/liter, preferred 0.001～1 mmole/liter, the concentration of compound (A) with the aluminium atom convert be generally 0.01～500 mmole/liter, preferred 0.1～100 mmole/liter, the concentration of compound (B) be generally 0.0001～5 mmole/liter, preferred 0.001～1 mmole/liter.
(preparation method of olefin polymer)
In the preparation method of olefin polymer of the present invention, with rare earth metal complex (1) as the catalyst for olefines polymerizing of catalyst for olefines polymerizing composition in the presence of, carry out the polymerization of alkene.
The alkene that uses in polymerization can use chain alkene, cyclic olefin etc., can use a kind of alkene to carry out independent polymerization, also can use the alkene more than 2 kinds to carry out copolymerization.Usually can to use carbonatoms be 2～20 alkene to this alkene.
Chain alkene can be enumerated ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butylene, 5-methyl isophthalic acid-hexene, 3,3-dimethyl-carbonatomss such as 1-amylene are 3～20 alpha-olefin; 1, the 5-hexadiene, 1, the 4-hexadiene, 1, the 4-pentadiene, 1, the 5-heptadiene, 1, the 6-heptadiene, 1, the 6-octadiene, 1, the 7-octadiene, 1, the 7-nonadiene, 1, the 8-nonadiene, 1, the 8-decadiene, 1, the 9-decadiene, 1,12-14 carbon diene, 1,13-14 carbon diene, the 4-methyl isophthalic acid, the 4-hexadiene, the 5-methyl isophthalic acid, the 4-hexadiene, the 7-methyl isophthalic acid, the 6-octadiene, the 3-methyl isophthalic acid, the 4-hexadiene, the 3-methyl isophthalic acid, the 5-hexadiene, 3-ethyl-1, the 4-hexadiene, 3-ethyl-1, the 5-hexadiene, 3,3-dimethyl-1,4-hexadiene, 3,3-dimethyl-1, the non-conjugated diene of 5-hexadiene etc.; 1,3-butadiene, isoprene, 1,3-hexadiene, 1, the conjugated diolefine of 3-octadiene etc. etc.
As cyclic olefin, alicyclic compound can be enumerated the monoolefine of vinyl pentamethylene, vinyl cyclohexane, vinyl suberane, norbornylene, 5-methyl-2-norbornylene, 5-ethyl-2-norbornylene, 5-butyl-2-norbornylene, tetracyclododecane, tricyclo decene, three ring undecylenes, five rings 15 carbenes, five rings cetene, 8-methyl tetracyclododecane, 8-ethyl tetracyclododecane etc.; 5-ethylidene-2-norbornene, Dicyclopentadiene (DCPD), 5-vinyl-2-norbornylene, norbornadiene, 5-methylene-2-norbornene, 1, the 5-cyclooctadiene, 7-methyl-2, the 5-norbornadiene, 7-ethyl-2, the 5-norbornadiene, 7-propyl group-2, the 5-norbornadiene, 7-butyl-2, the 5-norbornadiene, 7-amyl group-2, the 5-norbornadiene, 7-hexyl-2, the 5-norbornadiene, 7,7-dimethyl-2, the 5-norbornadiene, 7,7-methylethyl-2,5-norbornadiene, 7-chloro-2, the 5-norbornadiene, 7-bromo-2, the 5-norbornadiene, 7-fluoro-2, the 5-norbornadiene, 7,7-two chloro-2, the 5-norbornadiene, 1-methyl-2, the 5-norbornadiene, 1-ethyl-2, the 5-norbornadiene, 1-propyl group-2, the 5-norbornadiene, 1-butyl-2, the 5-norbornadiene, 1-chloro-2, the 5-norbornadiene, 1-bromo-2, the 5-norbornadiene, 5, methylene radical hexahydro naphthalene in the 8-, the non-conjugated diene of vinyl cyclohexane etc.; 1, the conjugated diolefine of 3-cyclooctadiene, 1 etc. etc.In addition, aromatic substance can be enumerated vinylbenzene, neighbour-vinyl toluene, a vinyl toluene, p-methylstyrene, neighbour, right-dimethyl styrene, neighbour-ethyl styrene, an ethyl styrene, to ethyl styrene, alpha-methyl styrene, Vinylstyrene etc.
The example of the alkene combination when carrying out olefin-copolymerization can be enumerated the combination of ethylene/propene, ethene/1-butylene, ethene/1-hexene, ethylene/propene/1-butylene, ethylene/propene/1-hexene, propylene/1-butene, propylene/chain alkene/chain alkene such as 1-hexene; The combination of chain alkene/cyclic olefins such as ethylene/vinyl basic ring hexane, ethene/norbornylene, ethene/tetracyclododecane, ethene/5-ethylidene-2-norbornene, propylene/ethylene basic ring hexane, propylene/norbornylene, propylene/tetracyclododecane, propylene/5-ethylidene-2-norbornene, ethylene/propene/5-ethylidene-2-norbornene etc.
Polymerization process does not limit especially, for example can be to use aliphatic hydrocarbon (butane, pentane, hexane, heptane, octane etc.), aromatic hydrocarbon (benzene, toluene etc.) or halon (methylene dichloride etc.) as vapour phase polymerization in the solution polymerization of solvent or slurry polymerization, the gasiform monomer etc., can be any of successive polymerization or batchwise polymerization.
Polymerization temperature is usually-50 ℃～300 ℃ scope, especially preferred-20 ℃～250 ℃ scope.Preferred normal pressure～the 90MPa of polymerization pressure.Polymerization time generally suitably determines according to kind, the reaction unit of purpose polymers, can adopt 1 minute～24 hours scope.In addition, the present invention also can add the chain-transfer agent of hydrogen etc. for the molecular weight of telomerized polymer.
The preparation method of＜polar monomer polymkeric substance 〉
Use rare earth class title complex of the present invention (1), can carry out the independent polymerization of polar monomer, perhaps the copolymerization of polar monomer of certain polar monomer and the kind that is different from it.The kind of this polar monomer does not limit especially, can enumerate for example lactone compound, olefinated oxygen compound, (methyl) acrylic compound etc.
(preparation method of lactone polymer)
The lactone compound that uses among the present invention can be enumerated beta-propiolactone, gamma-butyrolactone, δ-Wu Neizhi, 6-caprolactone, Beta-methyl propiolactone, 3,3,5-trimethylammonium-6-caprolactone etc., preferred 6-caprolactone.
The polymerization separately of these lactone compounds also can be with the lactone compound copolymerization more than 2 kinds.The method of the lactone compound copolymerization more than 2 kinds is not limited especially, for example can be set forth in the method that initiated polymerization under the simultaneous condition of lactone more than 2 kinds obtains random copolymers, by making polyisocyanate polyaddition in the 1st kind in advance, add the method that the 2nd kind of later lactone obtains segmented copolymer then.
Polymerization process does not limit especially, for example can be to use aliphatic hydrocarbon (butane, pentane, hexane, heptane, octane etc.), aromatic hydrocarbon (benzene, toluene etc.) or halon (methylene dichloride etc.) solution polymerization or the slurry polymerization as solvent, can be any of successive polymerization or batchwise polymerization.
Polymerization temperature is usually-80 ℃～150 ℃ scope, especially preferred-30 ℃～100 ℃ scope.Polymerization time generally suitably determines according to kind, the reaction unit of purpose polymers, for example can adopt 1 second～24 hours scope.
Polyreaction is preferably carried out under the such atmosphere of inert gases of nitrogen or argon.In order to obtain polymkeric substance efficiently, rare gas element or internal ester monomer thorough drying, not contain moisture be important.
The lactone polymer that obtains contains the metal catalyst composition, but when the polymerization degree was high, containing of this metal catalyst composition was proportional little, therefore also can not remove.When needs are removed, remove the metal catalyst composition by washing lactone polymers such as water or dilute hydrochloric acid, dry then, can not contained the lactone polymer of metal catalyst composition thus.
The polymkeric substance of lactone of the present invention can prepare under lower temperature, and at this moment, the impurity that is produced by the depolymerization of lactone polymer or thermolysis of existence is few, therefore has the also few feature of tone excellence, stink.
The gained lactone polymer can be used as film or fiber, foaming sheet and various forming composition and uses by the extruding machine granulating.
(preparation method of alkylene oxide polymer)
Can to enumerate carbonatomss such as oxyethane, propylene oxide, butylene oxide ring, cyclohexene oxide, suberene oxygen, cyclooctene oxygen be that 2～9 alpha-olefin oxide compound and then carbonatoms are alpha-olefin oxide compound, Styrene oxide 98min., Epicholorohydrin more than 10 etc. to the example of the olefinated oxygen compound of Shi Yonging in the present invention.
The polymerization separately of these olefinated oxygen compounds also can be with the olefinated oxygen compound copolymerization more than 2 kinds.The method of the olefinated oxygen compound copolymerization more than 2 kinds is not limited especially, for example can be set forth in the method that initiated polymerization under the simultaneous condition of olefinated oxygen compound more than 2 kinds obtains random copolymers, by making the 1st kind of alkylene oxide polymerization in advance, add the method that the 2nd kind of later alkylene oxide obtains segmented copolymer then.
The polymeric initiating method does not limit especially, for example can add alkylene oxide in the solution of rare earth metal complex (1) and come initiated polymerization, perhaps can add rare earth metal complex (1) yet and come initiated polymerization in the solution of alkylene oxide.
Polymerization process does not limit especially, for example can be to use aliphatic hydrocarbon (butane, pentane, hexane, heptane, octane etc.), aromatic hydrocarbon (benzene, toluene etc.), ether (Anaesthetie Ether, tetrahydrofuran (THF), 1,4-diox etc.) or halon (methylene dichloride, ethylene dichloride etc.) as the solution polymerization or the slurry polymerization of solvent, can be any of successive polymerization or batchwise polymerization.
Polymerization temperature is usually-80 ℃～150 ℃ scope, especially preferred-30 ℃～100 ℃ scope.Polymerization time generally suitably determines according to kind, the reaction unit of purpose polymers, for example can adopt 1 second～24 hours scope.
Polyreaction is preferably carried out under the such atmosphere of inert gases of nitrogen or argon.In order to obtain polymkeric substance efficiently, rare gas element or alkylene oxide thorough drying, not contain moisture be important.
The alkylene oxide polymer that obtains contains the metal catalyst composition, but when the polymerization degree was high, containing of this metal catalyst composition was proportional little, therefore also can not remove.When needs are removed, remove the metal catalyst composition by washing alkylene oxide polymers such as water or dilute hydrochloric acid, dry then, can obtain alkylene oxide polymer thus.
The alkylene oxide polymer that obtains can be used as film or fiber, foaming sheet and various forming composition are used.
(preparation method of (methyl) acrylic ester polymer)
The example of (methyl) acrylate of Shi Yonging can be enumerated methyl methacrylate in the present invention, Jia Jibingxisuanyizhi, isopropyl methacrylate, n-BMA, the methacrylic tert-butyl acrylate, cyclohexyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, benzyl methacrylate, allyl methacrylate(AMA), the methacrylic ester of isobornyl methacrylate etc., methyl acrylate, ethyl propenoate, isopropyl acrylate, n-butyl acrylate, the acrylate of tert-butyl acrylate etc.
These (methyl) acrylate polymerizations separately also can be with (methyl) acrylic ester copolymer more than 2 kinds.The method of (methyl) acrylic ester copolymer more than 2 kinds is not limited especially, for example can be set forth in the method that initiated polymerization under the simultaneous condition of (methyl) acrylate more than 2 kinds obtains random copolymers, by making the 1st kind of (methyl) acrylic ester polymerization in advance, add the method that the 2nd kind of later (methyl) acrylate obtains segmented copolymer then.
The polymeric initiating method does not limit especially, for example can in the solution of rare earth metal complex (1), add (methyl) acrylate and come initiated polymerization, perhaps also can in the solution of (methyl) acrylate, add rare earth metal complex (1) and come initiated polymerization.
Polymerization process does not limit especially, for example can be to use aliphatic hydrocarbon (butane, pentane, hexane, heptane, octane etc.), aromatic hydrocarbon (benzene, toluene etc.), ether (Anaesthetie Ether, tetrahydrofuran (THF), 1,4-diox etc.) or halon (methylene dichloride, ethylene dichloride etc.) as the solution polymerization or the slurry polymerization of solvent, can be any of successive polymerization or batchwise polymerization.
Polymerization temperature is usually-80 ℃～150 ℃ scope, especially preferred-30 ℃～100 ℃ scope.Polymerization time generally suitably determines according to kind, the reaction unit of purpose polymers, for example can adopt 1 second～24 hours scope.
Polyreaction is preferably carried out under the such atmosphere of inert gases of nitrogen or argon.In order to obtain polymkeric substance efficiently, rare gas element or (methyl) acrylate monomer thorough drying, not contain moisture be important.
(methyl) acrylic ester polymer that obtains contains the metal catalyst composition, but when the polymerization degree was high, containing of this metal catalyst composition was proportional little, therefore also can not remove.When needs are removed, remove the metal catalyst composition by washings such as water or dilute hydrochloric acid (methyl) acrylic ester polymer, dry then, can obtain (methyl) acrylic ester polymer thus.
(methyl) acrylic ester polymer that obtains can be used as film or fiber, foaming sheet and various forming composition are used.Perhaps (methyl) acrylic ester polymer that obtains can be used as the additive that adds in other polymkeric substance.
Embodiment
Below, by embodiment and then explain the present invention, but the present invention is not limited to these embodiment.
The preparation of＜rare earth metal complex 〉
Physical property measurement carries out with following method.
(1) proton NMR spectrometry ( 1H-NMR)
Device: NEC society system EX270 or, the system DPX-300 of Bruker society
Sample pool: 5mm φ manages (チ ユ-Block)
Measure solvent: CDCl 3Perhaps toluene-d 8
Sample concentration: 10mg/0.5mL (CDCl 3Perhaps toluene-d 8)
Measure temperature: room temperature (about 25 ℃)
Location parameter: 5mm φ probe (プ ロ-Block), MENUF NON, OBNUC 1H, integral number of times 16 times
Pulse angle: 45 degree
Repetition time: ACQTM3 second, PD4 second
Internal standard: CDCl 3(7.26ppm), toluene-d 8(2.09ppm)
(2) the nuclear magnetic resonance of carbon spectrography ( 13C-NMR)
Device: NEC society system EX270 or, the system DPX-300 of Bruker society
Sample pool: 5mm φ pipe
Measure solvent: CDCl 3Perhaps toluene-d 8
Sample concentration: 30mg/0.5mL (CDCl 3Perhaps toluene-d 8)
Measure temperature: room temperature (about 25 ℃)
Location parameter: 5mm φ probe, MENUFBCM, OBNUC 13C, integral number of times 256 times
Pulse angle: 45 degree
Repetition time: ACQTM 1.8 seconds, PD1.2 second
Internal standard: CDCl 3(77.47,77.00,76.53ppm)
(3) mass spectrum
[EIMS (EI-MS)]
Device: the system JMS-T100GC of NEC society
Ionization voltage: 70eV
Ion source temperature: 230 ℃
Acceleration voltage: 7kV
MASS?RANGE：m/z?35-1000
Embodiment 1
Synthesizing of (the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl) chlorine diethylsilane
Under the nitrogen atmosphere, with the 2-methoxyl group-(20.00g 77.77mmol) is dissolved in the 200mL Anaesthetie Ether 1-bromo-3-tertiary butyl-5-methylbenzene.At the 1.57M hexane solution (59.44mL, 93.32mmol) that drips n-Butyl Lithium below-50 ℃, be warming up to room temperature after, stirred 1 hour.Below-50 ℃, once add all diethyl dichlorosilanes (24.44g, 155.54mmol) of amount, slowly be warming up to room temperature.After refluxing in 1 hour, solution is carried out concentrating under reduced pressure.Add hexane, insolubles is carried out C salt (セ ラ イ ト) filter concentrating under reduced pressure filtrate.And then, obtain (the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl) chlorine diethylsilane at 70 ℃ of following lasting concentrating under reduced pressure 3 hours.Gained (the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl) chlorine diethylsilane and then make with extra care is used for following reaction.
1H—NMR(CDCl 3、δ(ppm))：1.04—1.17(m、10H)、1.39(s、9H)、2.32(s、3H)、3.75(s、3H)、7.24(s、1H)、7.31(s、1H)
13C—NMR(CDCl 3、δ(ppm))：6.96、9.29、21.07、31.37、35.07、64.20、127.41、131.58、132.72、135.51、141.89、162.92
Embodiment 2
Synthesizing of (the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl) (2,3,4,5-tetramethyl-ring pentadiene-1-yl) diethylsilane
Under the nitrogen atmosphere, in sodium hydride (60wt%, 1.14g, 47.42mmol), add THF76mL.The tetrahydrofuran (THF) slurry of this sodium hydride is warming up to 50 ℃.Add aniline (0.29g, 3.16mmol), descend and then stirred 1 hour at 50 ℃.In THF19mL, dissolve 1,2,3, the solution that 4-tetramethyl-ring pentadiene (4.25g, 34.78mmol) forms to wherein slowly dripping.After dripping end, descend and then stir the generation until hydrogen in 3 hours to finish at 50 ℃.After being cooled to 20 ℃, drip the solution that dissolving (the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl) chlorine diethylsilane (9.45g, 31.61mmol) forms in toluene 19mL, at room temperature continue to stir 3 hours.To 10% sodium bicarbonate aqueous solution 47mL and 10% V Soda aqueous solution 47mL are cooled to the reaction soln that 0 ℃ of mixed solution and dripping that forms obtains, termination reaction is added toluene 47mL and is also carried out separatory.After carrying out drying with sodium sulfate, solution is carried out concentrating under reduced pressure, obtain the mixture of (the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl) (2,3,4,5-tetramethyl-ring pentadiene-1-yl) diethylsilane thus.Utilize silica gel column chromatography to make with extra care (the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl) (2,3,4,5-tetramethyl-ring pentadiene-1-yl) diethylsilane.
1H-NMR (toluene-d 8, δ (ppm)): 0.96-1.00 (m, 10H), 1.44 (s, 9H), 1.81 (s, 6H), 1.84 (s, 6H), 2.20 (s, 3H), 3.46 (s, 1H), 3.58 (s, 3H), 7.11 (s, 1H), 7.18 (s, 1H)
13C-NMR (toluene-d 8, δ (ppm)): 4.62,8.38,11.38,14.62,21.21,30.31,31.41,35.22,129.92,130.11,131.91,133.72,135.90,135.94,141.88,164.14
Embodiment 3
[1-(diethyl { the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl } silyl)-2,3,4,5-tetramethyl-ring pentadienyl] two (neighbour-N, N-dimethylamino benzyl) scandium (following note join be compound (1)) synthetic as scandium
Synthesizing of＜three (neighbour-N, N-dimethylamino benzyl) scandium 〉
According to synthetic three (neighbour-N, the N-dimethylamino benzyl) scandium of known document (J.Am.Chem.Soc.1978,100,8068).
1H-NMR (toluene-d 8, δ (ppm)): 1.58 (s, 6H), 2.28 (s, 18H), 6.71-6.78 (m, 6H), 6.85-6.95 (m, 6H)
Mass spectrum (EI-MS, m/z): 313 (M +-134), 268,134,91,65
Synthesizing of＜scandium title complex (1) 〉
Under the nitrogen atmosphere, with three (neighbour-N, N-dimethylamino benzyl) scandium (0.50g, 1.12mmol) is dissolved among the THF6mL, at room temperature add (the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl) (2,3,4,5-tetramethyl-ring pentadiene-1-yl) diethylsilane (0.43g, 1.12mmol) is dissolved in the mixture that forms among the tetrahydrofuran (THF) 6mL.At room temperature continue to stir 3 days.Mixture is carried out concentrating under reduced pressure, and add hexane, obtain scandium title complex (1) (0.48g, yield 61.4%) as faint yellow solid thus.
1H-NMR (toluene-d 8, δ (ppm)): 1.22-1.70 (m, 10H), 1.40 (s, 9H), 1.54 (s, 4H), 1.73 (s, 6H), 1.76 (s, 6H), 2.30 (s, 3H), 2.39 (s, 12H), 2.84 (s, 3H), 6.71-6.83 (m, 4H), 6.93-7.12 (m, 4H), 7.18 (s, 1H), 7.39 (s, 1H)
Mass spectrum (EI-MS, m/z): 384 (M +-313), 355,325,235,207,177,161,117,57
Embodiment 4
Synthesizing of [1-(diethyl { the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl } silyl)-2,3,4,5-tetramethyl-ring pentadienyl] two (neighbour-N, N-dimethylamino benzyl) lutetiums (following note is made lutetium title complex (1))
Synthesizing of＜three (neighbour-N, N-dimethylamino benzyl) lutetium 〉
Except using lutecium chloride, other according to embodiment 3 in the synthetic identical method of three (neighbour-N, N-dimethylamino benzyl) scandium synthesize three (neighbour-N, N-dimethylamino benzyl) lutetium
1H-NMR (toluene-d 8, δ (ppm)): 1.41 (s, 6H), 2.18 (s, 18H), 6.65-6.78 (m, 6H), 6.91-7.07 (m, 6H)
Mass spectrum (EI-MS, m/z): 443 (M +-134), 268,134,120,118,91,65
Synthesizing of＜lutetium title complex (1) 〉
Under the nitrogen atmosphere, with three (neighbour-N, N-dimethylamino benzyl) lutetium (0.50g, 1.04mmol) is dissolved among the tetrahydrofuran (THF) 6mL, at room temperature add (the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl) (2,3,4,5-tetramethyl-ring pentadiene-1-yl) diethylsilane (0.40g, 1.04mmol) is dissolved in the mixture that forms among the tetrahydrofuran (THF) 6mL.At room temperature continue to stir after 3 days, stirred 6 hours down at 60 ℃.Mixture is carried out concentrating under reduced pressure, and add hexane, obtain lutetium title complex (1) (0.51g, yield 59.2%) as white solid thus.
1H-NMR (toluene-d 8, δ (ppm)): 1.23-1.65 (m, 10H), 1.35 (s, 4H), 1.40 (s, 9H), 1.83 (s, 12H), 2.27 (s, 3H), 2.32 (s, 12H), 2.88 (s, 3H), 6.66-6.80 (m, 4H), 6.94-7.15 (m, 4H), 7.19 (s, 1H), 7.43 (s, 1H)
Mass spectrum (EI-MS, m/z): 384 (M +-443), 355,325,263,235,207,179,135,120,89,57
Embodiment 5
[1-{1-(the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl)-1-methylethyl } cyclopentadienyl] two (neighbour-N, N-dimethylamino benzyl) yttriums (following note is made yttrium complex (1)) are synthetic
Synthesizing of＜three (neighbour-N, N-dimethylamino benzyl) yttrium 〉
Except using Yttrium trichloride, other according to embodiment 3 in the synthetic identical method of three (neighbour-N, N-dimethylamino benzyl) scandium synthesize three (neighbour-N, N-dimethylamino benzyl) yttrium.
1H-NMR (toluene-d 8, δ (ppm)): 1.54 (s, 6H), 2.11 (s, 18H), 6.58-6.66 (m, 3H), 6.80-6.82 (m, 3H), 6.90-7.03 (m, 6H)
Mass spectrum (EI-MS, m/z): 357 (M +-134), 268,134,120,91,65
＜6-the tertiary butyl-2-[1-(cyclopentadienyl)-1-methylethyl]-1-methoxyl group-4-methylbenzene synthetic 〉
Synthesize the 6-tertiary butyl-2-[1-(cyclopentadienyl)-1-methylethyl according to known document (spy opens flat 9-87313 communique)]-1-methoxyl group-4-methylbenzene.
Synthesizing of＜yttrium complex (1) 〉
Under the nitrogen atmosphere, with three (neighbour-N, N-dimethylamino benzyl) yttrium (0.50g, 1.02mmol) is dissolved among the tetrahydrofuran (THF) 5mL, at room temperature adds the 6-tertiary butyl-2-[1-(cyclopentadienyl)-1-methylethyl]-1-methoxyl group-4-methylbenzene (0.29g, 1.02mmol) is dissolved in the mixture that forms among the tetrahydrofuran (THF) 5mL.At room temperature continue to stir after 24 hours, mixture is carried out concentrating under reduced pressure, and add pentane, obtain yttrium complex (1) (0.34g, yield 52.4%) as white solid thus.
1H-NMR (toluene-d 8, δ (ppm)): 1.45 (s, 13H), 1.90 (s, 6H), 2.25 (s, 15H), 3.01 (s, 3H), 5.58 (br s, 2H), 5.71-5.75 (m, 2H), 6.66-6.78 (m, 4H), 6.91-7.04 (m, 4H), 7.10 (br s, 2H)
Mass spectrum (EI-MS, m/z): 640 (M +)
Embodiment 6
[1-{1-(the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl)-1-methylethyl } cyclopentadienyl] two (neighbour-N, N-dimethylamino benzyl) scandiums (following note is made scandium title complex (2)) synthetic
Synthesizing of＜scandium title complex (2) 〉
Under the nitrogen atmosphere, with three (neighbour-N, N-dimethylamino benzyl) scandium (0.50g, 1.12mmol) is dissolved among the tetrahydrofuran (THF) 6mL, at room temperature adds the 6-tertiary butyl-2-[1-(cyclopentadienyl)-1-methylethyl]-1-methoxyl group-4-methylbenzene (0.32g, 1.12mmol) is dissolved in the mixture that forms among the tetrahydrofuran (THF) 6mL.At room temperature continue to stir after 24 hours, mixture is carried out concentrating under reduced pressure, add pentane and be cooled to-20 ℃.Behind the elimination insolubles, filtrate is cooled to-20 ℃.Obtain scandium title complex (2) (0.25g, yield 37.3%) by precipitation as faint yellow solid with refrigerative pentane washing gained.
1H-NMR (toluene-d 8, δ (ppm)): 1.44 (s, 13H), 1.82 (s, 6H), 2.22 (s, 3H), 2.37 (s, 12H), 3.00 (s, 3H), 5.60 (br s, 2H), 5.70 (br s, 2H), 6.69-6.71 (m, 2H), 6.81-6.84 (m, 2H), 6.95-7.00 (m, 4H), 7.07-7.10 (m, 2H)
Mass spectrum (EI-MS, m/z): 596 (M +)
Embodiment 7
[1-{1-(the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl)-1-methylethyl } cyclopentadienyl] two (neighbour-N, N-dimethylamino benzyl) lutetiums (following note is made lutetium title complex (2)) synthetic
Synthesizing of＜lutetium title complex (2) 〉
Under the nitrogen atmosphere, with three (neighbour-N, N-dimethylamino benzyl) lutetium (0.70g, 1.21mmol) is dissolved among the tetrahydrofuran (THF) 6mL, at room temperature adds the 6-tertiary butyl-2-[1-(cyclopentadienyl)-1-methylethyl]-1-methoxyl group-4-methylbenzene (0.34g, 1.21mmol) is dissolved in the mixture that forms among the tetrahydrofuran (THF) 6mL.At room temperature continue to stir after 24 hours, mixture is carried out concentrating under reduced pressure, add pentane and be cooled to-20 ℃.By obtain lutetium title complex (2) (0.62g, yield 70.5%) with refrigerative pentane washing gained precipitation as white solid.
1H-NMR (toluene-d 8, δ (ppm)): 1.45 (s, 13H), 1.60-2.10 (br d, 6H), 2.24 (s, 3H), 2.20-2.47 (br s, 12H), 3.01 (s, 3H), 5.40-5.80 (br, 4H), 6.65-6.68 (m, 2H), 6.76-6.82 (m, 2H), 6.92-7.01 (m, 4H), 7.07-7.12 (m, 2H)
Mass spectrum (EI-MS, m/z): 726 (M +)
Embodiment 8
[1-{1-(the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl)-1-methylethyl } cyclopentadienyl] two (neighbour-N, N-dimethylamino benzyl) thuliums (following note is made thulium title complex (1)) synthetic
Synthesizing of＜three (neighbour-N, N-dimethylamino benzyl) thulium 〉
Except using thulium chloride, other according to embodiment 3 in the synthetic identical method of three (neighbour-N, N-dimethylamino benzyl) scandium synthesize three (neighbour-N, N-dimethylamino benzyl) thulium.Mass spectrum (EI-MS, m/z): 571 (M +), 437,134,120,91,65
Synthesizing of＜thulium title complex (1) 〉
Under the nitrogen atmosphere, with three (neighbour-N, N-dimethylamino benzyl) thulium (0.70g, 1.22mmol) is dissolved among the tetrahydrofuran (THF) 6mL, at room temperature adds the 6-tertiary butyl-2-[1-(cyclopentadienyl)-1-methylethyl]-1-methoxyl group-4-methylbenzene (0.35g, 1.22mmol) is dissolved in the mixture that forms among the tetrahydrofuran (THF) 6mL.At room temperature continue to stir after 24 hours, mixture is carried out concentrating under reduced pressure, add pentane and be cooled to-20 ℃.By obtain thulium title complex (1) (0.63g, yield 71.8%) with refrigerative pentane washing gained precipitation as yellow solid.
Mass spectrum (EI-MS, m/z): 720 (M +)
Embodiment 9
[1-{1-(the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl)-1-methylethyl } cyclopentadienyl] two (neighbour-N, N-dimethylamino benzyl) erbiums (following note is made erbium title complex (1)) synthetic
Synthesizing of＜three (neighbour-N, N-dimethylamino benzyl) erbium 〉
Except using Erbium trichloride, other according to embodiment 3 in the synthetic identical method of three (neighbour-N, N-dimethylamino benzyl) scandium synthesize three (neighbour-N, N-dimethylamino benzyl) erbium.Mass spectrum (EI-MS, m/z): 568 (M +), 434,134,120,91,65
Synthesizing of＜erbium title complex (1) 〉
Under the nitrogen atmosphere, with three (neighbour-N, N-dimethylamino benzyl) erbium (0.70g, 1.23mmol) is dissolved among the tetrahydrofuran (THF) 6mL, at room temperature adds the 6-tertiary butyl-2-[1-(cyclopentadienyl)-1-methylethyl]-1-methoxyl group-4-methylbenzene (0.35g, 1.23mmol) is dissolved in the mixture that forms among the tetrahydrofuran (THF) 6mL.At room temperature continue to stir after 24 hours, mixture is carried out concentrating under reduced pressure, add pentane and be cooled to-20 ℃.By obtaining as light peachiness solid erbium title complex (1) (0.65g, yield 74.1%) with refrigerative pentane washing gained precipitation.
Mass spectrum (EI-MS, m/z): 719 (M +)
Embodiment 10
[1-{1-(the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl)-1-methylethyl } cyclopentadienyl] two (neighbour-N, N-dimethylamino benzyl) holmiums (following note is made holmium title complex (1)) synthetic
Synthesizing of＜three (neighbour-N, N-dimethylamino benzyl) holmium 〉
Except using Holmium trichloride, other according to embodiment 3 in the synthetic identical method of three (neighbour-N, N-dimethylamino benzyl) scandium synthesize three (neighbour-N, N-dimethylamino benzyl) holmium.
Mass spectrum (EI-MS, m/z): 567 (M +), 433,135,120,91,65
Synthesizing of＜holmium title complex (1) 〉
Under the nitrogen atmosphere, with three (neighbour-N, N-dimethylamino benzyl) holmium (0.70g, 1.23mmol) is dissolved among the tetrahydrofuran (THF) 6mL, at room temperature adds the 6-tertiary butyl-2-[1-(cyclopentadienyl)-1-methylethyl]-1-methoxyl group-4-methylbenzene (0.35g, 1.23mmol) is dissolved in the mixture that forms among the tetrahydrofuran (THF) 6mL.At room temperature continue to stir after 24 hours, mixture is carried out concentrating under reduced pressure, add pentane and be cooled to-20 ℃.By obtaining as greenish orange look solid erbium title complex (1) (0.61g, yield 69.7%) with refrigerative pentane washing gained precipitation.
Mass spectrum (EI-MS, m/z): 716 (M +)
Embodiment 11
[1-{1-(the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl)-1-methylethyl } cyclopentadienyl] two (neighbour-N, N-dimethylamino benzyl) dysprosiums (following note is made dysprosium title complex (1)) synthetic
Synthesizing of＜three (neighbour-N, N-dimethylamino benzyl) dysprosium 〉
Except using Dysprosium trichloride, other according to embodiment 3 in the synthetic identical method of three (neighbour-N, N-dimethylamino benzyl) scandium synthesize three (neighbour-N, N-dimethylamino benzyl) dysprosium.
Mass spectrum (EI-MS, m/z): 432 (M +-133), 268,135,120,65
Synthesizing of＜dysprosium title complex (1) 〉
Under the nitrogen atmosphere, with three (neighbour-N, N-dimethylamino benzyl) dysprosium (0.70g, 1.24mmol) is dissolved among the tetrahydrofuran (THF) 6mL, at room temperature adds the 6-tertiary butyl-2-[1-(cyclopentadienyl)-1-methylethyl]-1-methoxyl group-4-methylbenzene (0.35g, 1.24mmol) is dissolved in the mixture that forms among the tetrahydrofuran (THF) 6mL.At room temperature continue to stir after 24 hours, mixture is carried out concentrating under reduced pressure, add pentane and be cooled to-20 ℃.By obtain dysprosium title complex (1) (0.63g, yield 71.6%) with refrigerative pentane washing gained precipitation as faint yellow solid.
Mass spectrum (EI-MS, m/z): 714 (M +)
Embodiment 12
[1-{1-(the 2-methoxyl group-3-tertiary butyl-5-aminomethyl phenyl)-1-methylethyl } cyclopentadienyl] two (neighbour-N, N-dimethylamino benzyl) terbiums (following note is made terbium coordination compound (1)) synthetic
Synthesizing of＜three (neighbour-N, N-dimethylamino benzyl) terbium 〉
Except using Dysprosium trichloride, other according to embodiment 3 in the synthetic identical method of three (neighbour-N, N-dimethylamino benzyl) scandium synthesize three (neighbour-N, N-dimethylamino benzyl) terbium.
Mass spectrum (EI-MS, m/z): 427 (M +-134), 268,135,120,91,65
Synthesizing of＜terbium coordination compound (1) 〉
Under the nitrogen atmosphere, with three (neighbour-N, N-dimethylamino benzyl) terbium (0.70g, 1.25mmol) is dissolved among the tetrahydrofuran (THF) 6mL, at room temperature adds the 6-tertiary butyl-2-[1-(cyclopentadienyl)-1-methylethyl]-1-methoxyl group-4-methylbenzene (0.35g, 1.25mmol) is dissolved in the mixture that forms among the tetrahydrofuran (THF) 6mL.At room temperature continue to stir after 24 hours, mixture is carried out concentrating under reduced pressure, add pentane and the insolubles elimination.Filtrate is cooled to-20 ℃.By obtain terbium coordination compound (1) (0.56g, yield 62.5%) with refrigerative pentane washing gained precipitation as yellow solid.
Mass spectrum (EI-MS, m/z): 710 (M +)
The preparation of＜ethene-alpha-olefin copolymer 〉
Physical property measurement carries out in order to following method.
(1) 1-hexene unit content (SCB, the unit: 1/1000C) in the multipolymer
Use infrared spectrophotometer (the system EQUINOX55 of Bruker society), try to achieve by infrared measure.And the characteristic absorbance of butyl side chain is used 1378cm -1～1303cm -1The peak, 1-hexene unit content is represented as the butyl branch number of per 1000 carbon in ethene-1-hexene copolymer.
(2) molecular weight and molecular weight distribution
Utilize gel permeation chromatography (GPC), measure under the following conditions.Molecular weight distribution is estimated with the weight-average molecular weight (Mw) and the ratio (Mw/Mn) of number-average molecular weight (Mn).
Device: the system Model305 (pump head 25.SC) of liquid feeding device (LC pump) Gilson society
Pillar: the system PLgel Mixed-B 10 μ m of PolymerLaboratories society (7.5mm φ * 300mm)
Measure temperature: 160 ℃
Moving phase: orthodichlorobenzene
Sample concentration: copolymer 1 mg/1,2,4-trichlorobenzene 1mL
Flow: 2mL/ branch
Reference material: (standard P S molecular weight) 5,000,10,050,28,500,65,500,185,400,483,000,1,013,000,3,390,000
The scandium title complex (1) that will obtain in embodiment 3 uses the system PPR of Symyx society (48 connect autoclave) to utilize following polymerizing condition to carry out the copolymerization of ethene and 1-hexene as the catalyst for olefines polymerizing composition.
Embodiment 13
Under the nitrogen atmosphere, the toluene 5.0mL that packs in autoclave, 1-hexene 60 μ L after making it stable under 40 ℃, are forced into 0.60MPa with ethene, make it stable.Add aikyiaiurnirsoxan beta (eastern ソ-Off ア イ Application ケ system society system MMAO, 5.8 weight %Al) 100 μ mol (Al atom scaled value), scandium title complex (1) 0.10 μ mol therein, carry out 30 minutes polymerization.The polymeric result is every 1mol catalyzer, the polymkeric substance 1.9 * 10 that can prepare the 1-hexene unit content (SCB)=10 in molecular weight (Mw)=676,000, molecular weight distribution (Mw/Mn)=11.2, the multipolymer in per 1 hour 6G.
Embodiment 14
Except the 1-hexene being changed over 50 μ L, polymerization temperature being changed over 70 ℃, other carry out polymerization similarly to Example 13, every 1mol catalyzer, can prepare the polymkeric substance 6.9 * 10 of the 1-hexene unit content (SCB)=8 in molecular weight (Mw)=262,000, molecular weight distribution (Mw/Mn)=9.0, the multipolymer in per 1 hour 6G.
Embodiment 15
Except the 1-hexene being changed over 40 μ L, polymerization temperature being changed over 130 ℃ and aikyiaiurnirsoxan beta made into the 10 μ mol, other carry out polymerization similarly to Example 13, every 1mol catalyzer, can prepare the polymkeric substance 20.5 * 10 of the 1-hexene unit content (SCB)=1 in molecular weight (Mw)=59,000, molecular weight distribution (Mw/Mn)=1.6, the multipolymer in per 1 hour 6G.
Embodiment 16
Under the nitrogen atmosphere, the toluene 5.0mL that packs in autoclave, 1-hexene 60 μ L after making it stable under 40 ℃, are forced into 0.60MPa with ethene, make it stable.Add hexane solution 40 μ L (Northeast chemistry society system, TIBA concentration are 1.0mol/L), three (pentafluorophenyl group) borine, 0.30 μ mol, scandium title complex (1) the 0.10 μ mol of triisobutyl aluminium (following note is made TIBA) therein, carry out 30 minutes polymerization.The polymeric result is every 1mol catalyzer, can prepares molecular weight (Mw)=1,867 in per 1 hour, and 000, the polymkeric substance 1.5 * 10 of the 1-hexene unit content (SCB)=6 in the molecular weight distribution (Mw/Mn)=1.8, multipolymer 6G.
Embodiment 17
Under the nitrogen atmosphere, the toluene 5.0mL that packs in autoclave, 1-hexene 60 μ L after making it stable under 40 ℃, are forced into 0.60MPa with ethene, make it stable.Add hexane solution 40 μ L (Northeast chemistry society system, TIBA concentration are 1.0mol/L), xylidine four (pentafluorophenyl group) borate 0.30 μ mol and scandium title complex (1) the 0.10 μ mol of TIBA therein, carry out 30 minutes polymerization.The polymeric result is every 1mol catalyzer, the polymkeric substance 44.2 * 10 that can prepare the 1-hexene unit content (SCB)=1 in molecular weight (Mw)=144,000, molecular weight distribution (Mw/Mn)=1.8, the multipolymer in per 1 hour 6G.
Embodiment 18
Except the 1-hexene being changed over 50 μ L, polymerization temperature being changed over 70 ℃, other carry out polymerization similarly to Example 17, every 1mol catalyzer, can prepare the polymkeric substance 205.0 * 10 of the 1-hexene unit content (SCB)=30 in molecular weight (Mw)=54,000, molecular weight distribution (Mw/Mn)=1.7, the multipolymer in per 1 hour 6G.
Embodiment 19
Except the 1-hexene being changed over 40 μ L, polymerization temperature being changed over 130 ℃ and the hexane solution of TIBA made into the 4 μ L, other carry out polymerization similarly to Example 17, every 1mol catalyzer, can prepare polymkeric substance 2.7 * 10 in per 1 hour 6G.
Embodiment 20
Under the nitrogen atmosphere, the toluene 5.0mL that packs in autoclave, 1-hexene 60 μ L after making it stable under 40 ℃, are forced into 0.60MPa with ethene, make it stable.Add hexane solution 40 μ L (Northeast chemistry society system, TIBA concentration are 1.0mol/L), trityl group four (pentafluorophenyl group) borate 0.30 μ mol and scandium title complex (1) the 0.10 μ mol of TIBA therein, carry out 30 minutes polymerization.The polymeric result is every 1mol catalyzer, the polymkeric substance 87.6 * 10 that can prepare the 1-hexene unit content (SCB)=5 in molecular weight (Mw)=230,000, molecular weight distribution (Mw/Mn)=1.9, the multipolymer in per 1 hour 6G.
Embodiment 21
Except the 1-hexene being changed over 50 μ L, polymerization temperature being changed over 70 ℃, other carry out polymerization similarly to Example 20, every 1mol catalyzer, can prepare the polymkeric substance 175.3 * 10 of the 1-hexene unit content (SCB)=36 in molecular weight (Mw)=98,000, molecular weight distribution (Mw/Mn)=1.7, the multipolymer in per 1 hour 6G.
Embodiment 22
Except the 1-hexene being changed over 40 μ L, polymerization temperature being changed over 130 ℃ and the hexane solution of TIBA made into the 4 μ L, other carry out polymerization similarly to Example 20, every 1mol catalyzer, can prepare polymkeric substance 1.4 * 10 in per 1 hour 6G.
Embodiment 23
Under the nitrogen atmosphere, the toluene 5.0mL that packs in autoclave, 1-hexene 50 μ L after making it stable under 70 ℃, are forced into 0.60MPa with ethene, make it stable.Add trityl group four (pentafluorophenyl group) borate 0.30 μ mol and scandium title complex (1) 0.10 μ mol therein, carry out 30 minutes polymerization.The polymeric result is every 1mol catalyzer, can prepares molecular weight (Mw)=1,527 in per 1 hour, and 000, the polymkeric substance 14.5 * 10 of the 1-hexene unit content (SCB)=199 in the molecular weight distribution (Mw/Mn)=1.4, multipolymer 6G.
The preparation of＜Alathon 〉
The scandium title complex (1) that will obtain in embodiment 3 uses the system PPR of Symyx society (48 connect autoclave) to utilize following polymerizing condition to carry out the homopolymerization of ethene as the catalyst for olefines polymerizing composition.
Embodiment 24
Under the nitrogen atmosphere, the toluene 5.0mL that packs in autoclave after making it stable under 40 ℃, is forced into 0.60MPa with ethene, makes it stable.Add aikyiaiurnirsoxan beta (eastern ソ-Off ア イ Application ケ system society system MMAO, 5.8 weight % Al) 100 μ mol (Al atom scaled value), scandium title complex (1) 0.10 μ mol therein, carry out 30 minutes polymerization.The polymeric result is every 1mol catalyzer, can prepares polymkeric substance 1.3 * 10 in per 1 hour 5G.
Embodiment 25
Except hexane solution 40 μ L (Northeast chemistry society system, TIBA concentration are 1.0mol/L), three (pentafluorophenyl group) borine, the 0.30 μ mol that uses TIBA replaced methylaluminoxane, other carried out polymerization similarly to Example 24.The polymeric result is every 1mol catalyzer, can prepares polymkeric substance 1.1 * 10 in per 1 hour 5G.
Embodiment 26
Except hexane solution 40 μ L (Northeast chemistry society system, TIBA concentration are 1.0mol/L), xylidine four (pentafluorophenyl group) the borate 0.30 μ mol that uses TIBA replaced methylaluminoxane, other carried out polymerization similarly to Example 24.The polymeric result is every 1mol catalyzer, can prepares polymkeric substance 24.2 * 10 in per 1 hour 6G.
Embodiment 27
Except hexane solution 40 μ L (Northeast chemistry society system, TIBA concentration are 1.0mol/L), trityl group four (pentafluorophenyl group) the borate 0.30 μ mol that uses TIBA replaced methylaluminoxane, other carried out polymerization similarly to Example 24.The polymeric result is every 1mol catalyzer, can prepares polymkeric substance 30.3 * 10 in per 1 hour 6G.
Embodiment 28
Except use trityl group four (pentafluorophenyl group) borate 0.30 μ mol replaced methylaluminoxane, other carried out polymerization similarly to Example 24.The polymeric result is every 1mol catalyzer, can prepares polymkeric substance 9.0 * 10 in per 1 hour 5G.
The lutetium title complex (1) that will obtain in embodiment 4 uses the system PPR of Symyx society (48 connect autoclave) to utilize following polymerizing condition to carry out the copolymerization of ethene and 1-hexene as the catalyst for olefines polymerizing composition.
Embodiment 29
Under the nitrogen atmosphere, the toluene 5.0mL that packs in autoclave, 1-hexene 50 μ L after making it stable under 70 ℃, are forced into 0.60MPa with ethene, make it stable.Add hexane solution 40 μ L (Northeast chemistry society system, TIBA concentration 1.0mol/L), xylidine four (pentafluorophenyl group) borate 0.30 μ mol and lutetium title complex (1) the 0.10 μ mol of TIBA therein, carry out 30 minutes polymerization.The polymeric result is every 1mol catalyzer, the polymkeric substance 1.6 * 10 that can prepare the 1-hexene unit content (SCB)=49 in molecular weight (Mw)=508,000, molecular weight distribution (Mw/Mn)=22.7, the multipolymer in per 1 hour 6G.
The preparation method of＜polar monomer polymkeric substance 〉
The preparation method of＜lactone polymer 〉
The mensuration of molecular weight and molecular weight distribution is carried out with following method by gel permeation chromatography (GPC).
Device: HLC-8120GPC (RI)
Pillar: TSKgel, GMHHR-M
Flow: 0.5mL/min
Measure temperature: 40 ℃
Moving phase: THF
Reference material: polystyrene
Embodiment 30
Under the nitrogen atmosphere, Yi Bian at room temperature use magnetic stirring apparatus vigorous stirring 6-caprolactone (2.87g, 25.2mmol), Yi Bian once add all toluene solutions (2mL) of the scandium title complex (2) (37.6mg, 0.063mmol) of amount.Added methyl alcohol (100mL) in back 1 minute in interpolation, stop polymerization, utilize and filter the white solid that collects.By carrying out vacuum-drying, obtain polycaprolactone (2.84g, yield 99%) at 60 ℃.Measure the weight-average molecular weight Mw=56700 of polystyrene conversion, molecular weight distribution mw/mn=1.39 by the polycaprolactone that obtains being carried out GPC.
Embodiment 31
Under the nitrogen atmosphere, Yi Bian at room temperature use magnetic stirring apparatus vigorous stirring 6-caprolactone (5.75g, 50.4mmol), Yi Bian once add all toluene solutions (4mL) of the scandium title complex (2) (38.5mg, 0.065mmol) of amount.Added methyl alcohol (100mL) in back 3 minutes in interpolation, stop polymerization, utilize and filter the white solid that collects.By carrying out vacuum-drying, obtain polycaprolactone (5.04g, yield 88%) at 60 ℃.Measure the weight-average molecular weight Mw=113000 of polystyrene conversion, molecular weight distribution mw/mn=1.58 by the polycaprolactone that obtains being carried out GPC.
Embodiment 32
Under the nitrogen atmosphere, Yi Bian at room temperature use magnetic stirring apparatus vigorous stirring 6-caprolactone (2.88g, 25.2mmol), Yi Bian once add all toluene solutions (2mL) of the scandium title complex (1) (43.9mg, 0.063mmol) of amount.Added methyl alcohol (100mL) in back 1 minute in interpolation, stop polymerization, utilize and filter the white solid that collects.By carrying out vacuum-drying, obtain polycaprolactone (2.73g, yield 95%) at 60 ℃.Measure weight-average molecular weight Mw=49400, molecular weight distribution mw/mn=1.77 by the polycaprolactone that obtains being carried out GPC.
Embodiment 33
Under the nitrogen atmosphere, Yi Bian at room temperature use magnetic stirring apparatus vigorous stirring 6-caprolactone (2.87g, 25.2mmol), Yi Bian once add all toluene solutions (2mL) of the yttrium complex (1) (41.0mg, 0.064mmol) of amount.Added methyl alcohol (100mL) in back 15 seconds in interpolation, stop polymerization, utilize and filter the white solid that collects.By carrying out vacuum-drying, obtain polycaprolactone (2.79g, yield 97%) at 60 ℃.Measure the weight-average molecular weight Mw=41900 of polystyrene conversion, molecular weight distribution mw/mn=1.88 by the polycaprolactone that obtains being carried out GPC.
Embodiment 34
Under the nitrogen atmosphere, Yi Bian at room temperature use magnetic stirring apparatus vigorous stirring 6-caprolactone (2.88g, 25.2mmol), Yi Bian once add all toluene solutions (2mL) of the lutetium title complex (2) (45.8mg, 0.063mmol) of amount.Added methyl alcohol (100mL) in back 10 seconds in interpolation, stop polymerization, utilize and filter the white solid that collects.By carrying out vacuum-drying, obtain polycaprolactone (2.79g, yield 97%) at 60 ℃.Measure the weight-average molecular weight Mw=57700 of polystyrene conversion, molecular weight distribution mw/mn=2.23 by the polycaprolactone that obtains being carried out GPC.
The preparation method of＜alkylene oxide polymer 〉
The mensuration of molecular weight and molecular weight distribution is carried out with following method by gel permeation chromatography (GPC).
Device: HLC-8120GPC (RI)
Pillar: TSKgel, GMH HR-M
Flow: 0.5mL/min
Measure temperature: 40 ℃
Moving phase: THF
Reference material: polystyrene
The polymerization of cyclohexene oxide
Embodiment 35
Under the nitrogen atmosphere, Yi Bian at room temperature stir cyclohexene oxide (2.47g, 25.20mmol), Yi Bian add scandium title complex (2) (44.3mg, 0.06mmol), initiated polymerization.At room temperature carry out 30 minutes polymerization, add methyl alcohol (100mL) and stop polymerization, filter and obtain polymkeric substance.Carry out vacuum-drying (50 ℃, 3 hours) by the polymkeric substance that will obtain and obtain poly-(cyclohexene oxide) (1.64g, yield 66%) as white solid.Poly-(cyclohexene oxide) of gained be with weight-average molecular weight Mw=495 of polystyrene conversion, and 000, molecular weight distribution mw/mn=2.06.
Embodiment 36
Under the nitrogen atmosphere, Yi Bian at room temperature stir cyclohexene oxide (2.47g, 25.20mmol), Yi Bian once add all catalyst solutions that dissolving scandium title complex (2) (37.6mg, 0.06mmol) forms in toluene (2mL) of amount, initiated polymerization.At room temperature carry out 6 hours polymerization, add methyl alcohol (100mL) and stop polymerization, filter and obtain polymkeric substance.Carry out vacuum-drying (60 ℃, 3 hours) by the polymkeric substance that will obtain and obtain poly-(cyclohexene oxide) (0.34g, yield 14%) as white solid.Poly-(cyclohexene oxide) of gained be with weight-average molecular weight Mw=436 of polystyrene conversion, and 000, molecular weight distribution mw/mn=2.01.
Embodiment 37
Under the nitrogen atmosphere, Yi Bian at room temperature stir cyclohexene oxide (2.47g, 25.20mmol), Yi Bian once add all catalyst solutions that dissolving scandium title complex (1) (37.6mg, 0.06mmol) forms in toluene (2mL) of amount, initiated polymerization.At room temperature carry out 6 hours polymerization, add methyl alcohol (100mL) and stop polymerization, filter and obtain polymkeric substance.Carry out vacuum-drying (60 ℃, 3 hours) by the polymkeric substance that will obtain and obtain poly-(cyclohexene oxide) (0.21g, yield 9%) as white solid.Poly-(cyclohexene oxide) of gained be with weight-average molecular weight Mw=207 of polystyrene conversion, and 000, molecular weight distribution mw/mn=1.54.
The preparation method of＜(methyl) acrylic ester polymer 〉
The mensuration of stereospecific by proton NMR spectrum figure ( 1H-NMR) (for example Organometallics 2007,26,187-195) carry out according to known document.
Device: NEC society system EX270 or, the system DPX-300 of Bruker society
Sample pool: 5mm φ pipe
Measure solvent: CDCl 3
Sample concentration: 30mg/0.5mL (CDCl 3)
Measure temperature: room temperature (about 25 ℃)
Location parameter: 5mm φ probe, MENUFNON, OBNUC 1H, integral number of times 16 times
Pulse angle: 45 degree
Repetition time: ACQTM 3 seconds, PD 4 seconds
Internal standard: CDCl 3(7.26ppm)
Embodiment 38
" Polymerization of Methyl "
Under the nitrogen atmosphere, Yi Bian at room temperature stir methyl methacrylate (2.52g, 25.20mmol), Yi Bian once add all catalyst solutions that dissolving scandium title complex (2) (37.6mg, 0.06mmol) forms in toluene (2mL) of amount, initiated polymerization.At room temperature carry out 6 hours polymerization, add methyl alcohol (100mL) and stop polymerization, filter and obtain polymkeric substance.Carry out vacuum-drying (80 ℃, 3 hours) by the polymkeric substance that will obtain and obtain poly-(methyl methacrylate) (0.26g, yield 11%) as white solid.Poly-(methyl methacrylate) of gained be with weight-average molecular weight Mw=72 of polystyrene conversion, and 800, molecular weight distribution mw/mn=2.13, stereospecific rr/mr/mm=73.0/22.8/4.2.

Claims (12)

1. rare earth metal complex, it is with formula (1) expression,
Formula (1):
Figure A200780025806C00021
In the formula,
A represents the 14th family's element of the periodic table of elements,
Cp represents to have the group that replaces or do not have the cyclopentadienyl type anion frame of replacement, and Ln represents the 3rd family's atoms metal or lanthanide series metal atom,
R 1, R 2, R 3, R 4, R 5And R 6Identical or different, expression hydrogen atom, halogen atom, carbonatoms are that 1～20 alkyl, carbonatoms are that 6～20 aryl, carbonatoms are 7～20 aralkyl, are that silyl, carbonatoms that 1～20 alkyl replaces are that 1～20 alkoxyl group, carbonatoms are 6～20 aryloxy, are that 7～20 aralkoxy or carbonatoms are the amino of 1～20 alkyl replacement with carbonatoms with carbonatoms
R 7The expression carbonatoms is that 1～20 alkyl, carbonatoms are that 6～20 aryl, carbonatoms are 7～20 aralkyl,
Wherein, at R 1～R 7In, alkyl, aryl, aralkyl, alkoxyl group, aryloxy, aralkoxy or alkyl also can replace with halogen atom,
R 1With R 2Also can in conjunction with and form ring,
R 3, R 4, R 5And R 6In abutting connection with group also can distinguish at random in conjunction with and form ring,
M X is identical or different, expression single anion part,
N Y is identical or different, the expression neutral ligand,
M represents 1～3 integer,
N represents 0～3 integer.
2. rare earth metal complex as claimed in claim 1, wherein, A is a Siliciumatom.
3. as claim 1 or 2 described rare earth metal complexes, wherein, Ln is scandium, yttrium, terbium, dysprosium, holmium, erbium, thulium or lutetium.
4. the preparation method of rare earth metal complex as claimed in claim 1 is characterized in that, make the replacement shown in the formula (2) or do not have the cyclopentadiene compound of replacement and the rare earth metal compound shown in the formula (3) reacts and prepares,
Formula (2):
Figure A200780025806C00031
In the formula, A, Cp, R 1, R 2, R 3, R 4, R 5, R 6And R 7Expression is described equivalent in meaning with claim 1,
Formula (3):
Figure A200780025806C00032
In the formula, Ln, X, Y, m and n represent with claim 1 described equivalent in meaning, R 8Represent the alkyl that also available silyl replaces, described silyl carbonatoms is 1～20 alkyl replacement, perhaps represents the also aralkyl of available amino end replacement, and described amino is 1～20 alkyl replacement with carbonatoms.
5. the catalyst for olefines polymerizing composition is characterized in that, contains rare earth metal complex as claimed in claim 1.
6. catalyst for olefines polymerizing, it makes catalyst for olefines polymerizing composition as claimed in claim 5 contact and get with being selected from least a kind the compound of following aluminum compound (A1)～(A3) with following boron compound (B1)～(B3),
Aluminum compound (A):
(A1): with formula (E 1) aAlZ (3-a)The organo-aluminium compound of expression;
(A2): have with formula { Al (E 2)-O-} bThe ring-type aikyiaiurnirsoxan beta of the structure of expression;
(A3): have the formula of using E 3{ Al (E 3)-O-} cAl (E 3) 2The line style aikyiaiurnirsoxan beta of the structure of expression
In the formula, a represents to satisfy the numerical value of 0＜a≤3, and b represents the integer more than 2, and c represents the integer more than 1, E 1, E 2And E 3Represent that respectively carbonatoms is 1～20 alkyl, a plurality of E 1, a plurality of E 2With a plurality of E 3Can be respectively identical, also can be different, and Z represents hydrogen atom or halogen atom, and a plurality of Z can be identical mutually, also can be different,
Boron compound (B):
(B1): use formula BQ 1Q 2Q 3The boron compound of expression;
(B2): use formula G +(BQ 1Q 2Q 3Q 4) -The boron compound of expression;
(B3): with formula (L 1-H) +(BQ 1Q 2Q 3Q 4) -The boron compound of expression
In the formula, B represents the boron atom of the valence state of 3 valencys, Q 1, Q 2, Q 3And Q 4Represent halogen atom, alkyl, halogenation alkyl respectively independently, replace silyl, alkoxyl group or 2 substituted-aminos, G +Represent inorganic or organic positively charged ion, L 1The expression neutral Lewis base.
7. the preparation method of olefin polymer is characterized in that, in the presence of catalyst for olefines polymerizing as claimed in claim 6, alkene is carried out polymerization.
8. the preparation method of ethene-alpha-olefin copolymer is characterized in that, in the presence of catalyst for olefines polymerizing as claimed in claim 6, with ethene and alpha-olefin copolymer.
9. the preparation method of polar monomer polymkeric substance is characterized in that, polar monomer is contacted with the rare earth metal complex with formula (1) expression as claimed in claim 1, carries out polymerization.
10. the preparation method of lactone polymkeric substance is characterized in that, lactone is contacted with the rare earth metal complex with formula (1) expression as claimed in claim 1, carries out ring-opening polymerization.
11. the preparation method of alkylene oxides polymkeric substance is characterized in that, alkylene oxides is contacted with the rare earth metal complex with formula (1) expression as claimed in claim 1, carries out ring-opening polymerization.
12. the preparation method of acrylic ester polymer or methacrylate polymers is characterized in that, acrylate or methacrylic ester are contacted with the rare earth metal complex with formula (1) expression as claimed in claim 1, carries out polymerization.
CNA2007800258064A 2006-07-07 2007-07-05 Rare earth metal complex, polymerization catalyst and method for producing polymer Pending CN101490069A (en)

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Cited By (5)

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CN102153701A (en) * 2011-01-24 2011-08-17 宁波工程学院 Catalyst for ternary polymerization of norbornene, acrylate and cyclohexene and preparation method thereof and ternary polymerization method
CN110372813A (en) * 2019-08-19 2019-10-25 迈瑞尔实验设备（上海）有限公司 A kind of carbon monoxide-olefin polymeric and its application preparing polyethylene wax for catalyzed ethylene polymerization
CN112250783A (en) * 2020-10-23 2021-01-22 中国科学院长春应用化学研究所 Copolymer of alpha-olefin and 2, 3-dimethyl-1, 3-butadiene, preparation method thereof and rare earth metal complex
CN113968884A (en) * 2021-10-26 2022-01-25 大连理工大学 Novel diphosphamide rare earth metal complex, preparation method and catalytic polymerization application
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102153701A (en) * 2011-01-24 2011-08-17 宁波工程学院 Catalyst for ternary polymerization of norbornene, acrylate and cyclohexene and preparation method thereof and ternary polymerization method
CN102153701B (en) * 2011-01-24 2013-07-10 宁波工程学院 Catalyst for ternary polymerization of norbornene, acrylate and cyclohexene and preparation method thereof and ternary polymerization method
CN110372813A (en) * 2019-08-19 2019-10-25 迈瑞尔实验设备（上海）有限公司 A kind of carbon monoxide-olefin polymeric and its application preparing polyethylene wax for catalyzed ethylene polymerization
CN112250783A (en) * 2020-10-23 2021-01-22 中国科学院长春应用化学研究所 Copolymer of alpha-olefin and 2, 3-dimethyl-1, 3-butadiene, preparation method thereof and rare earth metal complex
CN113968884A (en) * 2021-10-26 2022-01-25 大连理工大学 Novel diphosphamide rare earth metal complex, preparation method and catalytic polymerization application
CN113968884B (en) * 2021-10-26 2022-07-19 大连理工大学 Novel diphosphamide rare earth metal complex, preparation method and catalytic polymerization application
CN115232288A (en) * 2022-08-07 2022-10-25 苏州大学 X-ray-proof rare earth modified ferrocenyl polyurethane and preparation method thereof
CN115232288B (en) * 2022-08-07 2023-07-04 苏州大学 X-ray-resistant rare earth modified ferrocenyl polyurethane and preparation method thereof

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