CN1258292A - Olefin polymerization catalysts contg. group 8-10 transition metals, bidentate ligands, processes employing such catalysts and polymers obtained therefrom - Google Patents
Olefin polymerization catalysts contg. group 8-10 transition metals, bidentate ligands, processes employing such catalysts and polymers obtained therefrom Download PDFInfo
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- CN1258292A CN1258292A CN 98804802 CN98804802A CN1258292A CN 1258292 A CN1258292 A CN 1258292A CN 98804802 CN98804802 CN 98804802 CN 98804802 A CN98804802 A CN 98804802A CN 1258292 A CN1258292 A CN 1258292A
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Abstract
Methods for preparing olefin polymers, and catalysts for preparing olefin polymers are disclosed. The polymers can be prepared by contacting the corresponding monomers with a Group 8-10 transition metal catalyst and a solid support. The polymers are suitable for processing in conventional extrusion processes, and can be formed into high barrier sheets or films, or low molecular weight resins for use in synthetic waxes in wax coatings or as emulsions.
Description
The mutual reference of related application
The application requires the rights and interests of following patent application under 35U.S.C. § 119 (e): No. 60/059372 provisional application that No. 60/044691 provisional application that No. 60/043406 provisional application that No. 60/042925 provisional application that No. 60/041542 provisional application that No. 60/039945 provisional application that on March 10th, 1997 proposed, on March 25th, 1997 propose, on April 4th, 1997 propose, on April 4th, 1997 propose, on April 18th, 1997 propose and on September 18th, 1997 propose.
Invention field
The present invention relates to contain the 8-10 group 4 transition metal title complex, its in olefinic polymerization purposes and by the new olefin polymer of its generation.
Background of invention
Olefin polymer is used to the various product from the electric wire and cable sheath to film.Olefin polymer be used to for example injection moulding or compression moulding use in, be used for as the paper for example extruded film or the extrudate piece of the extruding veneer on printing paper and the digital recording paper etc.The improvement of catalyzer is controlled polymerization process and therefore influence the performance of bulk article better.Physical properties such as the luminance brightness, intensity, erosion resistance, perviousness, optical property etc. of having made constantly to make great efforts to improve plastics are to be fit to concrete purposes.Chain length, polymkeric substance branch and functionality have remarkably influenced to the physical properties of polymkeric substance.Therefore, always seek to obtain to control more effective and better the catalysis process that is used for olefinic polymerization of olefin polymerization process in the raw catalyst research.
Conventional polyolefine comprises homogeneous liquid phase, gas phase and slurry polymerization by various polymerization process preparations.Some transition-metal catalyst such as those be used in combination with the organoaluminum promotor based on titanium compound (TiCl for example
3Or TiCl
4) catalyzer be used to the linear and linear low density polyethylene of preparation and poly-alpha olefins such as polypropylene.These so-called " Z-N " type catalyzer are very responsive and to nonpolar and copolymerization polar monomer is invalid to oxygen.
Comprise following content in the new development aspect the non-Ziegler-Natta type olefin polymerization catalysis.
People such as L.K.Johnson disclose to use in International Patent Application WO 96/23010 and have contained diimine with the olefinic polymerization that positively charged ion nickel, palladium, iron and the cobalt complex of bisoxazoline ligand carry out.The document has also been described cycloolefin and the optional unsaturated acid or homopolymer or the multipolymer of polymerization so that alkene to be provided of ester such as vinylformic acid or alkyl acrylate of ethene, vinylformic acid alkene and/or selection.
European patent application series discloses for No. 381495 uses the palladium of the phosphorous bidentate ligand that comprises selection and the olefinic polymerization that nickel catalyzator carries out.
People such as L.K.Johnson are in nineteen ninety-five, and 117 volumes have been described the nickel and the palladium complex that use cationic alpha-diimine base and carried out the polymerization of alkene such as ethene, propylene and 1-hexene among 6414 pages the J.Am.Chem.Soc..These catalyzer are illustrated and are used for vinyl polymerization is become high molecular weight branched polyethylene.Except ethene, the Pd title complex is as the catalyzer of alkene and methyl acrylate polymerization and copolymerization.
People such as G.F.Schmidt were in 1985, and 107 roll up, and described among 1443 pages the J.Am.Chem.Soc. to have structure [C
5Me
5(L) CoCH
2CH
2-μ-H]
+Cobalt (III) cyclopentadienyl catalyst system, it provides " activity " polymerization of ethene.
People such as M.Brookhart are in nineteen ninety-five, and 28 volumes disclose synthetic middle this " activity " catalyzer that uses of functional polyethylene homopolymer endways among 5378 pages the Macromolecules.
The United States Patent (USP) 4906754,4716205,5030606 and 5175326 of U.Klabunde has been described to use with Ni (II) coordinate negatively charged ion phosphorus, oxygen and to body ethene has been transformed into polyethylene.This polyreaction is carried out under 25-100 ℃ temperature with moderate yield, produces to have the linear polyethylene of 8K to weight-average molecular weight between the 350K.In addition, Klabunde has described ethene and the preparation that contains functional group monomer's multipolymer.
People such as M.Peuckert are in nineteen eighty-three, the 2nd the 5th phase of volume, disclose among 594 pages the Organomet. and have used the oligomeric of the ethene that carries out to body with Ni (II) coordinate phosphine, carboxylicesters that demonstrates the most moderate catalytic activity (0.14-1.83 TO/s).This oligomeric at 60-95 ℃ temperature and 10-80 crust ethylene pressure under in toluene, carry out, be used to prepare linear alpha-alkene.
The United States Patent (USP) 4689437 and 4716138 of R.E.Murray has been introduced and has been used the oligomeric of the ethene that carries out to body with Ni (II) coordinate phosphine, sulphonate.These title complexs demonstrate approximately than with phosphine, catalytic activity that the carboxylicesters analogue is big 15 times.
People such as people such as W.Keim and V.M.Mohring are respectively in 1981,20 volumes, 116 pages and 1985,24 volumes, 1001 pages Angew.Chem.Int.Ed.Eng. disclose the oligomeric of the polymerization of using the ethene that amino two (imino-) phosphorane nickel catalyzators carry out and alpha-olefin; G.Wilke was in 1988, and 27 roll up, and 185 pages Angew.Chem.Int.Ed.Eng has described the nickel allyl group phosphine composition that is used for vinyl polymerization.
People such as K.A.O.Starzewski are in 1987, have described a series of two (inner salt) nickel complexes that are used for vinyl polymerization is become high molecular weight linear polyethylene in 26 volumes, 63 pages Angew.Chem.Int.Ed.Eng. and United States Patent (USP) 4691036.
International Patent Application WO 97/02298 discloses the olefinic polymerization that various neutral N, O, P or S that use nickel (O) compound and a kind of acid is used in combination carry out for the body ligand.
People's such as Brown WO 97/17380 has described the purposes in Pd alpha-diimine catalyzer comprises ethene in the presence of air and moisture the olefinic polymerization.
People's such as Fink United States Patent (USP) 4724273 has been described the composition that uses amino two (imino-) phosphorane nickel catalyzator alpha-olefine polymerizing that carries out and poly-(alpha-olefin) that obtain.
Other new development is described in JP 96-84344, JP 96-84343 and WO 9738024 by people such as Sugimura and is described among the JP 96-70332 by people such as Yorisue.
Although, still have needs to efficient, the practical 8-10 group 4 transition metal catalyzer that carries out olefinic polymerization in that these progress are arranged aspect the non-Ziegler-natta catalyst.In addition, also there are needs to the novel method of the olefinic polymerization of using this efficient 8-10 group 4 transition metal catalyzer.Specifically, still there are needs to the 8-10 group 4 transition metal olefin polymerization catalysis of temperature stability with improvement and functional group's compatibleness.Also have, still exist the needs of use with the olefine polymerizing process of the efficient 8-10 group 4 transition metal of a kind of Lewis acid bonded catalyzer (combine the Lewis acid use and can obtain more high reactivity and optionally catalyzer).
The present invention's general introduction
The present invention relates to new 8-10 group 4 transition metal catalyzer, relate to and use the olefinic polymerization that these catalyzer carry out in batches or continuously and relate to polymkeric substance prepared therefrom.
The inventive method comprises the olefinic monomer with one or more formulas LI:
RCH＝CHR
8 LI
R and R in the formula
8Each is represented hydrogen, alkyl or fluoro-alkyl independently and can be connected to form a kind of cycloolefin; With a kind of coordination a kind of 8-10 group 4 transition metal with bidentate ligand of formula X:
R in the formula
1And R
6Each is alkyl, substituted hydrocarbon radical or silyl independently, preferable space sterically hindered aryl;
Each is a separate base that heteroatoms is connected independently for A and B, and wherein the heteroatoms that is connected is selected from 15 or 16 families, is preferably N, O and S, and wherein A can be connected by an abutment with B; And choose any one kind of them Bronsted acid or Lewis acid contact; And carry out polymerization so that obtain a kind of polymkeric substance that comprises aforementioned olefin monomer unit.
In addition, the inventive method comprises that the monomer with one or more aforementioned formula LI contacts with a kind of catalyzer of the present invention with following formula XI:
R in the formula
1, R
6, identical in A and B and the top formula (X);
T represents a hydrogen or an alkyl;
L represents a kind of monoolefine or a kind of neutral Lewis base, and wherein the coordinate atom is nitrogen, oxygen or sulphur;
M represents the transition metal of a 8-10 family, preferred Ni (II), Pd (II), Co (II) or Fe (II), more preferably Ni (II) or Pd (II);
X
-It is a weak coordinate negatively charged ion; And carry out polymerization to obtain to comprise the polymkeric substance of aforementioned olefin monomer unit.
Also have, the inventive method comprises that the olefinic monomer with formula LI contacts with a kind of catalyzer of the present invention, and described catalyzer passes through the compound with a kind of formula (XII):
Combine and form with a kind of compound Y, described compound Y is selected from and can captures Q
-Or W
-And form a kind of weak anionic neutral lewis acid of coordinate, a kind of its gegenion is that a kind of weak anionic positively charged ion Lewis acid of coordinate or a kind of its conjugate base are a kind of weak anionic Bronsted acid of coordinate; With
R wherein
1, R
6, identical in A and B and the top formula (X);
Q represents alkyl, chlorine, iodine or a bromine;
W represents alkyl, chlorine, iodine or a bromine;
M represents the transition metal of a 8-10 of family, preferred Ni (II), Pd (II), Co (II) or Fe (II); And carry out polymerization to obtain to comprise the polymkeric substance of aforementioned olefin monomer unit.
The catalyzer that is used for the inventive method be easy to ethene and alpha-olefin be transformed into high-molecular weight polymer and can be under various conditions (comprise envrionment temperature and pressure and in solution) carry out olefinic polymerization.
Polymkeric substance of the present invention comprises that the homopolymer of alkene comprises the multipolymer that contains the functional group such as polyethylene, polypropylene etc. with olefin copolymer.For example, can by change catalyst structure, promotor is formed and the Alathon of reaction conditions (comprising pressure and temperature) preparation from the linear structure of strictness to hyperbranched structure.This paper has described the influence of these parameters to polymer architecture.These polymkeric substance and multipolymer have the purposes of wide region, comprise as wrapping material with as tackiness agent.
Therefore, a target of the present invention provides the raw catalyst of energy olefin polymerization (comprise and contain functional group's alkene).
Another target of the present invention is the catalyst system that proposes to be used for olefinic polymerization.
Another target of the present invention is the olefinic polymerization of explanation under mild conditions.
Also target of the present invention provides the raw catalyst and the method for homogeneous phase olefin catalytic.
Another target more of the present invention provides new polyolefine.
Of the present invention again and a target is the method that explanation change catalyst structure and polymeric reaction condition change the polyolefinic structure of formation.
By reference following detailed description and embodiment preferred, these and other target of the present invention, feature and advantage all become apparent.
Detailed description of the present invention
In the disclosure, some chemical group or compound are by some term and symbolic representation.These term definitions are as follows:
Unless add explanation in addition, the symbol that just is being usually used in element in the representative element periodictable has its normal meaning.Therefore N, O, S, P and Si represent nitrogen, oxygen, sulphur, phosphorus and silicon respectively.
The example of neutral lewis acid includes but not limited to methylaluminoxane (hereinafter being abbreviated as MAO) and other aluminum sesquioxide, R
7 3Al, R
7 2AlCl, R
7AlCl
2(R here
7Be alkyl), organoboron compound, halogenation boron, B (C
6F
5)
3, BPh
3And B (3,5-(CF
3) C
6H
3)
3The example that comprises the lewis acidic ionic compound of positively charged ion comprises: R
9 3Sn[BF
4] (R here
9Be alkyl), MgCl
2And H
+X
-(X here
-Be a kind of weakly coordinating anion).
The example of neutral Lewis base includes but not limited to (i) ether, for example ether or tetrahydrofuran (THF), (ii) organic nitrile acetonitrile for example, (iii) organic thioether, dimethyl thioether for example, or (iv) monoolefine, for example ethene, hexene or cyclopentenes.
" alkyl " is meant monovalence or divalence, linearity, branch or the cyclic group of a carbon atoms and hydrogen atom.The example of monovalence alkyl comprises: C
1-C
20Alkyl; By one or more C that are selected from
1-C
20Alkyl, C
3-C
8The C that the group of cycloalkyl or aryl replaces
1-C
20Alkyl; By one or more C that are selected from
1-C
20Alkyl, C
3-C
8The C that the group of cycloalkyl or aryl replaces
3-C
8Cycloalkyl; C
6-C
14Aryl; By one or more C that are selected from
1-C
20Alkyl, C
3-C
8The C that the group of cycloalkyl or aryl replaces
6-C
14Aryl; The term here " aryl " preferably is meant phenyl, naphthyl or anthryl.The example of divalence (bridging) alkyl comprises :-CH
2-,-CH
2CH
2-,-CH
2CH
2CH
2-and 1, the 2-phenylene.
" silyl " is meant SiR
3Group, wherein Si is a silicon, R is alkyl or substituted hydrocarbon radical or silyl as at Si (SiR
3)
3In.
" heteroatoms " is meant the atom that is not carbon or hydrogen.Preferred heteroatoms comprises oxygen, nitrogen, phosphorus, sulphur, selenium, arsenic, chlorine, bromine, silicon and fluorine.
" substituted hydrocarbon radical " is meant monovalence or the bivalent hydrocarbon radical that is replaced by one or more heteroatomss.The example of monovalence substituted hydrocarbon radical comprises: 2,6-dimethyl-4-p-methoxy-phenyl, 2,6-di-isopropyl-4-p-methoxy-phenyl, 4-cyano group-2, the 6-3,5-dimethylphenyl, 2,6-dimethyl-4-nitrophenyl, 2, the 6-difluorophenyl, 2, the 6-dibromo phenyl, 2, the 6-dichlorophenyl, 4-methoxycarbonyl-2, the 6-3,5-dimethylphenyl, the 2-tertiary butyl-6-chloro-phenyl-, 2,6-dimethyl-4-benzene sulfonyl phenyl, 2,6-dimethyl-4-trifluoromethyl, 2,6-dimethyl-4-TMA (TriMethylAmine) phenyl (being combined with a kind of weakly coordinating anion), 2,6-dimethyl-4-hydroxy phenyl, hydroxy-anthracene-9-10-base, 2-chloronaphthalene-1-base, the 4-p-methoxy-phenyl, the 4-nitrophenyl, 9-nitroanthracene-10-base, CH
2OCH
3, cyano group, trifluoromethyl or fluoroalkyl.The example of divalence (bridging) substituted hydrocarbon radical comprises: 4-methoxyl group-1,2-phenylene, 1-methoxymethyl-1,2-ethane two bases, 1, two (benzyloxymethyl)-1 of 2-, 2-ethane two bases or 1-(4-p-methoxy-phenyl)-1,2-ethane two bases.
" sterically hindered aryl " is meant that (i) has the substituent phenyl ring of alkyl, substituted hydrocarbon radical, F, Cl, Br or silyl on two positions of 2-and 6-position, choose wantonly in other position by alkyl, substituted hydrocarbon radical, F, Cl, Br, silyl, hydroxyl, methoxyl group, nitro, cyano group, benzenesulfonyl, CO
2Me, CO
2H, C (O) CH
3, CF
3Or the replacement of fluoroalkyl substituting group, (ii) naphthalene-1-the basic ring of 2-replacement is chosen other position wantonly by alkyl, substituted hydrocarbon radical, F, Cl, Br, silyl, hydroxyl, methoxyl group, nitro, cyano group, benzenesulfonyl, CO
2Me, CO
2H, C (O) CH
3, CF
3Or the replacement of fluoroalkyl substituting group, (iii) 9-anthryl ring is chosen other position quilt wantonly by alkyl, substituted hydrocarbon radical, F, Cl, Br, silyl, hydroxyl, methoxyl group, nitro, cyano group, benzenesulfonyl, CO
2Me, CO
2H, C (O) CH
3, CF
3Or the fluoroalkyl substituting group replaces; or (iv) has on the functionality aromatics substituted hydrocarbon radical that is equivalent to the resistive matter of (in the literary composition of the present invention) one or more following sterically hindered aryl position: 2; the 6-3,5-dimethylphenyl; 2; 4; the 6-trimethylphenyl; 2; the 6-diisopropyl phenyl; 2; 6-dimethyl-4-nitrophenyl; 2; 6-dimethyl-4-benzenesulfonyl phenyl; 2-sec.-propyl-6-aminomethyl phenyl; 2; two (trifluoromethyl) phenyl of 6-; 2; 6-dimethyl-4-p-methoxy-phenyl; 2-methylnaphthalene-1-base; the 9-anthryl; 2, the 6-dichlorophenyl; 2, the 6-dibromo phenyl; the 2-tertiary butyl-6-aminomethyl phenyl; 2-trimethyl silyl naphthalene-1-base; 2-chloro-6-aminomethyl phenyl; 4-cyano group-2; the 6-3,5-dimethylphenyl; 2; 6-di-isopropyl-4-p-methoxy-phenyl; 2,4,6-tri-tert phenyl and 2-chloro-6-tert-butyl-phenyl.
" single group that heteroatoms connects " is meant that heteroatoms is used as single group of tie point.Example comprises NH (2, the 6-3,5-dimethylphenyl) and SPh, and Ph is a phenyl here.Here provide multiple other example.
" Siliciumatom of replacement " is meant-SiR
9 2-group, wherein R
9Be alkyl or substituted hydrocarbon radical.
" phosphorus atom of replacement " is meant-P (O) (OR
9)-group, wherein R
9Be alkyl or substituted hydrocarbon radical.
" sulphur atom of replacement " be meant-S (O)-,-SO
2-or-S (NR
9)
2-group, wherein R
9Be alkyl or substituted hydrocarbon radical.
" bridged group " be meant bivalent hydrocarbon radical, bivalent substituted alkyl ,-C (O)-,-C (S)-, replace Siliciumatom, replace sulphur atom, replace phosphorus atom ,-CH
2C (O)-, C (O) C (O)-or 3,4,5,6-tetrafluoro-1,2-phenylene.
In some cases, described abutment can form the heterocycle that divalent heteroatom replaces jointly with group A and B; Example comprises:
" monoolefine " is meant the hydrocarbon that comprises a carbon-to-carbon double bond.
" metal carrier body that is fit to " is meant 8-10 family metallic compound, preferred Ni, Co, Pd and Fe compound, it can combine a kind of active olefin polymerizing catalyst of formation with compounds X (preferred following compound III, VI, IX, XVII or XVIII) and choose any one kind of them Lewis acid or Bronsted acid.Example comprises: (1, the 2-glycol dimethyl ether) nickel (II) dibromide, two [(μ-chlorine) (1,2,3-η
3-2-propenyl) nickel (II)], two [(μ-chlorine) (1,2,3-η
3-2-propenyl) palladium (II)], two [(μ-chlorine) (1,2,3-η
3-1-TMS oxygen-2-propenyl) nickel (II)], CoBr
2, FeBr
2, two (methyl ethyl diketone) nickel (II) and [four (acetonitrile) palladium (II)] [BF
4].
" the nickel parent that is fit to " is meant that described metal is the metal carrier body that is fit to of nickel.
" nickel (O) parent that is fit to " is meant a kind of metal carrier body that is fit to as the zero-valent nickel compound.
Term " fluoro-alkyl " used in this is meant the C that is replaced by one or more fluorine atoms
1-C
20Alkyl.
Used term " polymer " in this " be meant by monomeric unit and form and have 10 or the material of the higher polymerization degree (DP).
Term " alpha-olefin " used in this is meant the 1-alkene with 3-40 carbon atom.
" π-allyl group " is meant to have three with η
3-form is attached to a sp on the metal center
2The single anion group of carbon atom.Three sp
2Any one of carbon atom all can be replaced by the substituted hydrocarbon radical or the O-silyl-group of the alkyl of alkyl, substituted hydrocarbon radical, heteroatoms connection, heteroatoms connection.The example of π-allyl group comprises:
The structure here is understood that the single anion fragment.
Term π-benzyl group is meant described sp
2Two of carbon atom is the π-allyl group of the part of an aromatic nucleus.The example of π-benzyl group comprises:
The structure here is understood that the single anion fragment.
Term " weakly coordinating anion " itself is well known to those skilled in the art and generally is meant and can make described anionic negative charge delocalized large volume negatively charged ion.The weakly coordinating anion that is suitable for includes but not limited to PF
6 -, BF
4 -, SbF
6 -, (Ph)
4B
-(wherein Ph is a phenyl),
-BAr
4(wherein
-BAr
4=four [3, two (trifluoromethyl) phenyl of 5-] borate.This anionic coordination ability is known and is described in the document (Strauss, people such as S, Chem.Rev.1993,93 volumes, 927 pages).
Alkene or other monomeric compound before used term " monomer " or " olefinic monomer " are meant and are aggregated in this; Term " monomeric unit " is meant that part of of corresponding described polymer of monomers after the polymerization.
In some cases, need be as the compound Y of promotor.Compounds suitable for use Y comprises can capture Q
-Or W
-The Bronsted acid that to form a kind of neutral lewis acid of weakly coordinating anion, positively charged ion Lewis acid that its gegenion is weakly coordinating anion or a kind of its conjugate base be weakly coordinating anion.Preferred compound Y comprises: methylaluminoxane (hereinafter being called MAO) and other aluminum sesquioxide, R
7 3Al, R
7 2AlCl, R
7AlCl
2(R wherein
7Be alkyl), organoboron compound, halogenation boron, B (C
6F
5)
3, R
9 3Sn[BF
4] (R wherein
9Be alkyl), MgCl
2And H
+X
-(X wherein
-Be a kind of weakly coordinating anion).
The example of " solid carrier " comprises inorganic oxide support material such as talcum, silicon-dioxide, titanium dioxide, silicon-dioxide/chromic oxide, silicon-dioxide/chromic oxide/titanium dioxide, silica/alumina, zirconium dioxide, phosphaljel, the silicon-dioxide of silanization, silica hydrogel, silica xerogel, aerosil, silica cogel.
In one embodiment, the invention provides a kind of method in batches or continuously of olefinic polymerization, comprise one or more formulas RCH=CHR
8Compound contact with a kind of catalyzer, described catalyzer comprises (a) a kind of suitable metal carrier body and (b) ligand and optional (c) a kind of Bronsted acid or the Lewis acid of a kind of formula X,
Wherein R and R
8Each represents a hydrogen, alkyl or fluoro-alkyl independently, and can be in conjunction with forming cycloolefin;
R
1And R
6Each is alkyl, substituted hydrocarbon radical or silyl independently, is preferably sterically hindered aryl; N represents nitrogen;
Respectively being one independently is connected heteroatomic single group for A and B, and the heteroatoms of wherein said connection is selected from the 15th or 16 families; In addition, A can link to each other by an abutment with B.
In another aspect of this invention, provide a kind of composition, it comprises (a) 8-10 group 4 transition metal M, (b) one or more Lewis acids and (c) double-coreization or the multinucleation compound of formula X:
Wherein said Lewis acid combines with one or more heteroatomss, and this heteroatoms is pi-conjugated with the described donor atom that is attached on the described transition metal M;
R
1And R
6Each is alkyl, substituted hydrocarbon radical or silyl independently, is preferably sterically hindered aryl;
N represents nitrogen;
Respectively being one independently is connected heteroatomic single group for A and B, and the heteroatoms of wherein said connection is selected from the 15th or 16 families; In addition, A can link to each other by an abutment with B.
Preferred 8-10 group 4 transition metal is Ni, Pd, Fe and Co, more preferably Ni and Pd.
Preferred ligand X is as follows:
R wherein
1And R
6Definition with top identical;
R
2, R
3, R
4And R
5Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently; In addition, R
2, R
3, R
4Or R
5Any two can form an abutment jointly, prerequisite is for when described ligand is the ligand of formula VI or IX, described abutment is not the sulphur atom of a replacement or the phosphorus atom of replacement;
The synthetic general modification of the ligand of formula X, and explanation in detail in the following embodiments based on preceding method.
Coordination above the 8-10 group 4 transition metal complexes of bidentate ligand X also can be according to for example described title complex is active catalyst, its precursor, or described title complex is other state of catalyzer and the one or more other ligands of coordination.
In a preferred embodiment of the inventive method, the olefinic monomer of one or more aforementioned formula LI is contacted with following material:
(i) a kind of suitable nickel (O) parent is preferably two (1, the 5-cyclooctadiene) nickel (O) compounds;
(ii) a kind of its conjugate base is the Bronsted acid of weakly coordinating anion; With
The (iii) compound of a kind of aforementioned formula X is preferably the compound of a kind of above-mentioned formula III, VI, IX, XVII or XVIII; And carry out described polymerization to obtain to comprise the unitary polymkeric substance of aforementioned olefinic monomer.
In the another kind of preferred embodiment of the inventive method, the method in batches or continuously of olefinic polymerization is provided, comprise one or more formulas RCH=CHR
8Monomer contact with the catalyzer of a kind of formula XI:
Wherein R and R
8Each represents hydrogen, alkyl or fluorinated alkyl independently, and can be connected to form cycloolefin;
R
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently, preferable space sterically hindered aryl;
A and B are respectively independently for being connected heteroatomic single group, and the heteroatoms of wherein said connection is selected from the 15th or 16 families; In addition, A can be connected by abutment with B;
T represents hydrogen or alkyl;
L represents monoolefine or neutral Lewis base, and wherein said ligating atom is nitrogen, oxygen or sulphur;
M represents Ni (II), Pd (II), Co (II) or Fe (II), preferred Ni (II) or Pd (II);
N represents nitrogen; With
X
-Be a kind of weakly coordinating anion.
In a preferred embodiment, compounds X I is selected from following various compound:
R wherein
1, R
2, R
3, R
4, R
5, R
6, T, L and M meaning with top identical.
When polymer chain that increases when T representative and L are a kind of monoolefine, can be regarded as top various representative chainpropagation material.T and L can represent together one with M coordination and below formula in by the π-allyl group or the π-benzyl title complex of symbol G representative.Like this, in another embodiment preferred of the inventive method, at least a olefinic monomer LI contacts with a kind of catalyzer that is selected from following formula:
R wherein
1-R
6And X
-With top same meaning;
G is a π-allyl group or π-benzyl;
M is a kind of 8-10 group 4 transition metal, preferred Pd (II), Ni (II), Fe (II) or Co (II), more preferably Ni (II) or Pd (II);
And carry out described polymerization to obtain to comprise the unitary polymkeric substance of aforementioned olefinic monomer.
Another one embodiment of the present invention provides a kind of method in batches or continuously of olefinic polymerization, comprises one or more formulas RCH=CHR
8Monomer contact with a kind of catalyzer, described catalyzer is by with the compound of formula XII:
Combine and form with a kind of compound Y,
Wherein R and R
8Each represents hydrogen, alkyl or fluorinated alkyl independently, and can be connected to form cycloolefin;
R
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently, preferable space sterically hindered aryl;
A and B are respectively independently for being connected heteroatomic single group, and the heteroatoms of wherein said connection is selected from the 15th or 16 families; In addition, A can be connected by abutment with B;
Q represents alkyl, chlorine, iodine or bromine;
W represents alkyl, chlorine, iodine or bromine;
N represents nitrogen;
M represents Ni (II), Pd (II), Co (II) or Fe (II), preferred Ni (II) or Pd (II);
And Y is selected from and can captures Q
-Or W
-The Bronsted acid that to form a kind of neutral lewis acid of weakly coordinating anion, positively charged ion Lewis acid that its gegenion is weakly coordinating anion and a kind of its conjugate base be weakly coordinating anion.
In a kind of preferred embodiment, the compound of formula XII is selected from the compound of following formula:
R
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently, preferable space sterically hindered aryl;
R
2, R
3, R
4And R
5Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently; In addition, R
2, R
3, R
4And R
5Any two can connect by abutment, prerequisite is when described compound is the compound of formula V or VIII, described abutment is not to replace sulphur atom or replacement phosphorus atom;
Q represents alkyl, chlorine, iodine or bromine;
W represents alkyl, chlorine, iodine or bromine;
M represents Ni (II), Pd (II), Co (II) or Fe (II);
N represents nitrogen; O represents oxygen; S represents sulphur; With
X
-Be a kind of weakly coordinating anion.
As foregoing, catalyzer of the present invention can use in the olefin unit that will contain the functional group is incorporated polymerization process in the polymkeric substance of generation into.Various functionalized olefin polymers and multipolymer and the method that obtains it are described among the temporary patent application 60-062609 of pending trial when incorporating this paper into by reference.
The present invention also provides the method for preparing linear alpha-alkene, comprises with ethene and (a) a kind of suitable nickel parent (b) a kind of compound of following formula:
Contact with optional (c) a kind of Bronsted acid or Lewis acid, wherein
R
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently, preferred phenyl or 4-p-methoxy-phenyl;
R
2, R
3, R
4And R
5Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently; In addition, R
2, R
3, R
4And R
5Any two can form an abutment together;
N represents nitrogen; O represents oxygen; S represents sulphur.
As another preferred aspect, the method for preparing linear alpha-alkene is provided, comprise contacting with the compound of ethene and a kind of following formula
R wherein
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently, preferred phenyl or 4-p-methoxy-phenyl;
R
2, R
3, R
4And R
5Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently; In addition, R
2, R
3, R
4And R
5Any two can form an abutment together, prerequisite is when described compound is the compound of formula IV or VII, described abutment is not to replace sulphur atom or replace phosphorus atom;
T represents hydrogen or alkyl;
L represents a kind of monoolefine or a kind of neutral Lewis base, and wherein said ligating atom is nitrogen, oxygen or sulphur;
M represents Ni (II);
N represents nitrogen; O represents oxygen; S represents sulphur; With
X
-Be a kind of weakly coordinating anion.
As another preferred aspect of the present invention, the method for preparing alpha-olefin is provided, comprise ethene is contacted with a kind of catalyzer that described catalyzer is by the title complex of following formula:
Combine with compound Y and to form,
R wherein
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently, preferred phenyl or 4-p-methoxy-phenyl;
R
2, R
3, R
4And R
5Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently; In addition, R
2, R
3, R
4And R
5Any two can form an abutment together, prerequisite is when described title complex is the title complex of formula V or VIII, described abutment is not to replace sulphur atom or replace phosphorus atom;
Q representation hydrocarbyl, chlorine, iodine or bromine;
W representation hydrocarbyl, chlorine, iodine or bromine;
M represents Ni (II);
N represents nitrogen; O represents oxygen; S represents sulphur;
Be selected from Y and can capture Q
-Or W
-The Bronsted acid that to form a kind of neutral lewis acid of weakly coordinating anion, positively charged ion Lewis acid that its gegenion is weakly coordinating anion or a kind of its conjugate base be weakly coordinating anion.
Another embodiment of the present invention is a kind of ethene and formula CH
2=CH (CH
2)
nCO
2R
1The copolymerization process of comonomer, comprise ethene and a kind of formula CH
2=CH (CH
2)
nCO
2R
1Comonomer with by (it is selected from and can captures Q with first kind of compound Y
-Or W
-The Bronsted acid that to form a kind of neutral lewis acid of weakly coordinating anion, positively charged ion Lewis acid that its gegenion is weakly coordinating anion or a kind of its conjugate base be weakly coordinating anion) contact in conjunction with formed title complex with second kind of compound of formula XXIV:
R wherein
1Be hydrogen, alkyl, substituted hydrocarbon radical, fluoro-alkyl or silyl;
N is an integer greater than 3, is preferably greater than 5 and less than 25;
R
2And R
3Each is hydrogen, alkyl, substituted hydrocarbon radical or silyl independently, or can form a bridging alkyl, bridging substituted hydrocarbon radical or a replacement Siliciumatom jointly;
Q is alkyl, chlorine, iodine or bromine;
W is alkyl, chlorine, iodine or bromine;
N is a nitrogen;
Z is sulphur or oxygen; With
M is Ni (II).
As another aspect of the present invention, a kind of ethene and formula CH are provided
2=CH (CH
2)
nCO
2R
1The polymerization process of comonomer, comprise ethene and a kind of formula CH
2=CH (CH
2)
nCO
2R
1Comonomer and compound by (a) a kind of formula XLII; (b) a kind of suitable nickel (O) parent, the title complex that forms with the reaction product of (c) a kind of its conjugate base Bronsted acid that is weakly coordinating anion contacts,
R wherein
1Be hydrogen, alkyl, substituted hydrocarbon radical, fluoro-alkyl or silyl;
N is an integer greater than 3, is preferably greater than 5 and less than 25;
R
2And R
3Each be hydrogen, alkyl, substituted hydrocarbon radical or silyl independently, or can form jointly a bridging alkyl, bridging substituted hydrocarbon radical ,-C (O)-or replacement Siliciumatom;
N is a nitrogen; With
Z is sulphur or oxygen.
As another embodiment of the present invention, a kind of method of olefinic polymerization is provided, comprise one or more formulas RCH=CHR
8Monomer be coupled to a double-coreization or a multinucleation ligand on the 8-10 group 4 transition metal M and contact with one or more Lewis acids, wherein said Lewis acid is incorporated on one or more heteroatomss, this heteroatoms pi-conjugated to described transition metal M bonded donor atom on; R and R
8Each represents hydrogen, alkyl or fluoro-alkyl independently, and can be connected to form cycloolefin.
Catalyzer of the present invention comprises the group 4 transition metal by bidentate ligand X coordinate 8-10; They include but not limited to preferred compound I, the II, IV, V, VII, VIII, XI-XVI, XIX-XXVIII and the XXX-XLII that describe in detail in this.
A kind of more preferably example of catalyzer of the present invention is the compound of formula I:
R wherein
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently, preferred phenyl, 4-p-methoxy-phenyl or sterically hindered aryl;
R
2, R
3, R
4And R
5Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently; In addition, R
2, R
3, R
4And R
5Any two can form an abutment together;
T represents hydrogen or alkyl;
L represents a kind of monoolefine or neutral Lewis base, and wherein ligating atom is nitrogen, oxygen or sulphur;
M represents a kind of 8-10 group 4 transition metal, preferred Ni (II), Pd (II), Co (II) or Fe (II), more preferably Ni (II) or Pd (II);
N represents nitrogen; With
X
-Be weakly coordinating anion.
A kind of catalyzer that comprises formula II compound is also disclosed here:
R wherein
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently, preferred phenyl, 4-p-methoxy-phenyl or sterically hindered aryl;
R
2, R
3, R
4And R
5Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently; In addition, R
2, R
3, R
4And R
5Any two can form an abutment together;
Q representation hydrocarbyl, chlorine, iodine or bromine;
W representation hydrocarbyl, chlorine, iodine or bromine;
N represents nitrogen; With
M represents a kind of 8-10 group 4 transition metal, preferred Ni (II), Pd (II), Co (II) or Fe (II), more preferably Ni (II) or Pd (II).
Here the catalyzer that also openly comprises formula IV compound:
R wherein
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently, preferred phenyl, 4-p-methoxy-phenyl or sterically hindered aryl;
R
2And R
3Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently, in addition, can form bridging alkyl, bridging substituted hydrocarbon radical together or replace Siliciumatom;
T represents hydrogen or alkyl;
L represents monoolefine or neutral Lewis base, and wherein said ligating atom is nitrogen, oxygen or sulphur;
M represents Ni (II), Pd (II), Co (II) or Fe (II), more preferably Ni (II) or Pd (II);
N represents nitrogen; With
X
-Be a kind of weakly coordinating anion.
Disclosed in addition have a catalyzer that comprises formula V compound:
R wherein
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently, preferred phenyl or 4-p-methoxy-phenyl or sterically hindered aryl;
R
2And R
3Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently, in addition, can form bridging alkyl, bridging substituted hydrocarbon radical together or replace Siliciumatom;
Q representation hydrocarbyl, chlorine, iodine or bromine;
W representation hydrocarbyl, chlorine, iodine or bromine;
N is a nitrogen; With
M represents the transition metal of 8-10 family, preferred Ni (II), Pd (II), Co (II) or Fe (II), more preferably Ni (II) or Pd (II).
The invention discloses the purposes of the catalyzer of the compound that comprises formula VI in addition:
R wherein
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently, preferred phenyl, 4-p-methoxy-phenyl or sterically hindered aryl; With
R
2And R
3Each represents hydrogen, alkyl substituted hydrocarbon radical or silyl independently, in addition, can form bridging alkyl, bridging substituted hydrocarbon radical together or replace Siliciumatom.
A kind of catalyzer that comprises formula VII compound is also disclosed in this:
R wherein
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently, preferred phenyl, 4-p-methoxy-phenyl or sterically hindered aryl;
R
2And R
3Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently, in addition, can form bridging alkyl, bridging substituted hydrocarbon radical together or replace Siliciumatom;
T represents hydrogen or alkyl;
L represents monoolefine or neutral Lewis base, and wherein said ligating atom is nitrogen, oxygen or sulphur;
M represents Ni (II), Pd (II), Co (II) or Fe (II), more preferably Ni (II) or Pd (II);
N represents nitrogen; With
X
-Be a kind of weakly coordinating anion.
A kind of catalyzer that comprises formula VIII compound is also disclosed in this:
R wherein
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently, preferred phenyl, 4-p-methoxy-phenyl or sterically hindered aryl;
R
2And R
3Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently, in addition, can form bridging alkyl, bridging substituted hydrocarbon radical together or replace Siliciumatom;
Q representation hydrocarbyl, chlorine, iodine or bromine;
W representation hydrocarbyl, chlorine, iodine or bromine;
N represents nitrogen; With
M represents a kind of 8-10 group 4 transition metal, preferred Ni (II), Pd (II), Co (II) or Fe (II), more preferably Ni (II) or Pd (II).
A kind of catalyzer that comprises formula IX compound is also disclosed in this:
R wherein
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently, preferred phenyl, 4-p-methoxy-phenyl or sterically hindered aryl; With
R
2And R
3Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently, in addition, can form bridging alkyl, bridging substituted hydrocarbon radical together or replace Siliciumatom.
A kind of catalyzer that comprises formula XIII compound is also disclosed in this:
R wherein
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently, preferred phenyl, 4-p-methoxy-phenyl or sterically hindered aryl;
R
2, R
3And R
4Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently, in addition, can form abutment together;
T represents hydrogen or alkyl;
L represents monoolefine or neutral Lewis base, and wherein said ligating atom is nitrogen, oxygen or sulphur;
M represents Ni (II), Pd (II), Co (II) or Fe (II), more preferably Ni (II) or Pd (II);
N represents nitrogen; With
X
-Be a kind of weakly coordinating anion.
A kind of catalyzer that comprises formula XIV compound is also disclosed in this:
R wherein
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently, preferred phenyl, 4-p-methoxy-phenyl or sterically hindered aryl;
R
2And R
5Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently;
T represents hydrogen or alkyl;
L represents monoolefine or neutral Lewis base, and wherein said ligating atom is nitrogen, oxygen or sulphur;
M represents a 8-10 group 4 transition metal, preferred Ni (II), Pd (II), Co (II) or Fe (II), more preferably Ni (II) or Pd (II);
N represents nitrogen; With
X
-Be a kind of weakly coordinating anion.
A kind of catalyzer that comprises formula XV compound is also disclosed in this:
R wherein
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently, preferred phenyl, 4-p-methoxy-phenyl or sterically hindered aryl;
R
2, R
3And R
4Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently, in addition, can form abutment together;
Q representation hydrocarbyl, chlorine, iodine or bromine;
W representation hydrocarbyl, chlorine, iodine or bromine;
N represents nitrogen; With
M represents a kind of 8-10 group 4 transition metal, preferred Ni (II), Pd (II), Co (II) or Fe (II), more preferably Ni (II) or Pd (II).
A kind of catalyzer that comprises formula XVII compound is also disclosed in this:
R wherein
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently, preferred phenyl, 4-p-methoxy-phenyl or sterically hindered aryl; With
R
2, R
3And R
4Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently, in addition, and R
2, R
3Or R
4Any two can form abutment together.
A kind of catalyzer that comprises formula XVI compound is also disclosed in this:
R wherein
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently, preferred phenyl, 4-p-methoxy-phenyl or sterically hindered aryl;
R
2And R
5Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl, preferable space steric hindrance aryl independently;
Q representation hydrocarbyl, chlorine, iodine or bromine;
W representation hydrocarbyl, chlorine, iodine or bromine;
N represents nitrogen; With
M represents a kind of 8-10 group 4 transition metal, preferred Ni (II), Pd (II), Co (II) or Fe (II), more preferably Ni (II) or Pd (II).
A kind of catalyzer that comprises formula XVIII compound also is provided in this:
R wherein
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently, preferred phenyl, 4-p-methoxy-phenyl or sterically hindered aryl;
R
2And R
5Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently.
A kind of catalyzer that comprises formula XIX compound also is provided in this:
R wherein
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently, preferred phenyl, 4-p-methoxy-phenyl or sterically hindered aryl;
R
2, R
3, R
4And R
5Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently, in addition, and R
2, R
3, R
4And R
5Any two can form abutment together;
G is a π-allyl group or π-benzyl group;
M represents Ni (II) or Pd (II);
N represents nitrogen; With
X
-Be a kind of weakly coordinating anion.
A kind of catalyzer that comprises formula XX compound also is provided in this:
R wherein
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently, preferred phenyl, 4-p-methoxy-phenyl or sterically hindered aryl;
R
2And R
3Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently, in addition, can form bridging alkyl, bridging substituted hydrocarbon radical together or replace Siliciumatom;
G is a π-allyl group or π-benzyl group;
M represents Ni (II) or Pd (II);
N represents nitrogen; With
X
-Be a kind of weakly coordinating anion.
A kind of catalyzer that comprises formula XXI compound also is provided in this:
R wherein
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently, preferred phenyl, 4-p-methoxy-phenyl or sterically hindered aryl;
R
2And R
3Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently, in addition, can form bridging alkyl, bridging substituted hydrocarbon radical together or replace Siliciumatom;
G is a π-allyl group or π-benzyl group;
M represents Ni (II) or Pd (II);
N represents nitrogen; With
X
-Be a kind of weakly coordinating anion.
A kind of catalyzer that comprises formula XXII compound also is provided in this:
R wherein
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently, preferred phenyl, 4-p-methoxy-phenyl or sterically hindered aryl;
R
2, R
3And R
4Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently, in addition, and R
2, R
3And R
4Any two can form abutment together;
G is a π-allyl group or π-benzyl group;
M represents Ni (II) or Pd (II);
N represents nitrogen; With
X
-Be a kind of weakly coordinating anion.
A kind of catalyzer that comprises formula XXIII compound also is provided in this:
R wherein
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently, preferred phenyl, 4-p-methoxy-phenyl or sterically hindered aryl;
R
2And R
5Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently;
G is a π-allyl group or π-benzyl group;
M represents Ni (II) or Pd (II);
N represents nitrogen; With
X
-Be a kind of weakly coordinating anion.
Formula XXIV compound also is provided in this:
R wherein
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently, preferred phenyl, 4-p-methoxy-phenyl or sterically hindered aryl;
A and B are respectively independently for being connected heteroatomic single group, and the heteroatoms of wherein said connection is selected from the 15th or 16 families, and A can be connected by an abutment with B in addition;
T represents hydrogen or alkyl;
L represents monoolefine or neutral Lewis base, and wherein said ligating atom is nitrogen, oxygen or sulphur;
M represents Ni (II) or Pd (II);
N represents nitrogen; With
X
-Be a kind of weakly coordinating anion.
A kind of formula XXV catalyzer compound, that be used for olefinic polymerization that comprises also is provided in this:
R wherein
1And R
6Be 2, the 6-3,5-dimethylphenyl;
And X
-Be a kind of weakly coordinating anion.
A kind of catalyzer that is used for olefinic polymerization also is provided in this, and it comprises the compound of formula XXVI:
R wherein
1And R
6Be 2, the 6-diisopropyl phenyl;
And X
-Be a kind of weakly coordinating anion.
A kind of catalyzer that is used for olefinic polymerization also is provided in this, and it comprises the compound of formula XXVII:
R wherein
1And R
6Be 2, the 6-3,5-dimethylphenyl.
A kind of catalyzer that is used for olefinic polymerization also is provided in this, and it comprises the compound of formula XXVIII:
R wherein
1And R
6Be 2, the 6-diisopropyl phenyl.
A kind of catalyzer also is provided in this, and it comprises the compound of formula XXIX:
R wherein
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently, preferred phenyl, 4-p-methoxy-phenyl or sterically hindered aryl;
A and B are respectively independently for being connected heteroatomic single group, and the heteroatoms of wherein said connection is selected from the 15th or 16 families, and A can be connected by an abutment with B in addition;
Q representation hydrocarbyl, chlorine, iodine or bromine;
W representation hydrocarbyl, chlorine, iodine or bromine;
M represents Ni (II) or Pd (II); With
N represents nitrogen.
A kind of catalyzer that is used for olefinic polymerization also is provided in this, and it comprises the compound of formula XXX:
R wherein
1And R
6Be 2, the 6-3,5-dimethylphenyl;
And X
-Be a kind of weakly coordinating anion.
A kind of catalyzer that is used for olefinic polymerization also is provided in this, and it comprises the compound of formula XXXI:
R wherein
1And R
6Be 2, the 6-diisopropyl phenyl;
And X
-Be a kind of weakly coordinating anion.
A kind of catalyzer that is used for olefinic polymerization also is provided in this, and it comprises the compound of formula XXXII:
R wherein
1And R
6Be 2, the 6-3,5-dimethylphenyl.
A kind of catalyzer that is used for olefinic polymerization also is provided in this, and it comprises the compound of formula XXXIII:
R wherein
1And R
6Be 2, the 6-diisopropyl phenyl.
A kind of catalyzer that is used for olefinic polymerization also is provided in this, and it comprises the compound of formula XXXIV:
R wherein
1And R
6Be 2, the 6-diisopropyl phenyl;
And X
-Be a kind of weakly coordinating anion.
A kind of catalyzer that is used for olefinic polymerization also is provided in this, and it comprises the compound of formula XXXV:
R wherein
1And R
6Be 2, the 6-diisopropyl phenyl;
And X
-Be a kind of weakly coordinating anion.
A kind of catalyzer that is used for olefinic polymerization also is provided in this, and it comprises the compound of formula XXXVI:
R wherein
1And R
6Be 2, the 6-3,5-dimethylphenyl;
And X
-Be a kind of weakly coordinating anion.
A kind of catalyzer that is used for olefinic polymerization also is provided in this, and it comprises the compound of formula XXXVII:
R wherein
1And R
6Be 2, the 6-diisopropyl phenyl;
And X
-Be a kind of weakly coordinating anion.
A kind of catalyzer that is used for olefinic polymerization also is provided in this, and it comprises the compound of formula XXXVIII:
R wherein
1And R
6Be 2, the 6-3,5-dimethylphenyl.
A kind of catalyzer that is used for olefinic polymerization also is provided in this, and it comprises the compound of formula XXXIX:
R wherein
1And R
6Be 2, the 6-diisopropyl phenyl.
A kind of catalyzer that is used for olefinic polymerization also is provided in this, and it comprises the compound of formula XL:
R wherein
1, R
2, R
5And R
6Be 2,6-dimethyl-4-p-methoxy-phenyl;
And X
-Be a kind of weakly coordinating anion.
A kind of catalyzer that is used for olefinic polymerization also is provided in this, and it comprises the compound of formula XLI:
R wherein
1, R
2, R
5And R
6Be 2,6-dimethyl-4-p-methoxy-phenyl;
And X
-Be a kind of weakly coordinating anion.
The present invention also provides some new polymer composition.Therefore, another aspect of the present invention provides a kind of polymer composition, and it comprises the formula CH that comes from ethene and come from 0.1-50% (weight)
2=CH (CH
2)
nCO
2R
1The monomeric unit of comonomer, R wherein
1For hydrogen, alkyl, substituted hydrocarbon radical, fluoro-alkyl or silyl and n are a integer between 3 to 18; Except branch be since described comonomer sneak into caused, alkyl branch is present in the described polymer composition, wherein per 1000 carbon atoms exist 5 to 50 alkyl branches and most of alkyl to branch into methyl branch.
In an embodiment preferred, provide contain the composition that per 1000 carbon atoms have the ester of 5-30 alkyl ramose hemicrystalline copolymerization of ethylene a kind of comprising, wherein most of alkyl branches into branch's (coming from sneaking into of ester comonomer) of methyl branch and on average about 1-50 the ester end of each chain.
In another kind of embodiment preferred, provide to comprise and contain the composition that per 1000 carbon atoms have the alkene of 5-30 alkyl ramose hemicrystalline copolymerization of ethylene, wherein most of alkyl branches into branch's (coming from sneaking into of linear diene comonomer) of methyl branch and on average about 1-50 the alkene end of each chain.
Another aspect of the present invention provides to comprise that per 1000 carbon atoms have the polymer composition more than 125 alkyl ramose Alathons, can be used as tackiness agent or tackifier.
The available preferred alkenes comprises that ethene and alpha-olefin such as propylene, 1-butylene, 1-hexene, 1-octene, undecylene acetoacetic ester and cycloolefin are such as cyclopentenes in the enforcement of the inventive method.
Be aggregated in when carrying out in the liquid phase when described, described liquid phase can comprise solvent or pure monomer.The molar ratio scope of neutral lewis acid and transition metal complex can be 1-10000, preferred 10-1000.Pressure when carrying out vinyl polymerization and copolymerization can be pressed onto 1000 normal atmosphere from 1 atmosphere, preferred 1-100 normal atmosphere.
Although be not wishing to be bound by theory, the present inventor believe described Lewis acid can by with directly be not attached on the described transition metal M, but the effect of the catalyzer that further activation provides in this is played in pi-conjugated one or more those heteroatoms coordinations with being attached to nitrogen on the transition metal M.The substituting group that comprises other Louis's base (include but not limited to methoxyl group, be used for further promoting the combination of Lewis acid on this pi-conjugated heteroatoms) is also included within the present invention.Second kind of lewis acidic non-limiting example of institute's bonded comprises:
R wherein
1, R
2, R
5And R
6Be 2, the 6-3,5-dimethylphenyl; X
-Be a kind of weakly coordinating anion.
Described polymerization can be with solution polymerization, the polymerization of non-solvent slurry-type, use one or more alkene or other solvent to carry out as the slurry polymerization or the vapour phase polymerization form of polymerisation medium.Knownly disclosed by the inventionly it will be understood by those skilled in the art that described catalyzer can use suitable support of the catalyst and methods known in the art to be stated from the carrier.Can use basic inert solvent such as toluene, hydro carbons, methylene dichloride etc.Propylene and 1-butylene are good monomers in the slurry-type copolymerization, but the monomer flash distillation of usefulness new use of coming out to lay equal stress on not.
Temperature and alkene pressure have remarkable influence to copolymer structure, composition and molecular weight.The polymerization temperature that is suitable for is preferably-100 ℃ to about 200 ℃ approximately, more preferably 20 ℃ to 150 ℃.
When reaction proceed to be enough to produce the time of required polymkeric substance after, can from reaction mixture, reclaim polymkeric substance by the separation and/or the purification process of routine.
In general, polymkeric substance of the present invention can be used as component, elastomerics, wrapping material, film, polyester and the polyolefinic compatilizer of thermosetting material, the component of thickening composition and the component of adhesive material.
High molecular weight resin is easy to use extrusion molding, injection moulding, compression moulding and the processing of vacuum forming technology of routine known in the art.Useful articles prepared therefrom comprises film, fiber, bottle and other container, compressing tablet, moulded parts etc.
Low-molecular-weight resin for example can be used as synthetic wax and they can use in various wax coatings or emulsion form.They also can be specifically and Ethylene/vinyl acetate or ethylene/methyl acrylate type multipolymer be mixed in the purposes of paper coating or tackiness agent.
Although be not required, used conventional additives can be used in the new homopolymer and multipolymer of the present invention in olefin polymer or vinyl polymer.Conventional additives comprises pigment, tinting material, titanium dioxide, carbon black, antioxidant, stablizer, surface slip agent, fire retardant etc.This is familiar with these additives and its purposes in polymeric system as those skilled in the art.
Use refractive index to detect at the molecular weight data shown in the following example, measure down at 135 ℃ in the 4-trichlorobenzene, and use the narrow molecular weight distributions polystyrene standards to proofread and correct 1,2.
Embodiment
The following example is used to illustrate the present invention, but is not construed as limiting the invention, and the description people by the following example can understand further feature of the present invention.
Embodiment 1
N, the preparation of N '-two (2, the 6-3,5-dimethylphenyl) oxamide
With 2,6-xylidine, triethylamine and methylene dichloride are by the alkali alumina drying.Is furnished with the magnetic force splash bar and takes over 125 milliliters of sealing with nitrogen inlet 53.38 grams 2 of packing in the flask at the bottom of all pressing 1 liter of garden of dropping funnel at one, 6-xylidine, 250 milliliters of methylene dichloride and 44.76 gram triethylamines.Under nitrogen atmosphere, be accompanied by and stir and the ice bath cooling, with dripped in 1.2 hours 25.34 restrain oxalyl chlorides in 80 milliliters of methylene dichloride solution and obtain a kind of thick slurries, its must the time and reverberate with hand and to mix.Mixture was at room temperature stirred 14 hours, transfer to then in the separating funnel, wash with water three times, separate and the concentrated rough solids of 63 grams that obtains of decompression (10 mm Hg).Crude product is dissolved in the boiling mixture of 1.30 liters of toluene and 2.85 liters of dehydrated alcohols, cool to room temperature (about 23 ℃) also dilutes with 260 ml waters, allows its crystallization 16 hours then.The throw out that obtains is by isolated by vacuum filtration, obtain 39.1 gram (66%) white crystals with methyl alcohol (3 * 100 milliliters) washing and drying.Reclaim 9.5 grams (16.1%) in addition by further dilute filtrate with about 500 ml waters.The field desorption(FD) mass spectrum is presented at the parent ion peak at 296m/z place.
1H NMR (300MHz, CDCl
3, corresponding to being the chemical shift of unit with ppm at the TMS of 0ppm place): 2.29 (12p, s), 7.15 (6p, m), 8.86 (2p, br s).
Embodiment 2
N, the preparation of N '-two (2, the 6-diisopropyl phenyl) oxamide
With 2,6-diisopropyl aniline, triethylamine and methylene dichloride are by the alkali alumina drying.Is furnished with the magnetic force splash bar and takes over 125 milliliters of sealing with nitrogen inlet 34.73 grams 2 of packing in the flask at the bottom of all pressing 1 liter of garden of dropping funnel at one, 6-diisopropyl aniline (through fore-distillation), 180 milliliters of methylene dichloride and 18.30 gram triethylamines.Under nitrogen atmosphere, be accompanied by stir and the ice bath cooling with dropping in 38 minutes 10.57 restrain oxalyl chlorides in 43 milliliters of methylene dichloride solution and obtain a kind of thick slurries, its must the time and reverberate with hand and to mix.With mixture at room temperature (about 23 ℃) stirred 60 hours, be settled out product with the dilution of 700 ml waters then, with the product filtering separation, wash with water and from ebullient Virahol (4 liters) recrystallization obtain 22.38 and restrain (66%) white needles things.The field desorption(FD) mass spectrum is presented at the parent ion peak at 408m/z place.
1HNMR (500 MHz, CD
2Cl
2, corresponding to being the chemical shift of unit with ppm at the TMS of 0ppm place): 1.22 (24p, d, 6.8Hz), 3.08 (4p, septet, 6.8Hz), 7.25 (4p, d, 7.5Hz), 7.37 (2p, t, 7.5Hz), 8.86 (2p, br s).
Embodiment 3
N, the preparation of N '-two (4-methoxyl group-2,6-3,5-dimethylphenyl) oxamide
Triethylamine and methylene dichloride are passed through the alkali alumina drying.Be furnished with the magnetic force splash bar and take over the 1.5 gram 4-methoxyl groups-2 of packing in the flask at the bottom of 50 milliliters of gardens that seal little all press dropping funnel with nitrogen inlet at one, 6-xylidine, 8 milliliters of methylene dichloride and 1.38 gram triethylamines.Under nitrogen atmosphere, be accompanied by and stir and the ice bath cooling, dripped 0.39 with 35 minutes and restrain the solution of oxalyl chloride in 2 milliliters of methylene dichloride.Mixture was at room temperature stirred 14 hours, transfer to then in the separating funnel, wash with water, separate and the concentrated 1.75 gram solidss that obtain of decompression (10 mm Hg).Crude product is dissolved in 150 milliliters of ebullient dehydrated alcohols, separates out crystallization in cool to room temperature (the about 23 ℃) process.The throw out that obtains obtains 1.39 gram (86%) white crystals by isolated by vacuum filtration and drying.The field desorption(FD) mass spectrum is presented at the parent ion peak at 356m/z place.
Embodiment 4
N
1, N
2The preparation of-two (2, the 6-3,5-dimethylphenyl) oxalyl diimine acyl dichloro (oxalodiimidoyldichloride)
Be furnished with magnetic force splash bar and the nitrogen inlet that links to each other with scatterer with one at one and take over the 30.0 gram N that pack in the flask at the bottom of 1 liter of garden of the reflux exchanger that seals, N '-two (2, the 6-3,5-dimethylphenyl) oxamide, 58.8 gram phosphorus pentachloride and 150 milliliters of dry toluene.With 30 minutes mixture heating up is refluxed, under nitrogen atmosphere, keep again then refluxing other 95 minutes and forming a kind of yellow solution.Stop heating and allow mixture cool to room temperature (about 23 ℃).Connect the short-path distillation adapter that replaces condenser and receiving bottle and under decompression (1 mm Hg), beginning is in room temperature, remove volatile matter and obtain 20.1 gram (60%) granular, yellow solid at 100 ℃ then.The field desorption(FD) mass spectrum is presented at the parent ion peak at 332m/z place.
1H NMR (300MHz, C
6D
6, corresponding to being the chemical shift of unit with ppm at the TMS of 0ppm place): 2.04 (12p, s), 6.91 (6p, s).
Embodiment 5
N
1, N
2The preparation of-two (2, the 6-diisopropyl phenyl) oxalyl diimine acyl dichloro
Be furnished with magnetic force splash bar and the nitrogen inlet that links to each other with scatterer with one at one and take over the 2.5 gram N that pack in the flask at the bottom of 500 milliliters of gardens of the reflux exchanger that seals, N '-two (2, the 6-diisopropyl phenyl) oxamide, 3.58 gram phosphorus pentachloride and 36 milliliters of dry toluene.With 30 minutes mixture heating up is refluxed, under nitrogen atmosphere, keep again then refluxing other 210 minutes and forming a kind of glassy yellow solution.Stop heating and allow mixture cool to room temperature (about 23 ℃).Connect the short-path distillation adapter that replaces condenser and receiving bottle and under decompression (1 mm Hg), beginning is in room temperature, remove volatile matter and obtain a kind of yellow oil at 100 ℃ then, its slowly crystallization in process of cooling fully.Product is by column chromatography (SiO
2, Merck Grade 9385 230-400 orders, 60 dusts; 3% (volume) ethyl acetate isohexane solution) obtain 1.49 gram (55%) yellow crystals.The field desorption(FD) mass spectrum is presented at the parent ion peak at 444m/z place.
Embodiment 6
N
1, N
2The preparation of-two (4-methoxyl group-2,6-3,5-dimethylphenyl) oxalyl diimine acyl dichloro
Be furnished with magnetic force splash bar and the nitrogen inlet that links to each other with scatterer with one at one and take over the 1.37 gram N that pack in the flask at the bottom of 50 milliliters of gardens of the reflux exchanger that seals, N '-two (4-methoxyl group-2,6-3,5-dimethylphenyl) oxamide, 1.88 gram phosphorus pentachloride and 15 milliliters of dry toluene.Under agitation, mixture is heated down up to there not being HCl to overflow at about 100 ℃.Add 0.22 other gram PCl then
5And at 80 ℃ with mixture reheat 30 minutes.Behind the cool to room temperature, mixture is transferred in the separating funnel, occurred partial crystallization in the transfer process.Methylene dichloride shifts product fully and dissolving again by adding.Organic layer washs with saturated sodium bicarbonate aqueous solution, and vacuum concentration obtains 1.44 gram crystalline yellow solid then.The field desorption(FD) mass spectrum is presented at the parent ion peak at 392m/z place.
Embodiment 7
2, two (2,6-3,5-dimethylphenyl imino-)-1 of 3-, the preparation of 4-dithiane
504 milligrams of N pack in flask at the bottom of 50 milliliters of gardens of the reflux exchanger being furnished with the magnetic force splash bar and sealing with a nitrogen inlet adapter
1, N
2-two (2, the 6-3,5-dimethylphenyl) oxalyl diimine acyl dichloro, 136 milligrams of sodium hydrides (60% mineral oil dispersion), 4.0 milliliters of dry tetrahydrofuran and 0.140 milliliter of 1.Mixture heating up was refluxed 2 hours, after this add 66 milligrams of other sodium hydride dispersions and also again mixture was refluxed one hour.After the cooling, water and ether diluted mixture thing wash with water behind the separation ether layer again, obtain a kind of yellowish-orange oil with dried over mgso.Column chromatography (SiO
2, Merck Grade 9385 230-400 orders, 60 dusts; The hexane solution of 15% (volume) ethyl acetate) obtains 296 milligrams of yellow oils, by adding the hexane crystallization and obtaining 219 milligrams of yellow granular crystals by vacuum filtration.The field desorption(FD) mass spectrum is presented at the parent ion peak at 354m/z place.
1HNMR (300MHz, CDCl
3, corresponding to being the chemical shift of unit with ppm at the TMS of 0ppm place): 2.17 (12p, s), 3.27 (4p, br s), 6.4-7.12 (6p, m).
Embodiment 8
2, the preparation of two (2,6-diisopropyl phenyl imino-)-[1, the 4] dithiane of 3-
0.69 60% mineral oil dispersion, 3.34 that restrains sodium hydride of packing in proper order in flask at the bottom of 250 milliliters of gardens of the reflux exchanger being furnished with the magnetic force splash bar and sealing with an argon gas inlet connection restrains N
1, N
2-two (2, the 6-diisopropyl phenyl) oxalyl diimine acyl dichloro, 20 milliliters of dry tetrahydrofuran and 0.70 milliliter of 1.With mixture reflux 3 hours under argon gas, after this add 0.25 other gram sodium hydride dispersion and again mixture was refluxed 2.5 hours.After the cooling, water and ether diluted mixture thing wash with water behind the separation ether layer again, obtain a kind of yellowish-orange oil with dried over mgso.Column chromatography (SiO
2, Merck Grade 9385230-400 order, 60 dusts; The hexane solution of 10% (volume) ethyl acetate) obtains 3.14 gram yellowish-orange vitreums.The field desorption(FD) mass spectrum is presented at the parent ion peak at 466m/z place.
1H NMR (500MHz, CD
2Cl
2, corresponding to being the chemical shift of unit with ppm at the TMS of 0ppm place): 1.10-1.22 (12p, m), 1.22-1.40 (12p, m), 2.78-3.05 (4p, m), 3.30 (4p, br s), 7.05-7.25 (6p, m).
Embodiment 9
2, the preparation of two (phenylimino)-[1,4] of 3-dithiane
60% mineral oil dispersion of 0.69 gram sodium hydride, freshly prepd 2.08 gram N in proper order pack in flask at the bottom of 250 milliliters of gardens of the reflux exchanger being furnished with the magnetic force splash bar and sealing with an argon gas inlet pipe
1, N
2-phenylbenzene oxalyl diimine acyl dichloro solution and 0.70 milliliter of 1 in 20 milliliters of dry tetrahydrofuran.With mixture reflux 2 hours under argon gas atmosphere, after this add 0.30 other gram sodium hydride dispersion and again mixture was refluxed 3 hours.After the cooling, water and ether diluted mixture thing wash with water behind the separation ether layer again, obtain a kind of yellowish-orange colloidal solid thing with dried over mgso.Column chromatography (SiO
2, MerckGrade 9385 230-400 orders, 60 dusts; The hexane solution of 10% (volume) ethyl acetate) obtains 296 milligrams of yellow oils, obtain 0.161 gram yellowish-orange granular crystal by adding the hexane crystallization.The field desorption(FD) mass spectrum is presented at the parent ion peak at 298m/z place.
1H NMR (300MHz, CDCl
3, corresponding to being the chemical shift of unit with ppm at the TMS of 0ppm place): 3.27 (4p, br s), 7.02 (4p, apparent d, 8.1Hz), 7.19 (2p, apparent t, 7.2Hz), 7.40 (4p, apparent t, 7.8Hz).
Embodiment 10
2, two (2,6-3,5-dimethylphenyl imino-)-2 of 3-, the preparation of 3-dihydrobenzo [1,4] dithiine
Pack into 60% mineral oil dispersion of 0.294 gram sodium hydride, 4 milliliters of tetrahydrofuran (THF)s and 0.253 gram 1 of order in flask at the bottom of 100 milliliters of gardens of the reflux exchanger being furnished with the magnetic force splash bar and sealing with an argon gas inlet pipe, 2-diphenyl disulfide phenol.After foaming stops, adding 0.600 gram N
1, N
2-two (2, the 6-3,5-dimethylphenyl) oxalyl diimine acyl dichloro.Mixture at 25 ℃, is stirred after 45 minutes, be heated to backflow and kept backflow 1 hour with 15 minutes.After the cooling, water and ether diluted mixture thing wash with water behind the separation ether layer again, obtain a kind of yellowish-orange oil with dried over mgso and vacuum concentration.Column chromatography (SiO
2, Merck Grade 9385 230-400 orders, 60 dusts; The hexane solution of 2% (volume) ethyl acetate) obtain 0.412 the gram yellowish-orange vitreum.The field desorption(FD) mass spectrum is presented at the parent ion peak at 402m/z place.
1H NMR (300MHz, CDCl
3, corresponding to being the chemical shift of unit with ppm at the TMS of 0ppm place): 2.16 (12p, s), 7.01-7.24 (10p, m).
Embodiment 11
2, the preparation of two (4-methoxyl group-2,6-3,5-dimethylphenyl imino-)-[1, the 4] dithiane of 3-
One be furnished with the magnetic force splash bar and with 50 milliliters of gardens of the reflux exchanger of a nitrogen inlet channel closure at the bottom of the 420 milligrams of N that pack in the flask
1, N
2-two (4-methoxyl group-2,6-3,5-dimethylphenyl) oxalyl diimine acyl dichloro.In 50 milliliters of pyriform flasks, add 60% mineral oil dispersion of 171 milligrams of sodium hydrides, 1.75 milliliters of dry tetrahydrofuran and 0.11 milliliter of 1 of careful adding.The mixture that obtains is injected into N
1, N
2In-two (4-methoxyl group-2,6-3,5-dimethylphenyl) oxalyl diimine acyl two chlorine solution, finish transfer with 5 milliliters of tetrahydrofuran (THF)s.With reaction flask reflux 3 hours, after this add 45 milligrams of other sodium hydride dispersions and add 20 other microlitre dithioglycols, and mixture was refluxed 1 hour again.After the cooling, water and ether diluted mixture thing wash with water behind the separation ether layer again, also concentrate with dried over mgso and obtain a kind of yellowish-orange solids.Column chromatography (SiO
2, Merck Grade 9385 230-400 orders, 60 dusts; The hexane solution of 15% (volume) ethyl acetate) obtains 147 milligrams of yellow powders.The field desorption(FD) mass spectrum is presented at the parent ion peak at 414m/z place.
Embodiment 12
2, the preparation of two (2,6-3,5-dimethylphenyl imino-)-[1,4]-dioxs of 3-
One be furnished with the magnetic force splash bar and with 50 milliliters of gardens of the reflux exchanger of a nitrogen inlet channel closure at the bottom of the 504 milligrams of N that pack in the flask
1, N
260% mineral oil dispersion of-two (2, the 6-3,5-dimethylphenyl) oxalyl diimine acyl dichloro, 66 milligrams of sodium hydrides, 5.0 milliliters of dry tetrahydrofuran, 0.230 milliliter of triethylamine (by the aluminum oxide drying) and 0.093 milliliter of exsiccant ethylene glycol.Mixture heating up was refluxed 105 minutes, after this add 66 milligrams of other sodium hydride dispersions, and mixture was refluxed 1 hour again.After the cooling, water and ether diluted mixture thing wash with water behind the separation ether layer again, also concentrate with dried over mgso and obtain a kind of yellow oil, and crystallization obtains linen crystallization rosette bang (225 milligrams are gathered in the crops for the first time) from heptane.The field desorption(FD) mass spectrum is presented at the parent ion peak at 322 m/z places.
1H NMR (300 MHz, CDCl
3, corresponding to being the chemical shift of unit with ppm at the TMS of 0ppm place): 2.20 (12p, s), 4.35 (4p, s), 6.94 (2p, m), 7.05 (4p, m).
Embodiment 13
5-methoxymethyl-2, the preparation of two (2,6-3,5-dimethylphenyl imino-)-[1,4]-dioxs of 3-
504 milligrams of N pack in flask at the bottom of 50 milliliters of gardens of the reflux exchanger being furnished with the magnetic force splash bar and sealing with an argon gas inlet pipe
1, N
2-two (2, the 6-3,5-dimethylphenyl) oxalyl diimine acyl dichloro, 60% mineral oil dispersion of 155 milligrams of sodium hydrides, 3.5 milliliters of dry tetrahydrofuran and 188 milligrams of 3-methoxyl groups-1, the 2-propylene glycol.With 10 minutes mixture heating up to backflow and maintenance refluxed 2 hours.After the cooling,, obtain 329 milligrams of yellow oils with dried over mgso and vacuum concentration with ether diluted mixture thing and water (2 * 100 milliliters) washing.Column chromatography (SiO
2, Merck Grade 9385 230-400 orders, 60 dusts; The hexane solution of 20% (volume) ethyl acetate) obtains 216 milligrams of glassy yellow solids.The field desorption(FD) mass spectrum is presented at the parent ion peak at 366m/z place.
1H NMR (300MHz, CDCl
3, corresponding to being the chemical shift of unit with ppm at the TMS of 0ppm place): 2.18 (12p, s), 3.31 (3p, s), 3.45-3.65 (2p, m), 4.20-4.40 (2p, m), 4.40-4.55 (1p, m), 6.80-7.15 (6p, m).
Embodiment 14
2, two (benzyloxymethyl)-5 of 3-, two (2, the 6-3,5-dimethylphenyl imino-)-[preparations of 1,4] diox of 6-
In flask at the bottom of 100 milliliters of gardens of the reflux exchanger being furnished with the magnetic force splash bar and sealing, pack into 60% mineral oil dispersion of 265 milligrams of sodium hydrides, 7.5 milliliters of dry tetrahydrofuran, 1.0 gram 3-methoxyl groups-1 with an argon gas inlet pipe, 2-propylene glycol and 1.0 gram N
1, N
2-two (2, the 6-3,5-dimethylphenyl) oxalyl diimine acyl dichloro.With 15 minutes yellow mixture is heated to and refluxes and it becomes very sticking.Add 5 milliliters of tetrahydrofuran (THF)s again and stir the mixture, and then heated 30 minutes with glass rod.Then add 220 milligrams of sodium hydrides (60% mineral oil dispersion) and 10 milliliters of tetrahydrofuran (THF)s again.Add disappearance most of yellow second time along with sodium hydride, and make this very sticking reaction mixture become light brown.About 15 minutes of reheat, and after the cooling is with ether diluted mixture thing and wash with water and remove sodium-chlor.Column chromatography (SiO
2, MerckGrade 9385 230-400 orders, 60 dusts; The hexane solution of 2% (volume) ethyl acetate) obtains a kind of cream-coloured colloidal solid.The field desorption(FD) mass spectrum is presented at the parent ion peak at 562m/z place.
1HNMR (300MHz, CDCl
3, corresponding to being the chemical shift of unit with ppm at the TMS of 0ppm place): 2.17 (12p, s), 3.63 (4p, br s), 4.38 (2p, d, 12.6Hz), 4.47 (2p, d, 12.6Hz), 4.56 (2p, br s), 6.85-7.4 (16p, m).
Embodiment 15
2, two (2, the 6-diisopropyl phenyl imino-)-[preparations of 1,4] diox of 3-
One be furnished with the magnetic force splash bar and with 50 milliliters of gardens of the reflux exchanger of a nitrogen inlet channel closure at the bottom of the 1.0 gram N that pack in the flask
1, N
2-two (2, the 6-diisopropyl phenyl) oxalyl diimine acyl dichloro, 60% mineral oil dispersion of 268 milligrams of sodium hydrides, 4.0 milliliters of dry tetrahydrofuran and 212 milligrams of exsiccant ethylene glycol.Under argon gas atmosphere, kept 90 minutes with mixture heating up to 65 ℃ and in this temperature.Mixture is heated rapidly to the maintenance again that refluxes also to reflux 30 minutes.After the cooling,, wash with water, obtain a kind of light straw yellow oil (903 milligrams) with dried over mgso and vacuum concentration with 50 milliliters of ether diluted mixture things.Column chromatography (SiO
2, MerckGrade 9385 230-400 orders, 60 dusts; The hexane solution of 8% (volume) ethyl acetate) obtains 257 milligrams of pale green glass shape things.The field desorption(FD) mass spectrum is presented at the parent ion peak at 434m/z place.
1H NMR (300MHz, CDCl
3, corresponding to being the chemical shift of unit with ppm at the TMS of 0ppm place): 1.24 (24p, d, 6.6Hz), 3.00 (4p, septet, 6.6Hz), 4.31 (4p, br s), 7.04-7.20 (6p, m).
Embodiment 16
2, the preparation of two (2,6-3,5-dimethylphenyl the imino-)-4-methylmorpholines of 3-
503 milligrams of N pack in flask at the bottom of 50 milliliters of gardens of the reflux exchanger being furnished with the magnetic force splash bar and sealing with a nitrogen inlet adapter
1, N
2-two (2, the 6-3,5-dimethylphenyl) oxalyl diimine acyl dichloro, 346 milligrams of triethylamines, 4 milliliters of dryings are sloughed toluene and 0.135 milliliter of 2-(methylamino) ethanol of oxygen.Mixture heating up to backflow and maintenance refluxed 4.25 hours under nitrogen atmosphere with 30 minutes.After the cooling, with 45 milliliters of ether diluted mixture things and wash (110 milliliters altogether) with water three times.With the ether extract dried over mgso, filter and the concentrated a kind of light color solid (512 milligrams) that obtains of decompression (10mm Hg).Recrystallization obtains 138 milligrams of light canescence crystallizations (results for the first time) from heptane/methylene dichloride.The field desorption(FD) mass spectrum is presented at the parent ion peak at 335m/z place.
1H NMR (300MHz, CDCl
3, corresponding to being the chemical shift of unit with ppm at the TMS of 0ppm place): 1.73 (6p, s), 2.10 (6p, s), 3.27 (3p, s), 3.55-3.65 (2p, m), 4.16-4.26 (2p, m), 6.65-6.95 (6p, m).
Embodiment 17
2, the preparation of two (2,6-diisopropyl phenyl the imino-)-4-methylmorpholines of 3-
725 milligrams of N pack in flask at the bottom of 50 milliliters of gardens of the reflux exchanger being furnished with the magnetic force splash bar and sealing with a nitrogen inlet adapter
1, N
2-two (2, the 6-diisopropyl phenyl) oxalyl diimine acyl dichloro, 143 milligrams of sodium hydrides (60% mineral oil dispersion), 4 milliliters of dry tetrahydrofuran and 0.144 milliliter of 2-(methylamino) ethanol.Mixture was at room temperature stirred 4 hours, under room temperature, placed 5 days.With ether diluted mixture thing and wash with water.Decompression (10 mm Hg) concentrates ether extract and obtains a kind of yellow oil, and it crosses several hours partial crystallizations.Column chromatography (SiO
2, Merck Grade 9385 230-400 orders, 60 dusts; The hexane solution of 12% (volume) ethyl acetate) obtains 156 milligrams of faint yellow crystallizations.The field desorption(FD) mass spectrum is presented at the parent ion peak at 447m/z place.
1H NMR (300MHz, CDCl
3, corresponding to being the chemical shift of unit with ppm at the TMS of 0ppm place): 0.86 (6p, d, 7.2Hz), 1.04 (6p, d, 7.2Hz), 1.15 (6p, d, 7.2Hz), 1.18 (6p, d, 7.2Hz), 2.27 (2p, apparent septets, 7.2Hz), 2.97 (2p, apparent septet, 7.2Hz), (3.28 3p, br s), and 3.55-3.65 (2p, m), 4.14-4.22 (2p, m), 6.80-7.02 (6p, m).
Embodiment 18
1, two (2, the 6-3,5-dimethylphenyl)-4 of 3-, the preparation of two (2, the 6-3,5-dimethylphenyl imino-)-tetrahydroglyoxaline-2-ketone (imidazolidin-2-one) of 5-
In flask at the bottom of 250 milliliters of gardens, under argon gas atmosphere, restrain N with 1.0
1, N
2, N
3, N
4Careless amidine under agitation is dissolved in 35 milliliters of dryings, sloughs in the methylene dichloride of oxygen in-four (2, the 6-3,5-dimethylphenyl).Order adds 0.67 milliliter of dry triethylamine and 240 milligrams of triphosgene.Along with the adding of triphosgene, color is from the faint yellow chrome yellow that becomes.After mixture at room temperature stirred 16 hours, add 460 milligrams of triphosgene more in addition.After about 15 minutes, add 10 milligrams of dimethyl aminopyridines and 240 milligrams of other triphosgene.About more than 15 minutes behind the clock, add other 220 milligrams of triphosgene and about 0.5 gram dimethyl aminopyridine again.After mixture order usefulness saturated sodium bicarbonate aqueous solution and water washing, vacuum concentration obtains a kind of yellow powder.Column chromatography (SiO
2, Merck Grade 9385 230-400 orders, 60 dusts; The hexane solution of 4% (volume) ethyl acetate) obtains 763 milligrams of chrome yellow powder.The field desorption(FD) mass spectrum is presented at the parent ion peak at 528m/z place.
1H NMR (300 MHz, CDCl
3, corresponding to being the chemical shift of unit with ppm at the TMS of 0ppm place): 2.01 (12p, s), 2.32 (12p, s), 6.4-7.3 (12p, m).
Embodiment 19
1, two (4-methoxyl group-2, the 6-3,5-dimethylphenyls)-4 of 3-, the preparation of two (4-methoxyl group-2, the 6-3,5-dimethylphenyl imino-)-tetrahydroglyoxaline-2-ketone of 5-
One be furnished with pack in the flask at the bottom of 100 milliliters of gardens of magnetic stirring apparatus 0.75 milliliter of dry triethylamine, 6 milliliters of dryings and slough oxygen methylene dichloride and 0.335 the gram N
1, N
2, N
3, N
4The careless amidine of-four (4-methoxyl group-2,6-3,5-dimethylphenyls).Under agitation add 178 milligrams of triphosgene and flask is covered barrier film fast.Forming throw out and color becomes orange from yellow.2.5 it back adds 78 milligrams of other triphosgene, under agitation reacts 2 hours again.Add other 150 milligrams of triphosgene, and under agitation reacted again 16 hours.With 50 milliliters of ether diluted reaction mixtures and water (2 * 50 milliliters) washing.Washing water liquid dichloromethane extraction.Merge organic layer and through dried over mgso, vacuum concentration obtains a kind of orange oil.After joining ether in the described oil, form little orange crystallization.Obtain 216 milligrams of Huangs-orange microcrystal powder with described compound isolated by vacuum filtration and with the ether washing.The field desorption(FD) mass spectrum is presented at the parent ion peak at 648m/z place.
1H NMR (500MHz, CD
2Cl
2, corresponding to being the chemical shift of unit with ppm at the TMS of 0ppm place): 1.98 (12p, broad peaks), 2.25 (12p, broad peaks), 3.63 (6p, broad peaks), 3.75 (6p, broad peaks), 6.32 (4p, broad peaks), 6.59 (4p, broad peaks).
Embodiment 20
N
1, N
2, N
3, N
4The preparation of the careless amidine in-four (2, the 6-3,5-dimethylphenyl)
One be furnished with the magnetic force splash bar and with 1 liter of garden of the reflux exchanger of a nitrogen inlet channel closure at the bottom of the 5.6 gram N that pack in the flask
1, N
2-two (2, the 6-3,5-dimethylphenyl) oxalyl diimine acyl dichloro thing, 43 milliliters of dry toluene and 32.7 grams 2,6-xylidine (by the aluminum oxide drying).Under nitrogen atmosphere, mixture heating up is also kept refluxing 3 hours to refluxing again with 30 minutes.After the cooling, restrain water diluted mixture things and produce a large amount of throw outs with 206 gram dehydrated alcohols and 45., dry then and obtain 6.1 and restrain (72%) faint yellow crystallizations after the isolated by vacuum filtration with the washing of ethanol (600 milliliters) and heptane (600 milliliters).The field desorption(FD) mass spectrum is presented at the parent ion peak at 502m/z place.
1H NMR (300MHz, CDCl
3, corresponding to being the chemical shift of unit with ppm at the TMS of 0ppm place): 2.16 (24p, s), 6.75 (12p, s), 8.6 (2p, br s).
Embodiment 21
N
1, N
2, N
3, N
4The preparation of the careless amidine of-four (4-methoxyl group-2,6-3,5-dimethylphenyls)
One be furnished with the magnetic force splash bar and with 500 milliliters of gardens of the reflux exchanger of a nitrogen inlet channel closure at the bottom of the 1.0 gram N that pack in the flask
1, N
2-two (4-methoxyl group-2,6-3,5-dimethylphenyl) oxalyl diimine acyl dichloro, 24 milliliters of dry toluene and 854 milligrams of 4-methoxyl groups-2,6-xylidine and 0.90 milliliter of triethylamine (by the aluminum oxide drying).Under nitrogen atmosphere, mixture heating up is also kept refluxing 14 hours to refluxing again with 30 minutes.After the cooling, with methylene dichloride and water diluted mixture thing.Impure compound is adsorbed on SiO
2Go up and carry out column chromatography (SiO
2, Merck Grade 9385 230-400 orders, 60 dusts; The hexane solution of 12.5% (volume) ethyl acetate) obtains 340 milligrams of yellow powders.The field desorption(FD) mass spectrum is presented at the parent ion peak at 622m/z place.
Embodiment 22
1,4-dimethyl-2, the preparation of two (2, the 6-3,5-dimethylphenyl imino-) piperazines of 3-
0.50 gram N packs in flask at the bottom of 25 milliliters of gardens of the reflux exchanger being furnished with the magnetic force splash bar and sealing with a nitrogen inlet adapter
1, N
2-two (2, the 6-3,5-dimethylphenyl) oxalyl diimine acyl dichloro, 1.1 milliliters of N, N '-dimethyl-ethylenediamine and 4.0 milliliters of dry toluene.Under nitrogen atmosphere, mixture heating up is also kept refluxing 30 minutes to refluxing again with 15 minutes.After the cooling, with ether with mixture diluted and wash with water three times.The ether extract dried over mgso, after filtration and decompression (10 mm Hg) concentrate and to obtain a kind of yellow solid (0.50 gram).Recrystallization obtains a kind of light yellow crystal from heptane.The field desorption(FD) mass spectrum is presented at the parent ion peak at 348m/z place.
1H NMR (300MHz, CDCl
3, corresponding to being the chemical shift of unit with ppm at the TMS of 0ppm place): 1.83 (br s, 12p), 2-3.4 (peak of two non-constant widths, 4p), 3.42 (br s, 6p), 6.66 (t, 2p), 6.84 (d, 4p).
Embodiment 23
2, the preparation of the Nickel Bromide title complex of two (2,6-3,5-dimethylphenyl imino-)-[1, the 4] dithiane of 3-
Under inert atmosphere, be furnished with the magnetic force splash bar and be stamped in membranous 50 milliliters of Schlenk flasks and pack 100 milligram 2 into, two (2,6-3,5-dimethylphenyl imino-)-[1, the 4] dithiane of 3-and 79 milligrams of (1, the 2-glycol dimethyl ether) nickel (II) dibromide.Add dry, slough the methylene dichloride (5 milliliters) of oxygen and under argon gas atmosphere, stir the mixture, color becomes reddish-brown and slowly produces reddish-brown crystalline deposit thing in about 5 minutes.After 1 hour, add 5 milliliters of other methylene dichloride.With mixture at 21 ℃ of restir after 21 hours, with 10 milliliters of dryings, the hexane dilution of sloughing oxygen and restir 8 hours.Supernatant liquor removes by the sleeve pipe that covers the tip with filter paper, and residue drying under the vacuum of 1 mm Hg obtains 116 milligrams of reddish-brown crystallizations.
Embodiment 24
2, the preparation of the Nickel Bromide title complex of two (2,6-diisopropyl phenyl imino-)-[1, the 4] dithiane of 3-
Under argon gas atmosphere, in being furnished with the Schlenk flask of magnetic force splash bar, pack 79 milligram 2 into, two (2,6-diisopropyl phenyl imino-)-[1 of 3-, 4] dithiane (0.17 mmole) and 49 milligrams of (1, the 2-glycol dimethyl ether) nickel (II) dibromide (0.16 mmole).Add dry, slough the methylene dichloride (15 milliliters) of oxygen and under argon gas atmosphere, stir the mixture, color becomes reddish-brown in about 10 minutes.Final vacuum was removed methylene dichloride in 2 hours.The reddish-brown solids that obtains with 2 * 10 milliliters of hexane wash and under vacuum dry several hrs and obtain 76 milligrams of brown solid things.
Embodiment 25
2, the preparation of the Nickel Bromide title complex of two (phenylimino)-[1,4] of 3-dithiane
Under inert atmosphere, be furnished with the magnetic force splash bar and be stamped in membranous 50 milliliters of Schlenk flasks and pack 151 milligram 2 into, two (phenylimino)-[1, the 4] dithiane of 3-and 123 milligrams of (1, the 2-glycol dimethyl ether) nickel (II) dibromide.Add dry, slough the methylene dichloride (10 milliliters) of oxygen and under argon gas atmosphere, stir the mixture, color becomes dark-brown and slowly produces reddish-brown crystalline deposit thing in about 5 minutes.After 80 minutes, under argon gas stream, mixture is concentrated to dried, under 50 millitorr vacuum further dry 1 hour and obtain a kind of reddish-brown powder then.
Embodiment 26
2, two (2,6-3,5-dimethylphenyl imino-)-2 of 3-, the preparation of the Nickel Bromide title complex of 3-dihydrobenzo [1,4] dithine
Under inert atmosphere, be furnished with the magnetic force splash bar and be stamped in membranous 50 milliliters of Schlenk flasks and pack 110 milligram 2 into, 3-two (2,6-3,5-dimethylphenyl imino-)-2,3-dihydrobenzo [1,4] dithine and 71 milligrams of (1, the 2-glycol dimethyl ether) nickel (II) dibromide.Add dry, slough the methylene dichloride (8 milliliters) of oxygen and under argon gas atmosphere, stir the mixture, it becomes reddish-brown fast.Mixture was stirred 1 hour and under argon gas stream, is concentrated into dried, further dry and obtain a kind of reddish-brown crystalline powder under 50 millitorr vacuum then.
Embodiment 27
2, the preparation of the Nickel Bromide title complex of two (4-methoxyl group-2,6-3,5-dimethylphenyl imino-)-[1, the 4] dithiane of 3-
Under inert atmosphere, be furnished with the magnetic force splash bar and be stamped in membranous 50 milliliters of Schlenk flasks and pack 147 milligram 2 into, two (4-methoxyl group-2, the 6-3,5-dimethylphenyl imino-s)-[1 of 3-, 4] dithiane and 93 milligrams of (1, the 2-glycol dimethyl ether) nickel (II) dibromide.Add dry, slough the methylene dichloride (10 milliliters) of oxygen and under argon gas atmosphere, stir the mixture, it almost becomes dark-brown immediately and produces a kind of brown precipitate thing.The hexane of after 2 hours, add 10 milliliters of dryings, sloughing oxygen makes precipitation fully.Supernatant liquor removes by the sleeve pipe that covers the tip with filter paper, and residue drying under the vacuum of 0.5mm Hg obtained brown microcrystalline solids product in 14 hours.
Embodiment 28
2, the preparation of the Nickel Bromide title complex of two (2,6-3,5-dimethylphenyl imino-)-[1,4]-dioxs of 3-
Under inert atmosphere, be furnished with the magnetic force splash bar and be stamped in membranous 50 milliliters of Schlenk flasks and pack 100 milligram 2 into, two (2,6-3,5-dimethylphenyl imino-)-[1,4]-dioxs of 3-and 87 milligrams of (1, the 2-glycol dimethyl ether) nickel (II) dibromide.Add dry, slough the methylene dichloride (5 milliliters) of oxygen and under argon gas atmosphere, stir the mixture, it slowly produces a kind of brown crystalline deposit thing.After 1 hour, add other 5 milliliters of methylene dichloride.At 21 ℃ with mixture restir 21 hours, then with 10 milliliters of dryings, the hexane dilution of sloughing oxygen and restir 8 hours.Supernatant liquor removes by the sleeve pipe that covers the tip with filter paper, and residue drying under the vacuum of 1 mm Hg obtains 117 milligrams of brown crystals.
Embodiment 29
2, two (benzyloxymethyl)-5 of 3-, the preparation of the Nickel Bromide title complex of two (2,6-3,5-dimethylphenyl imino-)-[1,4]-dioxs of 6-
Under inert atmosphere, be furnished with the magnetic force splash bar and be stamped in membranous 50 milliliters of Schlenk flasks and pack 172 milligram 2 into, two (benzyloxymethyl)-5 of 3-, 6-two (2,6-3,5-dimethylphenyl imino-)-[1,4]-dioxs and 85 milligrams of (1, the 2-glycol dimethyl ether) nickel (II) dibromide.Add dry, slough the methylene dichloride (12 milliliters) of oxygen and under argon gas atmosphere, stir the mixture, it almost becomes reddish-brown immediately.1.75 after hour, mixture is concentrated into driedly under argon gas stream, further vacuum-drying obtains 182 milligrams of reddish-brown crystal powders then.
Embodiment 30
2, the preparation of the Nickel Bromide title complex of two (2,6-3,5-dimethylphenyl the imino-)-4-methylmorpholines of 3-
Under inert atmosphere, be furnished with the magnetic force splash bar and be stamped in membranous 25 milliliters of Schlenk flasks and pack 100 milligram 2 into, two (2,6-3,5-dimethylphenyl the imino-)-4-methylmorpholines of 3-and 84 milligrams of (1, the 2-glycol dimethyl ether) nickel (II) dibromide.Add dry, slough the methylene dichloride (5 milliliters) of oxygen and under argon gas atmosphere, stirred the mixture 1 hour, after this add other 5 milliliters of methylene dichloride.After 16 hours, with 10 milliliters of hexane diluted mixture things, supernatant liquor removes by the sleeve pipe that covers the tip with filter paper, and residue obtains 139 milligrams of green crystals in vacuum-drying.
Embodiment 31
1, two (2, the 6-3,5-dimethylphenyl)-4 of 3-, the reaction of two (2, the 6-3,5-dimethylphenyl imino-)-tetrahydroglyoxaline-2-ketone of 5-, (1, the 2-glycol dimethyl ether) nickel (II) dibromide and silver tetrafluoroborate
In a glove box that is full of argon gas, in the Schlenk flask of being furnished with the magnetic force splash bar of an oven dry, pack 159.6 milligram 1 into, 3-two (2, the 6-3,5-dimethylphenyl)-4,5-two (2,6-3,5-dimethylphenyl imino-)-tetrahydroglyoxaline-2-ketone and 92.7 milligrams of (1, the 2-glycol dimethyl ether) nickel (II) dibromide and 59.4 milligrams of silver tetrafluoroborates.Flask is encased with aluminium foil and placing under the argon gas atmosphere on the Schlenk pipeline, add 10 milliliters of dry tetrahydrofuran.Separate white depositions immediately.Mixture was stirred 25 minutes, then supernatant liquor is transferred in the dry bottle that a barrier film seals by the sleeve pipe that covers the tip with filter paper.Flow down 16 hours at dry argon gas described supernatant concentration is obtained 256 milligrams of yellow crystal powder to doing.
Embodiment 32
1, two (4-methoxyl group-2, the 6-3,5-dimethylphenyls)-4 of 3-, the preparation of two (4-methoxyl group-2,6-3,5-dimethylphenyl the imino-)-tetrahydroglyoxalines of 5--2-ketone Nickel Bromide title complex
Under inert atmosphere, be furnished with the magnetic force splash bar and be stamped in membranous 50 milliliters of Schlenk flasks and pack 101 milligram 1 into, two (the 4-methoxyl groups-2 of 3-, the 6-3,5-dimethylphenyl)-4, two (the 4-methoxyl groups-2 of 5-, 6-3,5-dimethylphenyl imino-)-tetrahydroglyoxaline-2-ketone and 40 milligrams of (1, the 2-glycol dimethyl ether) nickel (II) dibromide.Add dry, slough the methylene dichloride (10 milliliters) of oxygen and under nitrogen atmosphere, stir the mixture, slowly become dark red brown after 3 hours.After 2 hours, supernatant liquor is transferred in the Schlenk flask of an oven dry by the sleeve pipe that covers the tip with filter paper, with the hexane dilution of 10 milliliters of dryings, deoxidation and under nitrogen gas stream, be concentrated into and do and obtain a kind of brown microcrystal powder and greatly and the dark-brown crystalline mixture of sharp outline.The latter is separated and just need not to be further purified and to use.
Embodiment 33
1,4-dimethyl-2, the preparation of two (2,6-3,5-dimethylphenyl imino-) the piperazine Nickel Bromide title complexs of 3-
Under inert atmosphere, be furnished with the magnetic force splash bar and be stamped in membranous 50 milliliters of Schlenk flasks and pack 48 milligram 1 into, 4-dimethyl-2, two (2, the 6-3,5-dimethylphenyl imino-) piperazines of 3-and 35 milligrams of (1, the 2-glycol dimethyl ether) nickel (II) dibromide.Add dry, slough the methylene dichloride (5 milliliters) of oxygen and under argon gas atmosphere, stir the mixture, become green in its about 5 minutes and slowly produce a kind of green precipitate thing.After 7 hours, decompression (1 mm Hg) is removed volatile matter and the ether of residue with 2 * 5 milliliters of dryings, deoxidation is washed altogether.The green solid thing that obtains is in decompression (1 mm Hg) drying.
Embodiment 34
Synthesizing of following formula material
In a glove box, in the Schlenk flask, pack 500 milligram 2 into, two (2,6-diisopropyl phenyl imino-)-[1, the 4] dithiane of 3-and 250 milligrams of (1, the 5-cyclooctadiene) palladium Methochlorides.Shift out flask and place under the argon gas atmosphere from glove box.Add 20 milliliters of methylene dichloride in the solid mixture and obtain a kind of orange solution.Mixture was stirred 4 hours.Add 20 milliliters of hexanes then and obtain the orange solids throw out.Sleeve pipe stays red/orange solids thing except that desolvating after filtration.Use 3 * 10 milliliters of hexane wash solidss subsequently and its drying under vacuum is obtained 490 milligrams of described title complexs (83% yield).
1H NMR meets described structure.
Embodiment 35
Synthesizing of following formula material
In a glove box, in the Schlenk flask, pack 490 milligram 2 into, two (2,6-diisopropyl phenyl imino-)-[1,4] dithiane palladium Methochloride and the 738 milligrams of NaBAr of 3-
4(Ar=3 wherein, 5-is two-trifluoromethyl).Shift out flask and place under the argon gas atmosphere from glove box.Add 25 milliliters of methylene dichloride in the solid mixture and 0.2 milliliter of acetonitrile obtains a kind of orange solution.Mixture was stirred 3 hours.Then with solution after filtration sleeve pipe remove and to desolvate and stay gray solid thing (NaCl).Solvent removed in vacuo obtains a kind of orange glassy mass (the described title complex of 1.1 grams, 90% yield) subsequently.
1H NMR meets described structure.
Embodiment 36
With 2, the Nickel Bromide title complex of two (2,6-3,5-dimethylphenyl imino-)-[1, the 4] dithiane of 3-carries out the polymerization of ethene in the presence of MAO
Be furnished with the magnetic force splash bar and be stamped in membranous 200 milliliters of pyriform Schlenk flasks and pack 5.3 milligram 2 into, the Nickel Bromide title complex of two (2,6-3,5-dimethylphenyl imino-)-[1, the 4] dithiane of 3-.Flask is found time and reinstall ethene, the toluene of pack into then 75 milliliters of dryings, deoxidation.The suspension that obtains is cooled to 0 ℃ and with 1 atmospheric ethene balance 15 minutes, uses the toluene solution processing of 4.0 milliliter of 10% (weight) MAO then and under 1 atmospheric ethene, stir.Observing white polyethylene throw out (having light reddish-brown) in several minutes forms.After 10 minutes, by adding acetone (50 milliliters), methyl alcohol (50 milliliters) and the 6NHCl aqueous solution (100 milliliters) with the mixture quenching.Swollen polyethylene and water, methyl alcohol and the washing with acetone of separating out by isolated by vacuum filtration, dry 48 hours of decompression (0.05-0.1 mm Hg) and obtain 2.5 gram white polyethylenes then.Use 0.104 milligram of nickel complex (100 microlitres are dissolved in the 1.04mg/mL stock solution of 1,2-Difluorobenzene) to carry out similar reaction at 21.5 ℃ and obtain 426 milligrams of polyethylene (359000TO/h) after 14 minutes.
1A H NMR:24 branch/1000 carbon atoms.GPC：M
n＝810000；M
w/M
n＝2.3。
Embodiment 37
Use is by 2, two (2,6-3,5-dimethylphenyl imino-)-[1, the 4] dithiane of 3-, two (1, the 5-cyclooctadiene) nickel (O) and HB (Ar)
4The catalyzer of [Ar=3, two (trifluoromethyl) phenyl of 5-] preparation on the spot carries out the polymerization of ethene
Are being furnished with magnetic force splash bar and being stamped pack in membranous 250 milliliters of pyriform Schlenk flasks 20 milligrams of two (1, the 5-cyclooctadiene) nickel (O), 33 milligram 2, two (2,6-3,5-dimethylphenyl imino-)-[1,4] dithiane and the 83 milligrams of HB (Ar) of 3-
4The ether solvent thing.Flask is found time and reinstall ethene, the toluene of pack into then 75 milliliters of dryings, deoxidation.Under ethene atmosphere, at 25 ℃ the deep purple solution that obtains was stirred 30 minutes, then by adding acetone (50 milliliters) and methyl alcohol (50 milliliters) with the mixture quenching.The polyethylene of separating out by isolated by vacuum filtration also use washing with acetone, then decompression (0.5 mm Hg) drying 18 hours and obtain 339 milligrams of white polyethylenes (332TO/h).
1A H NMR:47 branch/1000 carbon atoms.GPC：M
n＝180000；M
w/M
n＝2.4。
Embodiment 38
With 2, the Nickel Bromide title complex of two (2,6-3,5-dimethylphenyl imino-)-[1, the 4] dithiane of 3-carries out the polymerization of ethene in the presence of MAO
In being furnished with 200 milliliters of pyriform Schlenk flasks of magnetic force splash bar, pack 0.5 milliliter 2 into, the stock solution (10 milligrams of per 10 milliliters of methylene dichloride) of the Nickel Bromide title complex of two (2,6-3,5-dimethylphenyl imino-)-[1, the 4] dithiane of 3-.Flask is found time and reinstall ethene, the toluene of pack into then 75 milliliters of dryings, deoxidation.Place water-bath (23 ℃) also to handle and under 1 atmospheric ethene, stir reaction flask with the toluene solution of 1.0 milliliter of 10% (weight) MAO.Observing the white polyethylene throw out in the several seconds forms.After 5 minutes, by adding acetone, methyl alcohol and the 6N HCl aqueous solution with the mixture quenching.The swollen polyethylene of separating out by isolated by vacuum filtration is also used washing with acetone.With dry several hrs in the vacuum drying oven of polymkeric substance under 80 ℃ that obtains.Isolate 580 milligrams of white rubber shape solidss (285000 TO/h).DSC:(heats for the second time) wide fusion range, the heat absorption maximum value is at 87 ℃.
1A H NMR:37 branch/1000 carbon atoms.GPC：M
n＝186000；M
w/M
n＝2.06。
Embodiment 39
With 2, the Nickel Bromide title complex of two (2,6-diisopropyl phenyl imino-)-[1, the 4] dithiane of 3-carries out the polymerization of ethene in the presence of MAO
In being furnished with 200 milliliters of pyriform Schlenk flasks of magnetic force splash bar, pack 0.5 milliliter 2 into, the stock solution (10 milligrams of per 10 milliliters of methylene dichloride) of the Nickel Bromide title complex of two (2,6-diisopropyl phenyl imino-)-[1, the 4] dithiane of 3-.Flask is found time and reinstall ethene, the toluene of pack into then 75 milliliters of dryings, deoxidation.Place water-bath also to handle and under 1 atmospheric ethene, stir reaction flask with the toluene solution of 1.0 milliliter of 10% (weight) MAO.After 10 minutes, by adding acetone, methyl alcohol and the 6N HCl aqueous solution with the mixture quenching.The swollen polyethylene of separating out by isolated by vacuum filtration is also used washing with acetone.With dry several hrs in the vacuum drying oven of polymkeric substance under 80 ℃ that obtains.Isolate 210 milligrams of white rubber shape amorphous polymers (63000TO/h).DSC:(heats for the second time) wide fusion range, reach the heat absorption maximum value at 6 ℃.
1A H NMR:92 branch/1000 carbon atoms.GPC：M
n＝146000；M
w/M
n＝1.85。
Embodiment 40
In the MMAO (methylaluminoxane of modification; 23% isobutyl aluminium alkoxide) existence is down with 2, and the Nickel Bromide title complex of two (2,6-3,5-dimethylphenyl imino-)-[1, the 4] dithiane of 3-carries out the polymerization of ethene
At first with 600 milliliters of Parr
Autoclave under high vacuum, be heated to about 100 ℃ to guarantee the reactor drying.Clean with reactor cooling and with argon gas.Under argon gas atmosphere, add 150 milliliters of toluene and 0.3 milliliter 2, the stock solution (10 milligrams of per 10 milliliters of methylene dichloride) of the Nickel Bromide title complex of two (2,6-3,5-dimethylphenyl imino-)-[1, the 4] dithiane of 3-in the autoclave.Autoclave is heated to 40 ℃ and add the n-heptane solution (6.42% aluminium) of 2 milliliters of MMAO.(gauge pressure psig) and with temperature is raised to 50 ℃ with ethene reactor to be pressurized to 100 pounds/square inch fast.At 50 ℃ after 10 minutes, will react all standing by adding acetone and methyl alcohol.Dry several hrs in swollen polyethylene of separating out by separation and the vacuum drying oven under 80 ℃.Isolate 4.8 gram white rubber shape solidss (2000000TO/h).DSC:(heats for the second time) wide fusion range, the heat absorption maximum value is at 97 ℃.
1A H NMR:28 branch/1000 carbon atoms.GPC：M
n＝155000；M
w/M
n＝2.10。
Embodiment 41
With 2, the Nickel Bromide title complex of two (2,6-3,5-dimethylphenyl imino-)-[1, the 4] dithiane of 3-carries out the polymerization of ethene in the presence of MMAO (23% isobutyl aluminium alkoxide)
At first with 600 milliliters of Parr
Autoclave under high vacuum, be heated to about 100 ℃ to guarantee the reactor drying.Clean with reactor cooling and with argon gas.Under argon gas atmosphere, add 150 milliliters of toluene and 0.3 milliliter 2, the stock solution (10 milligrams of per 10 milliliters of methylene dichloride) of the Nickel Bromide title complex of two (2,6-3,5-dimethylphenyl imino-)-[1, the 4] dithiane of 3-in the autoclave.Autoclave is cooled to 15 ℃ and add the n-heptane solution (6.42% (weight) aluminium) of 2 milliliters of MMAO.(gauge pressure psig) and with temperature is raised to 25 ℃ with ethene autoclave to be pressurized to 100 pounds/square inch fast.At 25 ℃ after 10 minutes, will react all standing by adding acetone and methyl alcohol.Dry several hrs in swollen polyethylene that separation is separated out and the vacuum drying oven under 80 ℃.Isolate 4.4 gram white rubber shaped polyethylenes (1800000TO/h).DSC:(heats for the second time) fusion, the heat absorption maximum value is at 125 ℃.
1A H NMR:6 branch/1000 carbon atoms.GPC：M
n＝598000；M
w/M
n＝2.12。
Embodiment 42
With 2, the Nickel Bromide title complex of two (2,6-3,5-dimethylphenyl imino-)-[1, the 4] dithiane of 3-carries out the polymerization of ethene in the presence of MMAO (23% isobutyl aluminium alkoxide)
At first with 600 milliliters of Parr
Autoclave under high vacuum, be heated to about 100 ℃ to guarantee the reactor drying.Clean with reactor cooling and with argon gas.Under argon gas atmosphere, add 150 milliliters of toluene and 1.0 milliliter 2, the stock solution (10 milligrams of per 10 milliliters of methylene dichloride) of the Nickel Bromide title complex of two (2,6-3,5-dimethylphenyl imino-)-[1, the 4] dithiane of 3-in the autoclave.Autoclave is heated to 55 ℃ and add the n-heptane solution (6.42% (weight) aluminium) of 2 milliliters of MMAO.With ethene autoclave is pressurized to 100psig fast and temperature is raised to 65 ℃.At 65 ℃ after 10 minutes, will react all standing by adding acetone and methyl alcohol.Dry several hrs in swollen polyethylene that separation is separated out and the vacuum drying oven under 80 ℃.Isolate 5.3 gram white rubber shape solidss (640000TO/h).DSC:(heats for the second time) fusion, the heat absorption maximum value is at 78 ℃.
1A H NMR:47 branch/1000 carbon atoms.GPC：M
n＝86000；M
w/M
n＝1.95。
Embodiment 43
With 2, the Nickel Bromide title complex of two (2,6-3,5-dimethylphenyl imino-)-[1, the 4] dithiane of 3-carries out the polymerization of ethene in the presence of MMAO (23% isobutyl aluminium alkoxide)
At first with 600 milliliters of Parr
Autoclave under high vacuum, be heated to about 100 ℃ to guarantee the reactor drying.Clean with reactor cooling and with argon gas.Under argon gas atmosphere, add 150 milliliters of toluene and 1.0 milliliter 2, the stock solution (10 milligrams of per 10 milliliters of methylene dichloride) of the Nickel Bromide title complex of two (2,6-3,5-dimethylphenyl imino-)-[1, the 4] dithiane of 3-in the autoclave.Autoclave is heated to 70 ℃ and add the n-heptane solution (6.42% (weight) aluminium) of 2 milliliters of MMAO.With ethene autoclave is pressurized to 100psig fast and temperature is raised to 80 ℃.At 80 ℃ after 10 minutes, will react all standing by adding acetone and methyl alcohol.Dry several hrs in swollen polyethylene that separation is separated out and the vacuum drying oven under 80 ℃.Isolate 3.5 gram white rubber shape solidss (440000TO/h).DSC:(heats for the second time) fusion, the heat absorption maximum value is at 67 ℃.
1A H NMR:53 branch/1000 carbon atoms.GPC：M
n＝87000；M
w/M
n＝1.66。
Embodiment 44
With 2, the Nickel Bromide title complex of two (2,6-diisopropyl phenyl imino-)-[1, the 4] dithiane of 3-carries out the polymerization of ethene in the presence of MMAO (23% isobutyl aluminium alkoxide)
At first with 600 milliliters of Parr
Autoclave under high vacuum, be heated to about 100 ℃ to guarantee the reactor drying.Clean with reactor cooling and with argon gas.Under argon gas atmosphere, add 150 milliliters of toluene and 0.5 milliliter 2, the stock solution (10 milligrams of per 10 milliliters of methylene dichloride) of the Nickel Bromide title complex of two (2,6-diisopropyl phenyl imino-)-[1, the 4] dithiane of 3-in the autoclave.Autoclave is heated to 40 ℃ and add the n-heptane solution (6.42% (weight) aluminium) of 2 milliliters of MMAO.With ethene autoclave is pressurized to 100psig fast and temperature is raised to 50 ℃.At 50 ℃ after 10 minutes, will react all standing by adding acetone and methyl alcohol.Dry several hrs in swollen polyethylene that separation is separated out and the vacuum drying oven under 80 ℃.Isolate 2.4 gram white rubber shape solidss (700000TO/h).DSC:(heats for the second time) fusion, the heat absorption maximum value is at 46 ℃.
1A H NMR:75 branch/1000 carbon atoms.GPC：M
n＝966000；M
w/M
n＝1.70。
Embodiment 45
With 2, the Nickel Bromide title complex of two (2,6-diisopropyl phenyl imino-)-[1, the 4] dithiane of 3-carries out the polymerization of ethene in the presence of MMAO (23% isobutyl aluminium alkoxide)
Except be aggregated in carry out under 80 ℃, carry out polymerization according to the described step of embodiment 44.Isolate 1.4 gram white rubber shape solidss (400000TO/h).DSC:(heats for the second time) fusion, the heat absorption maximum value is at 0 ℃.
1A H NMR:95 branch/1000 carbon atoms.GPC：M
n＝406000；M
w/M
n＝2.05。
Embodiment 46
With 2, the Nickel Bromide title complex of two (2,6-diisopropyl phenyl imino-)-[1, the 4] dithiane of 3-carries out the polymerization of ethene in the presence of MMAO (23% isobutyl aluminium alkoxide)
Except be aggregated in carry out under 65 ℃, carry out polymerization according to the described step of embodiment 44.Isolate 2.15 gram white rubber shape solidss (630000TO/h).DSC:(heats for the second time) fusion, the heat absorption maximum value is at 15 ℃.
1A H NMR:89 branch/1000 carbon atoms.GPC：M
n＝502000；M
w/M
n＝1.78。
Embodiment 47
With 2, the Nickel Bromide title complex of two (2,6-diisopropyl phenyl imino-)-[1, the 4] dithiane of 3-carries out the polymerization of ethene in the presence of MMAO (23% isobutyl aluminium alkoxide)
Except be aggregated in carry out under 25 ℃, carry out polymerization according to the described step of embodiment 44.Isolate 1.9 gram white rubber shape solidss (560000TO/h).DSC:(heats for the second time) fusion, the heat absorption maximum value is at 90 ℃.
1A H NMR:33 branch/1000 carbon atoms.GPC：M
n＝839000；M
w/M
n＝1.37。
Embodiment 48
With 2, the Nickel Bromide title complex of two (phenylimino)-[1,4] of 3-dithiane becomes alpha-olefin with ethylene oligomerization in the presence of MAO
One liter of Fischer-Porter bottle is connected on the pressure cover of being furnished with mechanical stirrer and gas-liquid material hole, is pressurized to 75psig and pressure relief several times with ethene then to environmental stress.Immerse bottle in 21.5 ℃ of water-baths and add the toluene of 50 milliliters of dryings, deoxidation by syringe, then add 100 microlitres 15.3 milligram 2, two (phenylimino)-[1 of 3-, 4] stock solution of the Nickel Bromide title complex of dithiane in 15.0 milliliters of methylene dichloride then adds other 50 milliliters of toluene again.Under the 75psig ethylene pressure, made solution saturated in 5 minutes in mixture, release pressure then, and add 10% (weight) toluene solution of 4.0 milliliters of MAO fast by ethene with 300 rev/mins (rpm) stirring.Flask is pressurized to 75psig with ethene more immediately and stirs with 300rpm.After 30 minutes, release pressure and make the reaction all standing by adding 10 ml methanol.Behind the device of dismantling, add 40 ml methanol, 50 milliliters of the 6N HCl aqueous solution and 10 milliliters of acetone in addition and stir the mixture and make the MAO complete hydrolysis.The organic layer that separation obtains after the 6NHCl aqueous solution (1 * 25 milliliter) and water (2 * 50 milliliters) washing, concentrates a kind of oil of acquisition in 40 ℃ of decompressions (15 holder).It is handled and reconcentration twice with toluene (50 milliliters), use acetone (50 milliliters) processing and reconcentration then and obtain a kind of wax shape white polyethylene solids.Acquisition in dry 14 hours 0.180 restrains to contain about 85% alpha-olefin and 15% internal olefin and have and is about 517 M under 100 ℃ of vacuum (250 mm Hg)
nPolymkeric substance.
Embodiment 49
In the presence of MAO with 2, two (2,6-3,5-dimethylphenyl imino-)-2 of 3-, the Nickel Bromide title complex of 3-dihydrobenzo [1,4] dithine carries out vinyl polymerization
Be furnished with the magnetic force splash bar and be stamped the toluene of pack in membranous 200 milliliters of pyriform Schlenk flasks 100 milliliters of dryings, deoxidation.Flask placed water-bath and with 1 atmospheric ethene balance 10 minutes, add 0.25 milliliter then by 10.2 milligram 2,3-two (2,6-3,5-dimethylphenyl imino-)-2, the Nickel Bromide title complex of 3-dihydrobenzo [1,4] dithine is dry at 13.11 grams, the stock solution of the dichloromethane solution preparation of deoxidation.Use the toluene solution of 4.0 milliliter of 10% (weight) MAO to handle this reaction mixture and under 1 atmospheric ethene, stir then.Observe the suction and the sedimentary formation of polyethylene of ethene.6.5 after minute, by adding acetone (50 milliliters), methyl alcohol (50 milliliters) and the 6N HCl aqueous solution (100 milliliters) with the mixture quenching.The swollen polyethylene of separating out by isolated by vacuum filtration and under 80 ℃ of vacuum dry several hours.Isolate 287 milligrams of white powder shaped polyethylenes (236000TO/h).DSC:(heats for the second time) fusion, the heat absorption maximum value is at 88 ℃.
1H NMR shows that this material contains about 36 branch/1000 carbon atoms.GPC：M
n＝145000；M
w/M
n＝2.35。
Embodiment 50
Use is by 2, two (2,6-diisopropyl phenyl imino-)-[1,4]-dithiane of 3-and [Pd (NCCH
3)
4] [BF
4]
2Zhi Bei catalyzer carries out the polymerization of ethene on the spot
Be furnished with the magnetic force splash bar and be stamped 0.022 gram 2 of packing in membranous 200 milliliters of pyriform Schlenk flasks, two (2,6-diisopropyl phenyl imino-)-[1,4]-dithiane of 3-and 0.019 gram [Pd (NCCH
3)
4] [BF
4]
2Flask found time and reinstall ethene, then by pack into the methylene dichloride of 100 milliliters of dryings, deoxidation and the reaction mixture that obtains stirred under 1 atmospheric ethene at 25 ℃ of syringe.Observing considerably less ethene is ingested.After 10 minutes, add 0.412 gram B (C
6F
5)
3The ethene uptake rate is increased.After 84 minutes, come reaction mixture altogether, repeat with the methanol wash residue to extract B (C by under nitrogen gas stream, evaporating methylene dichloride
6F
5)
3, and residue dried under vacuum obtained 0.57 gram amorphous polyethylene, its M
nBe about 17000; M
n/ M
wBe 1.3.
1H NMR shows about 105 branch/1000 carbon atoms.
Embodiment 51
With 2, the Nickel Bromide title complex of two (4-methoxyl group-2,6-3,5-dimethylphenyl imino-)-[1, the 4] dithiane of 3-carries out vinyl polymerization in the presence of MAO
To reinstall ethene after flask is found time, dried at the bottom of 500 milliliters of gardens that Schlenk takes over being furnished with the magnetic force splash bar and being stamped barrier film and being furnished with.Flask placed the toluene of the water-bath under the room temperature (about 23 ℃) and pack into 100 milliliters of dryings, deoxidation and with 1 atmospheric ethene balance 30 minutes.Then reaction mixture is handled and stirred under 1 normal atmosphere ethene with 10% (weight) toluene solution of 4.0 milliliters of MAO, add 0.10 milliliter then by 6.3 milligram 2, two (the 4-methoxyl groups-2 of 3-, the stock solutions of the Nickel Bromide title complex of dithiane and 6.5 milliliters of methylene dichloride preparation 6-3,5-dimethylphenyl imino-)-[1,4].After 10 minutes, by adding acetone, methyl alcohol and the 6N HCl aqueous solution with the reaction mixture quenching.Polyethylene and water, methyl alcohol and the washing with acetone of separating out by isolated by vacuum filtration, after on the strainer dry 2 hours in 80 ℃ of vacuum drying ovens dry 13 days again.Isolate 182 milligrams of white polyethylenes (254000TO/n).DSC:(heats for the second time) fusion, the heat absorption maximum value is at 124 ℃.
1A H NMR:13 branch/1000 carbon atoms.GPC：M
n＝145600；M
w/M
n＝2.6。
Embodiment 52
At (CH
3CH
2)
2The existence of AlCl is down with 2, and the Nickel Bromide title complex of two (2,6-diisopropyl phenyl imino-)-[1, the 4] dithiane of 3-carries out the polymerization of ethene
At first with 600 milliliters of Parr
Autoclave under high vacuum, be heated to about 100 ℃ to guarantee the reactor drying.Clean with reactor cooling and with argon gas.Under argon gas atmosphere, add 150 milliliters of toluene and 0.5 milliliter 2, the stock solution (10 milligrams of per 10 milliliters of methylene dichloride) of the Nickel Bromide title complex of two (2,6-diisopropyl phenyl imino-)-[1, the 4] dithiane of 3-in the autoclave.Autoclave is heated to 45 ℃ and add 2 milliliters of (CH
3CH
2)
2The toluene solution of AlCl (5000equiv.).Autoclave is pressurized to 100psig fast and temperature is raised to 50 ℃.At 50 ℃ after 10 minutes, will react all standing by adding acetone and methyl alcohol.Dry several hrs obtains 1.9 gram white rubber shape solidss (560000TO/h) in swollen polyethylene of separating out by filtering separation and the vacuum drying oven under 80 ℃.DSC:(heats for the second time) wide fusion range, the heat absorption maximum value is at 30 ℃.
1A H NMR:87 branch/1000 carbon atoms.GPC：M
n＝557000；M
w/M
n＝1.82。
Embodiment 53
At (CH
3CH
2)
2The existence of AlCl is down with 2, and the Nickel Bromide title complex of two (2,6-diisopropyl phenyl imino-)-[1, the 4] dithiane of 3-carries out the polymerization of ethene
At first with 600 milliliters of Parr
Autoclave under high vacuum, be heated to about 100 ℃ to guarantee the reactor drying.Clean with reactor cooling and with argon gas.Under argon gas atmosphere, add 150 milliliters of toluene and 0.5 milliliter 2, the stock solution (10 milligrams of per 10 milliliters of methylene dichloride) of the Nickel Bromide title complex of two (2,6-diisopropyl phenyl imino-)-[1, the 4] dithiane of 3-in the autoclave.Autoclave is heated to 45 ℃ and add 0.2 milliliter of (CH
3CH
2)
2The toluene solution of AlCl (500equiv.).Reactor is pressurized to 100psig fast and temperature is raised to 50 ℃.At 50 ℃ after 10 minutes, will react all standing by adding acetone and methyl alcohol.Dry several hrs obtains 2 gram white rubber shape solidss (590000TO/h) in swollen polyethylene of separating out by filtering separation and the vacuum drying oven under 80 ℃.DSC:(heats for the second time) wide fusion range, the heat absorption maximum value is at 30 ℃.
1A H NMR:85 branch/1000 carbon atoms.GPC：M
n＝515000；M
w/M
n＝1.81。
Embodiment 54
At (CH
3CH
2)
2The existence of AlCl is down with 2, and the Nickel Bromide title complex of two (2,6-diisopropyl phenyl imino-)-[1, the 4] dithiane of 3-carries out the polymerization of ethene
At first with 600 milliliters of Parr
Autoclave under high vacuum, be heated to about 100 ℃ to guarantee the reactor drying.Clean with reactor cooling and with argon gas.Under argon gas atmosphere, add 150 milliliters of toluene and 0.5 milliliter 2, the stock solution (10 milligrams of per 10 milliliters of methylene dichloride) of the Nickel Bromide title complex of two (2,6-diisopropyl phenyl imino-)-[1, the 4] dithiane of 3-toward autoclave.Autoclave is heated to 45 ℃ and add 0.04 milliliter of (CH
3CH
2)
2The toluene solution of AlCl (100equiv.).Autoclave is pressurized to 100psig fast and temperature is raised to 50 ℃.At 50 ℃ after 10 minutes, will react all standing by adding acetone and methyl alcohol.Dry several hrs obtains 1.5 gram white rubber shape solidss (440000TO/h) in swollen polyethylene of separating out by filtering separation and the vacuum drying oven under 80 ℃.DSC:(heats for the second time) wide fusion range, the heat absorption maximum value is at 29 ℃.
1A H NMR:80 branch/1000 carbon atoms.GPC：M
n＝422000；M
w/M
n＝1.97。
Embodiment 55
With 2, the Nickel Bromide title complex of two (2,6-3,5-dimethylphenyl imino-)-[1, the 4] dithiane of 3-carries out the copolymerization of ethene and undecylene acetoacetic ester in the presence of MMAO (23% isobutyl aluminium alkoxide)
Pack in the Schlenk flask of an oven dry of being furnished with splash bar and diaphragm of rubber 50 milliliters of toluene and 5 milligram 2, the Nickel Bromide title complex of two (2,6-3,5-dimethylphenyl imino-)-[1, the 4] dithiane of 3-.In ice-water-bath, flask is cooled to 0 ℃ and the ethene of packing into (1 normal atmosphere).The n-heptane solution (6.42% (weight) aluminium) that adds 2.0 milliliters of MMAO in the flask.In 5 seconds, add 5 milliliters of undecylene acetoacetic esters and obtain a kind of purple solution.Mixture was stirred 16 hours.Add that acetone, methyl alcohol and 6M HCl make the reaction all standing and with polymer precipitation.By the suction strainer collected polymer and with a large amount of washing with acetones to guarantee removing all undecylene acetoacetic ester comonomers, obtain 100 milligrams of white powder shaped polymers.Nuclear magnetic resonance spectroscopy result with to prepare to contain the ester group multipolymer consistent.In addition, also there is the Alathon that is produced by the preceding short reaction time of undecylene acetoacetic ester adding.
1H NMR: sneaked into 7.5% (weight) undecylene acetoacetic ester.GPC：M
n＝9500；M
w/M
n＝16.6。DSC：T
m＝128℃。
Embodiment 56
With 2, the Nickel Bromide title complex of two (2,6-3,5-dimethylphenyl imino-)-[1, the 4] dithiane of 3-carries out ethene and 1, the copolymerization of 13-14 carbon diene in the presence of MAO
200 milliliters of pyriform Schlenk flasks being furnished with magnetic force splash bar and diaphragm of rubber are dried and reinstall ethene under vacuum, the order toluene, 6.0 milliliters that add 50 milliliters of dryings, deoxidation is sloughed 1 of oxygen then, 13-14 carbon diene and 1.0 milliliters 11.8 milligrams 2,3-two (2,6-3,5-dimethylphenyl imino-)-[1,4] stock solution of the Nickel Bromide title complex of dithiane in the methylene dichloride of 10.0 milliliters of dryings, deoxidation.Flask placed 23 ℃ of water-baths and allow it with 1 atmospheric ethene balance 5 minutes, add 10% toluene solution of 4.0 milliliters of MAO then and mixture is stirred under 1 atmospheric ethene.Observe the absorption of ethene and the mixture thickness that becomes fast.After 7 minutes, will react all standing by adding acetone (50 milliliters), methyl alcohol (50 milliliters) and the 6NHCl aqueous solution (100 milliliters).The described multipolymer of separating out by isolated by vacuum filtration also obtained 0.72 gram rubber-like white polymer in dry 24 hours under 100 ℃ of vacuum, it forms gel in attempting to be dissolved in again the orthodichlorobenzene of heat the time.
Embodiment 57
With 2, the Nickel Bromide title complex of two (2,6-3,5-dimethylphenyl imino-)-[1,4]-dioxs of 3-carries out vinyl polymerization in the presence of MAO
Add 3.4 milligram 2 toward being furnished with the magnetic force splash bar and being stamped in membranous 200 milliliters of pyriform Schlenk flasks, two (2,6-3,5-dimethylphenyl imino-)-[the Nickel Bromide title complexs of 1,4] diox of 3-.Reinstall ethene after flask found time, the 75 milliliters of dryings of packing into then, slough the toluene of oxygen.The suspension that obtains is cooled to 0 ℃ and with 1 atmospheric ethene balance 15 minutes, uses 10% (weight) toluene solution processing of 4.0 milliliters of MAO then and under 1 normal atmosphere ethene, stir.Observe white polyethylene throw out (Huang that tool is light-orange) in several minutes.After 38 minutes, by adding acetone (50 milliliters), methyl alcohol (50 milliliters) and the 6N HCl aqueous solution (100 milliliters) with the reaction mixture quenching.By swollen polyethylene and water, methyl alcohol and washing with acetone that isolated by vacuum filtration is separated out, decompression (0.05-0.1 mm Hg) obtained 6.0 gram white polyethylenes (54000TO/h) in dry 18 hours then.
1A H NMR:19 branch/1000 carbon atoms.GPC：M
n＝504000；M
w/M
n＝2.3。
Embodiment 58
In the presence of MAO with 2, two (benzyloxymethyl)-5 of 3-, 6-is two, and (2,6-3,5-dimethylphenyl imino-)-[the Nickel Bromide title complex of 1,4] diox carries out vinyl polymerization
Will be furnished with the magnetic force splash bar and be stamped barrier film and be furnished with 500 milliliters of gardens that Schlenk takes at the bottom of flask pack into the 100ml drying, slough the toluene of oxygen.Flask placed water-bath and with 1 atmospheric ethene balance 19 minutes.Add 0.25 milliliter then by 10 milligram 2, two (benzyloxymethyl)-5 of 3-, 6-two (2, the 6-3,5-dimethylphenyl imino-)-[stock solutions of the Nickel Bromide title complex of 1,4] diox and 10 milliliters of methylene dichloride preparations.Then reaction mixture is handled and stirred under 1 normal atmosphere ethene with 10% (weight) toluene solution of 4.0 milliliters of MAO.Observe the absorption and the sedimentary formation of polyethylene of ethene.6.5 after minute, by adding acetone, methyl alcohol and the 6N HCl aqueous solution with the reaction mixture quenching.The swollen polyethylene of separating out by isolated by vacuum filtration is then at 80 ℃ of vacuum-drying several hrs.Isolate 392 milligrams of white polyethylenes (404000TO/h).DSC:(heats for the second time) fusion, the heat absorption maximum value is at 120 ℃.
1A H NMR:16 branch/1000 carbon atoms.GPC：M
n＝125000；M
w/M
n＝2.8。
Embodiment 59
With 5-methoxymethyl-2, the Nickel Bromide title complex of two (2,6-3,5-dimethylphenyl imino-)-[1,4]-dioxs of 3-carries out vinyl polymerization in the presence of MAO
Add 3.8 milligrams of 5-methoxymethyies-2 in membranous 200 milliliters of pyriform Schlenk flasks, two (2,6-3,5-dimethylphenyl imino-)-[the Nickel Bromide title complexs of 1,4] diox of 3-toward being furnished with the magnetic force splash bar and being stamped.Reinstall ethene after flask found time, the 75 milliliters of dryings of packing into then, slough the toluene of oxygen.The suspension that obtains is cooled to 0 ℃ and with 1 atmospheric ethene balance 15 minutes, uses 10% (weight) toluene solution processing of 4.0 milliliters of MAO then and under 1 normal atmosphere ethene, stir.After 10 minutes, by adding acetone (50 milliliters), methyl alcohol (50 milliliters) and the 6N HCl aqueous solution (100 milliliters) with the reaction mixture quenching.By swollen polyethylene and water, methyl alcohol and washing with acetone that isolated by vacuum filtration is separated out, decompression (0.05-0.1mm Hg) obtained 1.04 gram white powder shaped polyethylenes in dry 48 hours then.Use 11.6 milligrams of 5-methoxymethyies-2 of 0.655 gram, 3-two (2,6-3,5-dimethylphenyl imino-)-[1,4] the Nickel Bromide title complex of diox is at the stock solutions (be equivalent to 0.57 milligram described nickel complex) of 13.238 grams in the methylene dichloride, obtains 291 milligrams of white powder shaped polyethylenes at 0 ℃ after similarly reacting 15 minutes.
Embodiment 60
In the presence of MMAO (23% isobutyl aluminium alkoxide), with 2,3-is two, and (2,6-3,5-dimethylphenyl imino-)-[the Nickel Bromide title complex of 1,4] diox carries out the polymerization of ethene
At first with 600 milliliters of Parr
Autoclave under high vacuum, be heated to about 100 ℃ to guarantee the reactor drying.Clean with reactor cooling and with argon gas.Under argon gas atmosphere, add 150 milliliters of toluene and 0.3 milliliter 2, two (2, the 6-3,5-dimethylphenyl imino-)-[stock solutions of the Nickel Bromide title complex of 1,4] diox (10 milligrams of per 10 milliliters of methylene dichloride) of 3-in the autoclave.Autoclave is heated to 60 ℃ and add the n-heptane solution (6.42% (weight) aluminium) of 2 milliliters of MMAO.Reactor is pressurized to 100psig fast and temperature is raised to 65 ℃.At 65 ℃ after 10 minutes, will react all standing by adding acetone and methyl alcohol.Dry several hrs in swollen polyethylene of separating out by filtering separation and the vacuum drying oven under 80 ℃.Isolate 1.3 gram white rubber shape solidss (480000TO/h).DSC:(heats for the second time) fusion, the heat absorption maximum value is at 76 ℃.
1A H NMR:33 branch/1000 carbon atoms.GPC：M
n＝42000；M
w/M
n＝1.82。
Embodiment 61
With 2,3-is two, and (2,6-3,5-dimethylphenyl imino-)-[the Nickel Bromide title complex of 1,4] diox carries out the polymerization of ethene in the presence of MMAO (23% isobutyl aluminium alkoxide)
Except be aggregated in carry out under 25 ℃, carry out polymerization according to the described step of embodiment 60, obtain 0.59 the gram polyethylene (226000TO/h).DSC:(heats for the second time) fusion, the heat absorption maximum value is at 125 ℃.
1A H NMR:9 branch/1000 carbon atoms.GPC：M
n＝237000；M
w/M
n＝2.15。
Embodiment 62
With 2,3-is two, and (2,6-3,5-dimethylphenyl imino-)-[the Nickel Bromide title complex of 1,4] diox carries out the polymerization of ethene in the presence of MMAO (23% isobutyl aluminium alkoxide)
Except be aggregated in carry out under 80 ℃, carry out polymerization according to the described step of embodiment 60, obtain 0.29 the gram polyethylene (110000TO/h).
1A H NMR:69 branch/1000 carbon atoms.GPC：M
n＝23000；M
w/M
n＝1.65。
Embodiment 63
With 2,3-is two, and (2,6-3,5-dimethylphenyl imino-)-[the Nickel Bromide title complex of 1,4] diox carries out the polymerization of ethene in the presence of MMAO (23% isobutyl aluminium alkoxide)
Except be aggregated in carry out under 50 ℃, carry out polymerization according to the described step of embodiment 60, obtain 3.1 the gram polyethylene (1200000TO/h).DSC:(heats for the second time) fusion, the heat absorption maximum value is at 95 ℃.
1A H NMR:48 branch/1000 carbon atoms.GPC：M
n＝63000；M
w/M
n＝1.92。
Embodiment 64
With 2,3-is two, and (2,6-diisopropyl phenyl imino-)-[the Nickel Bromide title complex of 1,4] diox carries out the polymerization of ethene in the presence of MMAO (23% isobutyl aluminium alkoxide)
At first with 600 milliliters of Parr
Autoclave under high vacuum, be heated to about 100 ℃ to guarantee the reactor drying.Clean with reactor cooling and with argon gas.Under argon gas atmosphere, add 150 milliliters of toluene and 0.5 milliliter 2, two (2, the 6-diisopropyl phenyl imino-)-[stock solutions of the Nickel Bromide title complex of 1,4] diox (10 milligrams of per 10 milliliters of methylene dichloride) of 3-in the autoclave.Autoclave is heated to 60 ℃ and add the n-heptane solution (6.42% (weight) aluminium) of 2 milliliters of MMAO.Reactor is pressurized to 100psig fast and temperature is raised to 65 ℃.At 65 ℃ after 10 minutes, will react all standing by adding acetone and methyl alcohol.Dry several hrs in swollen polyethylene of separating out by filtering separation and the vacuum drying oven under 80 ℃.Isolate 2.5 gram white rubber shape solidss (660000TO/h).DSC:(heats for the second time) wide fusion range, the heat absorption maximum value is at 30 ℃.
1A H NMR:82 branch/1000 carbon atoms.GPC：M
n＝147000；M
w/M
n＝1.91。
Embodiment 65
With 2,3-is two, and (2,6-diisopropyl phenyl imino-)-[the Nickel Bromide title complex of 1,4] diox carries out the polymerization of ethene in the presence of MMAO (23% isobutyl aluminium alkoxide)
Except be aggregated in carry out under 50 ℃, carry out polymerization according to the described step of embodiment 64, obtain 3.4 the gram polyethylene (900000TO/h).DSC:(heats for the second time) fusion, the heat absorption maximum value is at 50 ℃.
1A H NMR:65 branch/1000 carbon atoms.GPC：M
n＝219000；M
w/M
n＝1.85。
Embodiment 66
With 2,3-is two, and (2,6-diisopropyl phenyl imino-)-[the Nickel Bromide title complex of 1,4] diox carries out the polymerization of ethene in the presence of MMAO (23% isobutyl aluminium alkoxide)
Except be aggregated in carry out under 25 ℃, carry out polymerization according to the described step of embodiment 64, obtain 1.22 the gram polyethylene (320000TO/h).DSC:(heats for the second time) fusion, the heat absorption maximum value is at 112 ℃.
1A H NMR:17 branch/1000 carbon atoms.GPC：M
n＝476000；M
w/M
n＝2.02。
Embodiment 67
With 2,3-is two, and (2,6-diisopropyl phenyl imino-)-[the Nickel Bromide title complex of 1,4] diox carries out the polymerization of ethene in the presence of MMAO (23% isobutyl aluminium alkoxide)
Except be aggregated in carry out under 80 ℃, carry out polymerization according to the described step of embodiment 64, obtain 0.9 the gram polyethylene (240000TO/h).DSC:(heats for the second time) fusion, the heat absorption maximum value is at 10 ℃.
1A H NMR:99 branch/1000 carbon atoms.GPC：M
n＝98800；M
w/M
n＝1.81。
Embodiment 68
With 2, the Nickel Bromide title complex of two (2,6-3,5-dimethylphenyl imino-)-[1, the 4] dioxs of 3-carries out the copolymerization of ethene and undecylene acetoacetic ester in the presence of MMAO (23% isobutyl aluminium alkoxide)
Pack in the Schlenk flask of an oven dry of being furnished with splash bar and diaphragm of rubber 50 milliliters of toluene and 6 milligram 2, two (2,6-3,5-dimethylphenyl imino-)-[the Nickel Bromide title complexs of 1,4] diox of 3-.Flask is cooled to 0 ℃ and the ethene of packing into (1 normal atmosphere) in ice-water-bath.The n-heptane solution (6.42% (weight) aluminium) that adds 2.0 milliliters of MMAO in the flask.In 15 seconds, add 2.5 milliliters of undecylene acetoacetic esters and obtain a kind of purple solution.Mixture was stirred 16 hours.Add that acetone, methyl alcohol and 6 M HCl make the reaction all standing and with polymer precipitation.By the suction strainer collected polymer and with a large amount of washing with acetones to guarantee removing all undecylene acetoacetic ester comonomers, obtain 510 milligrams of white powder shaped polymers.Nuclear magnetic resonance spectroscopy result with to prepare to contain the ester group multipolymer consistent.In addition, also there is the Alathon that adds preceding short reaction time generation by the undecylene acetoacetic ester.Infrared spectra (IR): at 1742cm
-1The CO ν of place.
1H NMR: sneaked into 1.0% (weight) undecylene acetoacetic ester.GPC：M
n＝61000；M
w/M
n＝6.4。DSC：T
m＝125℃。
Embodiment 69
With 2, two (2,6-diisopropyl phenyl the imino-)-Nickel Bromide title complexs of 4-methylmorpholine of 3-carry out the polymerization of ethene in the presence of MAO
A Fischer-Porter bottle is connected on the pressure cover of being furnished with mechanical stirrer and gas-liquid material hole, is pressurized to 75psig and release of pressure several times with ethene then to environmental stress.Immerse bottle in 54 ℃ of water-baths and add the toluene of 100 milliliters of dryings, deoxidation by syringe.Mixture is pressurized to 75psig and made solution saturated by ethene in 5 minutes with 300 rev/mins (rpm) stirring with ethene again, and then release pressure, and add 10% (weight) toluene solution of 4.0 milliliters of MAO fast.This device is pressurized to 75psig and saturated to guarantee by ethene with 300rpm restir 5 minutes with ethene more immediately.Pressure is released environmental stress again and is then added 0.5 milliliter immediately by 10.0 milligram 2,3-two (2,6-diisopropyl phenyl imino-)-and the Nickel Bromide title complex of 4-methylmorpholine and the stock solution of 10 milliliters of methylene dichloride preparations, then be pressurized to 75psig fast with ethene again.After 7 minutes, pressure is released normal pressure and made the reaction all standing by adding 5 ml methanol.Behind the device of dismantling, add 50 ml methanol, 50 milliliters of 6N HCl aqueous solution and 20 milliliters of acetone in addition.Separate the organic layer obtain, after the 6N HCl aqueous solution (1 * 25 milliliter) and water (2 * 50 milliliters) washing, concentrated at 40 ℃, decompression (10 holder) rotary evaporation.Residue is obtained the transparent polyethylene (55000TO/h) of 134 milligrams of utmost points like rubber with toluene (50 milliliters) processing and reconcentration.
1A H NMR:134 branch/1000 carbon atoms.GPC：M
n＝169000；M
w/M
n＝1.4。
Embodiment 70
With 2, two (2,6-3,5-dimethylphenyl the imino-)-Nickel Bromide title complexs of 4-methylmorpholine of 3-carry out the polymerization of ethene in the presence of MMAO
At first with 600 milliliters of Parr
Autoclave under high vacuum, be heated to about 100 ℃ to guarantee the reactor drying.Clean with reactor cooling and with argon gas.Under argon gas atmosphere, add 150 milliliters of toluene and 1 milliliter 2 in the autoclave, the stock solution of the Nickel Bromide title complex of two (2,6-3,5-dimethylphenyl the imino-)-4-methylmorpholines of 3-(in per 20 milliliters of methylene dichloride 10 milligrams).Autoclave is heated to 45 ℃ and add the n-heptane solution (6.42% (weight) aluminium) of 3 milliliters of MMAO.Reactor is pressurized to 100psig fast and temperature is raised to 50 ℃.At 50 ℃ after 10 minutes, will react all standing by adding acetone and methyl alcohol.Dry several hrs obtains 0.87 gram white rubber shape solids (138000TO/h) in swollen polyethylene of separating out by filtering separation and the vacuum drying oven under 80 ℃.
1A H NMR:97 branch/1000 carbon atoms.
Embodiment 71
In the presence of MAO with 1, two (4-methoxyl group-2, the 6-3,5-dimethylphenyls)-4 of 3-, the Nickel Bromide title complex of two (4-methoxyl group-2, the 6-3,5-dimethylphenyl imino-) tetrahydroglyoxaline-2-ketone of 5-carries out vinyl polymerization
To reinstall ethene after flask is found time, dried at the bottom of 500 milliliters of gardens that Schlenk takes over being furnished with the magnetic force splash bar and being stamped barrier film and being furnished with.Flask placed the toluene of the water-bath under the room temperature (about 23 ℃) and pack into 100 milliliters of dryings, deoxidation and with 1 atmospheric ethene balance 30 minutes, simultaneously with the speed stirring of 1000rpm.Then reaction mixture is handled and stirred under 1 normal atmosphere ethene with 10% (weight) toluene solution of 4.0 milliliters of MAO, add 0.10 milliliter then by 6.0 milligram 1, two (the 4-methoxyl groups-2 of 3-, the 6-3,5-dimethylphenyl)-4, the stock solution of the Nickel Bromide title complex of two (4-methoxyl group-2, the 6-3,5-dimethylphenyl imino-) tetrahydroglyoxaline-2-ketone of 5-and 6.0 milliliters of methylene dichloride preparations.After about 7 minutes 20 seconds, add 0.25 milliliter of described stock solution again.After 15 minutes, by adding acetone, methyl alcohol and the 6N HCl aqueous solution with the reaction mixture quenching.Polyethylene and water, methyl alcohol and the washing with acetone of separating out by isolated by vacuum filtration obtained 172 milligrams of white polyethylenes again in dry 13 days in 80 ℃ of vacuum drying ovens after on the strainer dry 2 hours.DSC:(heats for the second time) fusion, the heat absorption maximum value is at 124 ℃.
1H NMR shows that this material comprises about 18 branch/1000 carbon atoms.GPC：M
n＝56500；M
w/M
n＝3.55。
Embodiment 72
In the presence of MAO with 1, two (2, the 6-3,5-dimethylphenyl)-4 of 3-, the reaction product of two (2, the 6-3,5-dimethylphenyl imino-) tetrahydroglyoxalines-2-ketone of 5-, (1, the 2-glycol dimethyl ether) Nickel Bromide (II) and silver tetrafluoroborate is carried out vinyl polymerization
Be furnished with the magnetic force splash bar and be stamped barrier film and be furnished with the toluene of pack in the flask at the bottom of 500 milliliters of gardens that Schlenk takes over 100 milliliters of dryings, deoxidation.Flask placed water-bath and with 1 atmospheric ethene balance 10 minutes.Add 0.10 milliliter of stock solution then (by 240 milligram 1,3-two (2, the 6-3,5-dimethylphenyl)-4,5-two (2,6-3,5-dimethylphenyl imino-) reaction product of tetrahydroglyoxaline-2-ketone, (1, the 2-glycol dimethyl ether) Nickel Bromide (II) and silver tetrafluoroborate preparation newly in the methylene dichloride of 10 milliliters of dryings, deoxidation).Then reaction mixture is handled and stirred under 1 normal atmosphere ethene with 10% (weight) toluene solution of 4.0 milliliters of MAO.Observe the absorption and the sedimentary formation of polyethylene of ethene.6.33 after minute, by adding acetone (50 milliliters), methyl alcohol (50 milliliters) and the 6N HCl aqueous solution (100 milliliters) with the reaction mixture quenching.The swollen polyethylene of separating out by isolated by vacuum filtration and under 80 ℃ of vacuum dry several hrs.Isolate 860 milligrams of white powder shaped polyethylenes (87000TO/h).
1A H NMR:15 branch/1000 carbon atoms.GPC：M
n＝76000；M
w/M
n＝2.6。
Embodiment 73
Use is by the careless amidine in four (2, the 6-3,5-dimethylphenyl), two (1, the 5-cyclooctadiene) nickel (O) and HB (Ar)
4The catalyzer of [Ar=3, two (trifluoromethyl) phenyl of 5-] preparation on the spot carries out the polymerization of ethene
Be furnished with the magnetic force splash bar and be stamped pack in membranous 250 milliliters of pyriform Schlenk flasks 8.0 milligrams of two (1, the 5-cyclooctadiene) nickel (O), 19 milligrams of N
1, N
2, N
3, N
4-four (2, the 6-3,5-dimethylphenyl) careless amidine and 33 milligrams of HB (Ar)
4The ether solvent thing.Flask is found time and reinstall ethene, the toluene of pack into then 75 milliliters of dryings, deoxidation.Under ethene atmosphere, the yellow solution that obtains was stirred 30 minutes at 0 ℃, be heated to then 25 ℃ and under ethene atmosphere restir 30 minutes, then by adding acetone (50 milliliters) and methyl alcohol (50 milliliters) with the mixture quenching.Polyethylene and water, methyl alcohol and the washing with acetone of separating out by isolated by vacuum filtration, dry 14 hours of decompression (0.5 mm Hg) and obtain 0.70 gram elasticity white polyethylene (average 860TO/h) then.
1A H NMR:83 branch/1000 carbon atoms.GPC：M
n＝173000；M
w/M
n＝2.8。
Embodiment 74
In the presence of MAO, use 1,4-dimethyl-2, two (2,6-3,5-dimethylphenyl imino-) the Nickel Bromide title complexs of piperazine of 3-carry out the polymerization of ethene
Be furnished with the magnetic force splash bar and be stamped in membranous 250 milliliters of pyriform Schlenk flasks and pack 10.4 milligram 1 into, 4-dimethyl-2, the Nickel Bromide title complex of two (2, the 6-3,5-dimethylphenyl imino-) piperazines of 3-.Flask is found time and reinstall ethene, the toluene of pack into then 75 milliliters of dryings, deoxidation.The suspension that obtains is cooled to 0 ℃ and with 1 normal atmosphere ethene balance 15 minutes, uses 10% (weight) toluene solution processing of 4.0 milliliters of MAO then.Under ethene atmosphere, the yellow solution that obtains was stirred 1 hour, then by adding acetone (50 milliliters), methyl alcohol (50 milliliters) and the 6NHCl aqueous solution (100ml) the mixture quenching at 0 ℃.Separate out by isolated by vacuum filtration, swollen polyethylene and water, methyl alcohol and washing with acetone, dry 14 hours of decompression (0.5 mmHg) and obtain 1.3 gram transparent elastic polyethylene (2531TO/h) then.
1A H NMR:91 branch/1000 carbon atoms.GPC：M
n＝127000；M
w/M
n＝1.3。
Embodiment 75
Use title complex XXXV to carry out vinyl polymerization
The title complex XXXV of 50 milliliters of methylene dichloride and 50 milligrams of palladiums packs in the Schlenk flask of an oven dry of being furnished with splash bar and diaphragm of rubber.This flask is placed (1 normal atmosphere) under the ethene atmosphere.Mixture was stirred 20 hours.Adding acetone and methyl alcohol makes the reaction all standing and is settled out polymkeric substance.Collected polymer is also dry and obtain 2.6 gram sticky polymers under vacuum.The NMR spectroscopic analysis is consistent with the Alathon that will prepare.
1H NMR: hyperbranched polyethylene.GPC：M
n＝34000；M
w/M
n＝2.5。DSC：T
m＝-39℃，T
g＝-69℃。
Embodiment 76
Use title complex XXXV to carry out propylene polymerization
The title complex XXXV of 50 milliliters of methylene dichloride and 50 milligrams of palladiums packs in the Schlenk flask of an oven dry of being furnished with splash bar and diaphragm of rubber.This flask is placed (1 normal atmosphere) under the ethene atmosphere.Mixture was stirred 20 hours.Adding acetone and methyl alcohol makes the reaction all standing and is settled out polymkeric substance.Collected polymer is also dry and obtain 580 milligrams of sticky polymers under vacuum.
1A H NMR:192 tapping point/1000 carbon atoms.GPC：M
n＝17000；M
w/M
n＝2.08。DSC：T
g＝-53℃。
Embodiment 77
Use title complex XXXV to carry out the copolymerization of ethylene/vinyl base ethylene carbonate
In being full of the glove box of argon gas, (2,6-diisopropyl phenyl imino-)-[1,4] dithiane palladium (II) catalyzer XXXV (100 milligrams) packs in 200 milliliters of pyriform Schlenk flasks being furnished with the oven dry that magnetic force splash bar and barrier film seal.After shifting out from glove box, flask is found time and pack ethene into.In methylene dichloride (25 milliliters), also use vinylethylene carbonate (5 milliliters) to handle immediately described catalyst dissolution.The orange solution (1 normal atmosphere) under ethene atmosphere that obtains was stirred 20 hours at 23 ℃.Small amount of polymer is precipitated out from solution.Polyreaction is with methyl alcohol and acetone all standing and obtain adhering to grey oily matter on the flask walls.With polymkeric substance with acetone and methanol wash several times to remove any residual monomer.With polymer dissolution in methylene dichloride and transfer in the hold tank.Obtain 2.15 gram viscous solids (1100TO)～80 ℃ of vacuum-dryings 3 days with solvent evaporation and with the oily polymer that obtains.
1H NMR confirms that this multipolymer comprises about 96.5% (weight) ethene and 3.5% (weight) vinylethylene carbonate monomeric unit; M
n=40200g/mol; M
w=92100g/mol.DSC：T
g＝-68℃，T
m＝-38℃。
Embodiment 78
Use title complex XXXV to carry out the copolymerization of ethylene/vinyl base ethylene carbonate
In being full of the glove box of argon gas, (2,6-diisopropyl phenyl imino-)-[1,4] dithiane palladium (II) catalyzer XXXV (100 milligrams) packs in the pyriform Schlenk flask of 200 milliliters of oven dry of being furnished with the magnetic force splash bar and sealing with barrier film.After from glove box, shifting out, flask is found time and pack ethene into.In methylene dichloride (20 milliliters), also use vinylethylene carbonate (10 milliliters) to handle immediately described catalyst dissolution.The orange solution (1 normal atmosphere) under ethene atmosphere that obtains was stirred 28 hours at 23 ℃.Small amount of polymer is precipitated out from solution.Polyreaction is with methyl alcohol and acetone all standing and obtain adhering to grey oily matter on the flask walls.With polymer dissolution in methylene dichloride and transfer in the hold tank.With solvent evaporation and with the oily polymer that obtains with acetone and methanol wash several times with remove any residual monomer and obtain～80 ℃ of vacuum-dryings 1 day a kind of viscous solid (1.15 grams, 613TO).
1H NMR confirms that this multipolymer comprises about 95.5% (weight) ethene and 4.5% (weight) vinylethylene carbonate monomeric unit; M
n=15400g/mol; M
w=96000g/mol.DSC：T
g＝-64℃，T
m＝-31℃。
Embodiment 79
2, two (2, the 6-diisopropyl phenyl imino-)-[preparations of the Nickel Bromide title complex of 1,4] diox of 3-
Under argon gas atmosphere, in a Schlenk flask of being furnished with the magnetic force splash bar, pack 100 milligram 2 into, two (2,6-diisopropyl phenyl imino-)-[1 of 3-, 4] dioxs (0.25 mmole) and 71 milligrams of (1, the 2-glycol dimethyl ether) nickel (II) dibromide (0.23 mmole).Add the methylene dichloride (15 milliliters) of dry, deoxidation and mixture is stirred under argon gas atmosphere, become reddish-brown in about 10 minutes.After 2 hours, through the filter sleeve pipe with described red/orange solution transfers in the Schlenk flask of a new oven dry so that remove trace unreacted (1, the 2-glycol dimethyl ether) nickel (II) dibromide.Vacuum is removed methylene dichloride.The reddish-brown solids that obtains was with 2 * 10 milliliters of hexane wash and under vacuum dry several hours and obtain 80 milligrams of brown solid things.
Embodiment 80
2, two (2,6-3,5-dimethylphenyl imino-)-2 of 3-, the 3-glyoxalidine is the preparation of [2,1-b] thiazole also
752 milligrams of N pack in flask at the bottom of 50 milliliters of gardens of the reflux exchanger being furnished with the magnetic force splash bar and sealing with a nitrogen inlet adapter
1, N
2-two (2, the 6-3,5-dimethylphenyl) oxalyl diimine acyl dichloro, 200 milliliters of sodium hydrides (60% mineral oil dispersion), 5.0 milliliters of dry tetrahydrofuran and 250 milligrams of 2-mercaptoimidazoles.Mixture heating up was refluxed 120 minutes.After the cooling, water and methylene dichloride diluted mixture thing separate organic layer and concentrate and obtain a kind of Huang-orange.Column chromatography (SiO
2, Merck Grade 9385 230-400 orders, 60 dusts; The hexane solution of 12% (volume) ethyl acetate) obtains 487 milligrams of Huangs-orange solids thing.Recrystallization obtains 366 milligrams of Huangs-orange prism from heptane.The field desorption(FD) mass spectrum is presented at the parent ion peak at 360m/z place.
Embodiment 81
N
1, N
2The preparation of-two (2, the 6-3,5-dimethylphenyl) ethane imide base (diimido) selenic acid diphenyl ester
One be furnished with the magnetic force splash bar and with 50 milliliters of gardens of the reflux exchanger of a nitrogen inlet channel closure at the bottom of the 961 milligrams of N that pack in the flask
1, N
2-two (2, the 6-3,5-dimethylphenyl) oxalyl diimine acyl dichloro, 287 milligrams of sodium hydrides (60% mineral oil dispersion), 8.2 milliliters of dry tetrahydrofuran and .068 milliliter benzene selenol.Mixture heating up was refluxed 45 minutes.After the cooling, water and ether diluted mixture thing separate the ether layer and wash with water, then vacuum concentration and obtain a kind of Huang-orange crystalline solid.Solid is dissolved in the hot hexane, filters then and reconcentration.Recrystallization obtains 745 milligrams of orange prisms from heptane, for the first time results.The field desorption(FD) mass spectrum is presented at the parent ion different mountain at 570-578m/z place.
1H NMR (300MHz, CDCl
3, corresponding to being the chemical shift of unit with ppm at the TMS of 0ppm place): 1.95 (12p, s), 6.75 (6p, apparent, s), 7.02-7.20 (6p, m), 7.39-7.48 (4p, m).
Embodiment 82
Use is by N
1, N
2-two (2, the 6-3,5-dimethylphenyl) ethane imide base selenic acid diphenyl ester, two (1, the 5-cyclooctadiene) nickel (O) and HB (Ar)
4The catalyzer of [Ar=3, two (trifluoromethyl) phenyl of 5-] preparation on the spot carries out the polymerization of ethene
Be furnished with the magnetic force splash bar and be stamped pack in membranous 250 milliliters of pyriform Schlenk flasks 5 milligrams of two (1, the 5-cyclooctadiene) nickel (O), 10 milligrams of N
1, N
2-two (2, the 6-3,5-dimethylphenyl) ethane imide base selenic acid diphenyl esters and 25 milligrams of HB (Ar)
4The ether solvent thing.Flask is found time and reinstall ethene, the toluene of pack into then 45 milliliters of dryings, deoxidation.Under ethene, the yellow solution that obtains was stirred 10 minutes, then by adding methyl alcohol (50 milliliters) quenching at 21 ℃.The polyethylene of separating out by isolated by vacuum filtration also use methanol wash, then dry 14 hours of decompression (0.5mm Hg) and obtain 0.060 and restrain elasticity blue-green polyethylene.
1A H NMR:24 branch/1000 carbon atoms.GPC：M
n＝181000；M
w/M
n＝3.5。
Embodiment 83
2, two (2,6-3,5-dimethylphenyl imino-)-2 of 3-, the 3-glyoxalidine is the preparation of the Nickel Bromide title complex of [2,1-b] thiazole also
Under inert atmosphere, be furnished with the magnetic force splash bar and be stamped in membranous 50 milliliters of Schlenk flasks and pack 141 milligram 2 into, 3-two (2,6-3,5-dimethylphenyl imino-)-2, the 3-glyoxalidine is [2,1-b] thiazole and 110 milligrams of (1, the 2-glycol dimethyl ether) nickel (II) dibromide also.Add dry, slough the methylene dichloride (5 milliliters) of oxygen and under argon gas atmosphere, stir the mixture, add 5 milliliters of methylene dichloride after 1 hour again.With mixture 21 ℃ of restir 16 hours, then with the hexane dilution of 10 milliliters of dryings, deoxidation and restir 3 hours.By the sleeve pipe that covers the tip with filter paper supernatant liquor is removed, residue is dry and obtain 66 milligrams of brown microcrystalline solids under 1 mm Hg vacuum.
Embodiment 84
In the presence of MAO with 2, two (2,6-3,5-dimethylphenyl imino-)-2 of 3-, 3-glyoxalidine also [2,1-b] Nickel Bromide title complex of thiazole carries out the polymerization of ethene
Be furnished with the magnetic force splash bar and be stamped in membranous 200 milliliters of pyriform Schlenk flasks and pack 2.5 milligram 2 into, two (2,6-3,5-dimethylphenyl imino-)-2 of 3-, the 3-glyoxalidine is the Nickel Bromide title complex of [2,1-b] thiazole also.Flask is found time and reinstall ethene, the toluene of pack into then 75 milliliters of dryings, deoxidation.The suspension that obtains is handled and stirred under 1 atmospheric ethene with 1 atmospheric ethene balance 15 minutes and with the toluene solution of 200 microlitre 10% (weight) MAO down at 21 ℃.After 21 minutes, by adding acetone (50 milliliters), methyl alcohol (50 milliliters) and the 6N HCl aqueous solution (100 milliliters) with the reactant quenching.Swollen polyethylene and water, methyl alcohol and the washing with acetone of separating out by isolated by vacuum filtration, dry 24 hours of decompression (0.05-0.1 mm Hg) and obtain 198 milligrams of white polyethylenes then.
1A H NMR:13 branch/1000 carbon atoms.GPC: bimodal, M
n=23000; M
p=366000; M
w/ M
n=13.5.
Embodiment 85
N
1, N
2, N
3, N
4The preparation of the Nickel Bromide title complex of the careless amidine in-four (2, the 6-3,5-dimethylphenyl)
Under inert atmosphere, be furnished with the magnetic force splash bar and be stamped the 100 milligrams of N that pack in membranous 50 milliliters of Schlenk flasks
1, N
2, N
3, N
4-four (2, the 6-3,5-dimethylphenyl) careless amidines and 55 milligrams of (1, the 2-glycol dimethyl ether) nickel (II) dibromide.Add the methylene dichloride (5 milliliters) of dry, deoxidation and mixture is stirred under argon gas atmosphere.After 1 hour, add other 5 milliliters of methylene dichloride.With mixture at 21 ℃ of restir after 16 hours, with the hexane dilution of 10 milliliters of dryings, deoxidation and restir 3 hours.By the sleeve pipe that covers the tip with filter paper supernatant liquor is removed, residue is dry and obtain 95 milligrams of light green crystallizations under 1 mm Hg vacuum.
Embodiment 86
In the presence of MAO, use N
1, N
2, N
3, N
4The Nickel Bromide title complex of the careless amidine in-four (2, the 6-3,5-dimethylphenyl) carries out vinyl polymerization
Be furnished with the magnetic force splash bar and be stamped the 2.4 milligrams of N that pack in membranous 200 milliliters of pyriform Schlenk flasks
1, N
2, N
3, N
4The Nickel Bromide title complex of the careless amidine in-four (2, the 6-3,5-dimethylphenyl).Flask is found time and reinstall ethene, the toluene of pack into then 75 milliliters of dryings, deoxidation.The suspension that obtains is handled and stirred under 1 atmospheric ethene with 1 atmospheric ethene balance 15 minutes and with the toluene solution of 4.0 milliliter of 10% (weight) MAO down at 21 ℃.After 30 minutes, will react all standing by adding acetone (50 milliliters), methyl alcohol (50 milliliters) and the 6N HCl aqueous solution (100 milliliters).Swollen polyethylene and water, methyl alcohol and the washing with acetone of separating out by isolated by vacuum filtration, dry 24 hours of decompression (0.05-0.1 mm Hg) and obtain 743 milligrams of white polyethylenes then.
1A H NMR:112 branch/1000 carbon atoms.GPC：M
n＝330000；M
w/M
n＝1.4。
Embodiment 87
With 2, the Nickel Bromide title complex of two (2,6-3,5-dimethylphenyl imino-)-[1, the 4] dithiane of 3-carries out the copolymerization of ethene and 1-amylene in the presence of MAO
In 200 milliliters of pyriform Schlenk flasks being furnished with the magnetic force splash bar and sealing, pack into 0.5 milliliter 12.4 milligram 2 with barrier film, the stock solution of Nickel Bromide title complex in 10 milliliters of methylene dichloride of two (2,6-3,5-dimethylphenyl imino-)-[1, the 4] dithiane of 3-.Flask is found time and reinstall ethene, the toluene of pack into then 100 milliliters of dryings, deoxidation and 5.0 milliliters of 1-amylenes.Be cooled to the suspension that obtains in 0 ℃ and allow it, use the toluene solution of 4.0 milliliter of 10% (weight) MAO to handle and under 1 atmospheric ethene, stir then with 1 atmospheric ethene balance 15 minutes.After 45 minutes, will react all standing by adding acetone (50 milliliters), methyl alcohol (50 milliliters) and the 6N HCl aqueous solution (100 milliliters).Swollen multipolymer and water, methyl alcohol and washing with acetone by isolated by vacuum filtration is separated out obtain 2.0 gram white copolymer dry 24 hours of 100 ℃ of decompressions (255 mm Hg) then.
1A H NMR:24 branch/1000 carbon atoms.
13HNMR:7.6 methyl branch/1000 carbon atom, 1.2 ethyl branch/1000 carbon atoms, 9.1 propyl group branch/1000 carbon atoms, 2.1 butyl branch/1000 carbon atoms, 3.4 amyl groups and high-grade alkyl branch/1000 carbon atom more.GPC：M
n＝274000；M
w/M
n＝2.3。
Embodiment 88
With 2, the Nickel Bromide title complex of two (2,6-3,5-dimethylphenyl imino-)-[1, the 4] dithiane of 3-carries out the copolymerization of ethene and 1-heptene in the presence of MAO
Be furnished with pack in membranous 200 milliliters of pyriform Schlenk flasks 0.5 milliliter 12.4 milligram 2 of magnetic force splash bar and being stamped, the stock solution of Nickel Bromide title complex in 10 milliliters of methylene dichloride of two (2,6-3,5-dimethylphenyl imino-)-[1, the 4] dithiane of 3-.Flask is found time and reinstall ethene, the toluene of pack into then 100 milliliters of dryings, deoxidation and 5.0 milliliters of 1-heptene.Be cooled to the suspension that obtains in 0 ℃ and allow it, use the toluene solution of 4.0 milliliter of 10% (weight) MAO to handle and under 1 atmospheric ethene, stir then with 1 atmospheric ethene balance 15 minutes.After 33 minutes, will react all standing by adding acetone (50 milliliters), methyl alcohol (50 milliliters) and the 6N HCl aqueous solution (100 milliliters).Swollen multipolymer and water, methyl alcohol and washing with acetone by isolated by vacuum filtration is separated out obtain 1.25 gram white copolymer dry 24 hours of 100 ℃ of decompressions (255 mm Hg) then.
1A H NMR:19 branch/1000 carbon atoms.
13H NMR:5.9 methyl branch/1000 carbon atom, less than 1 ethyl branch/1000 carbon atom, less than 1 propyl group branch/1000 carbon atom, 1.8 butyl branch/1000 carbon atoms, 11.5 amyl groups and high-grade alkyl branch/1000 carbon atom more.GPC：M
n＝223000；M
w/M
n＝2.3。
Embodiment 89
With 2, the Nickel Bromide title complex of two (2,6-3,5-dimethylphenyl imino-)-[1, the 4] dithiane of 3-carries out the polymerization of 1-hexene in the presence of MAO
Under argon gas, be furnished with the magnetic force splash bar and be stamped in membranous 22 milliliters of glass tube vials and pack 1.8 milligram 2 in proper order, 10% (weight) toluene solution of two (2,6-3,5-dimethylphenyl the imino-)-Nickel Bromide title complexs of [1,4] dithiane of 3-, 4.0 milliliters of 1-hexenes and 2.0 milliliters of MAO.The purple mixture that obtains is obviously multiviscosisty in several minutes.After 34 minutes, make the reaction all standing with acetone, methyl alcohol and the 6N HCl aqueous solution.The polyhexene that filtration is separated out and vacuum (0.4mmHg) down drying obtain 428 milligrams of elasticity polyhexene.
1A H NMR:173 branch/1000 carbon atoms.GPC：M
n＝92000；M
w/M
n＝2.0。
Embodiment 90
In the presence of MAO with 2, two (2,6-3,5-dimethylphenyl imino-)-2 of 3-, 3-glyoxalidine also [2,1-b] Nickel Bromide title complex of thiazole carries out the polymerization of 1-hexene
Under argon gas, be furnished with the magnetic force splash bar and be stamped in membranous 22 milliliters of glass tube vials and pack 2.1 milligram 2 in proper order, 3-two (2,6-3,5-dimethylphenyl imino-)-2, the 3-glyoxalidine is 10% (weight) toluene solution of Nickel Bromide title complex, 4.0 milliliters of 1-hexenes and 2.0 milliliters of MAO of [2,1-b] thiazole also.Dark purple-the brown mixture that obtains is obviously multiviscosisty in 10-20 minute.After 53 minutes, make the reaction all standing with acetone, methyl alcohol and the 6N HCl aqueous solution.The polyhexene that filtration is separated out and vacuum (0.4 mm Hg) down drying obtain 283 milligrams of elasticity polyhexene.
1A H NMR:110 branch/1000 carbon atoms.GPC：M
n＝91000；M
w/M
n＝1.9。
Embodiment 91
In the presence of MAO, use 1,4-dimethyl-2, two (2,6-3,5-dimethylphenyl imino-) the Nickel Bromide title complexs of piperazine of 3-carry out the polymerization of 1-hexene
Under argon gas, be furnished with the magnetic force splash bar and be stamped in membranous 22 milliliters of glass tube vials and pack 2.1 milligram 1 in proper order, 4-dimethyl-2,10% (weight) toluene solution of two (2,6-3,5-dimethylphenyl imino-) the Nickel Bromide title complexs of piperazine of 3-, 4.0 milliliters of 1-hexenes and 2.0 milliliters of MAO.The yellow transparent solution that obtains was stirred 400 minutes at 23 ℃, make the reaction all standing with acetone, methyl alcohol and the 6 N HCl aqueous solution then.The polyhexene that filtration is separated out and vacuum (0.4 mm Hg) down drying obtain 408 milligrams of elasticity polyhexene.
1A H NMR:90 branch/1000 carbon atoms.GPC：M
n＝47000；M
w/M
n＝1.7。
Obviously, the present invention can be carried out numerous modifications and variations according to the above description.Therefore be appreciated that within the scope of the appended claims and can implement the present invention by the approach beyond concrete described in this.
Claims (204)
1. the method in batches or continuously of an olefinic polymerization comprises one or more are selected from formula RCH=CHR
8The monomer of compound contact with a kind of catalyzer, described catalyzer comprises (a) a kind of suitable metal carrier body and (b) ligand and optional (c) a kind of Bronsted acid or the Lewis acid of a kind of formula X,
Wherein R and R
8Each represents hydrogen, alkyl or fluoro-alkyl independently, and can be in conjunction with forming cycloolefin;
R
1And R
6Each is alkyl, substituted hydrocarbon radical or silyl independently; N represents nitrogen;
Respectively being one independently is connected heteroatomic single group for A and B, and the heteroatoms of wherein said connection is selected from the 15th or 16 families; In addition, A can link to each other by an abutment with B.
2. the process of claim 1 wherein that described suitable metal carrier body is a kind of Ni compound.
3. the process of claim 1 wherein that described suitable metal carrier body is a kind of Co compound.
4. the process of claim 1 wherein that described suitable metal carrier body is a kind of Pd compound.
5. the process of claim 1 wherein that described suitable metal carrier body is a kind of Fe compound.
6. the process of claim 1 wherein formula RCH=CHR
8Monomer be selected from ethene, propylene, 1-butylene, 1-hexene and 1-octene.
7. the method for claim 2, its Chinese style RCH=CHR
8Monomer be selected from ethene, propylene, 1-butylene, 1-hexene and 1-octene.
8. the method for claim 4, wherein said monomer also comprises methyl acrylate.
9. the method for claim 4, wherein said monomer also comprises vinyl-acetic ester.
10. the method for claim 2 has wherein used a kind of Lewis acid and described Lewis acid to be diethyl aluminum chloride.
11. the method for claim 2 has wherein used a kind of Lewis acid and described Lewis acid to be methylaluminoxane.
12. the method for claim 2, wherein R
1And R
6Be 2, the 6-3,5-dimethylphenyl.
13. the method for claim 2, wherein R
1And R
6Be 2, the 6-diisopropyl phenyl.
14. the method for claim 2, wherein said being aggregated in a kind of inert solvent carried out.
15. the method for claim 14, wherein said inert solvent are selected from linearity or ramose hydro carbons, toluene or its mixture.
16. the method for claim 2, wherein said catalyzer is attached on a kind of solid carrier.
17. the method for claim 2, wherein temperature is between about 150 ℃ of about 25-, and pressure is between about 1000 normal atmosphere of about 1-.
18. the method in batches or continuously of an olefinic polymerization comprises one or more formulas RCH=CHR
8Monomer contact with the catalyzer of a kind of formula XI:
Wherein R and R
8Each represents hydrogen, alkyl or fluoro-alkyl independently, and can be connected to form cycloolefin;
R
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently;
A and B are respectively independently for being connected heteroatomic single group, and the heteroatoms of wherein said connection is selected from the 15th or 16 families; In addition, A can be connected by abutment with B;
T represents hydrogen or alkyl;
L represents monoolefine or neutral Lewis base, and wherein said ligating atom is nitrogen, oxygen or sulphur;
M represents Ni (II), Pd (II), Co (II) or Fe (II);
N represents nitrogen; With
X
-Be a kind of weakly coordinating anion.
19. the method for claim 18, wherein M is Ni (II).
20. the method for claim 18, wherein M is Co (II).
21. the method for claim 18, wherein M is Pd (II).
22. the method for claim 18, wherein M is Fe (II).
23. the method for claim 18, its Chinese style RCH=CHR
8Monomer be selected from ethene, propylene, 1-butylene, 1-hexene and 1-octene.
24. the method for claim 19, its Chinese style RCH=CHR
8Monomer be selected from ethene, propylene, 1-butylene, 1-hexene and 1-octene.
25. the method for claim 21, wherein said monomer also comprises methyl acrylate.
26. the method for claim 21, wherein said monomer also comprises vinyl-acetic ester.
27. the method for claim 19, wherein R
1And R
6Be 2, the 6-3,5-dimethylphenyl.
28. the method for claim 19, wherein R
1And R
6Be 2, the 6-diisopropyl phenyl.
29. the method for claim 19, wherein said being aggregated in a kind of inert solvent carried out.
30. the method for claim 29, wherein said inert solvent are selected from linearity or ramose hydro carbons, toluene or its mixture.
31. the method for claim 19, wherein said catalyzer is attached on a kind of solid carrier.
32. the method for claim 19, wherein temperature is between about 150 ℃ of about 25-, and pressure is between about 1000 normal atmosphere of about 1-.
33. the method in batches or continuously of an olefinic polymerization comprises one or more formulas RCH=CHR
8Monomer contact with a kind of catalyzer, described catalyzer is by with the compound of formula XII:
Combine and form with a kind of compound Y,
Wherein R and R
8Each represents hydrogen, alkyl or fluoro-alkyl independently, and can be connected to form cycloolefin;
R
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently;
A and B are respectively independently for being connected heteroatomic single group, and the heteroatoms of wherein said connection is selected from the 15th or 16 families; In addition, A can be connected by abutment with B;
Q represents alkyl, chlorine, iodine or bromine;
W represents alkyl, chlorine, iodine or bromine;
N represents nitrogen; With
M represents Ni (II), Pd (II), Co (II) or Fe (II);
And Y is selected from and can captures Q
-Or W
-The Bronsted acid that to form a kind of neutral lewis acid of weakly coordinating anion, positively charged ion Lewis acid that its gegenion is weakly coordinating anion and a kind of its conjugate base be weakly coordinating anion.
34. the method for claim 33, wherein M is Ni (II).
35. the method for claim 33, wherein M is Co (II).
36. the method for claim 33, wherein M is Pd (II).
37. the method for claim 33, wherein M is Fe (II).
38. the method for claim 33, its Chinese style RCH=CHR
8Monomer be selected from ethene, propylene, 1-butylene, 1-hexene and 1-octene.
39. the method for claim 34, its Chinese style RCH=CHR
8Monomer be selected from ethene, propylene, 1-butylene, 1-hexene and 1-octene.
40. the method for claim 34, wherein Y is that a kind of Lewis acid and described Lewis acid are diethyl aluminum chloride.
41. the method for claim 34, wherein Y is that a kind of Lewis acid and described Lewis acid are methylaluminoxane.
42. the method for claim 34, wherein R
1And R
6Be 2, the 6-3,5-dimethylphenyl.
43. the method for claim 34, wherein R
1And R
6Be 2, the 6-diisopropyl phenyl.
44. the method for claim 34, wherein said being aggregated in a kind of inert solvent carried out.
45. the method for claim 44, wherein said inert solvent are selected from linearity or ramose hydro carbons, toluene or its mixture.
46. the method for claim 34, wherein said catalyzer is attached on a kind of solid carrier.
47. the method for claim 34, wherein temperature is between about 150 ℃ of about 25-, and pressure is between about 1000 normal atmosphere of about 1-.
48. the method for claim 18, the catalyzer of wherein said formula XI is selected from:
R wherein
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently;
R
2, R
3, R
4And R
5Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently; In addition, R
2, R
3, R
4And R
5Any two can form an abutment jointly, prerequisite is for when described catalyzer is the catalyzer of formula IV or VII, described abutment is not the sulphur atom of a replacement or the phosphorus atom of replacement;
T represents hydrogen or alkyl;
L represents monoolefine or neutral Lewis base, and wherein said ligating atom is nitrogen, oxygen or sulphur;
M represents Ni (II), Pd (II), Co (II) or Fe (II);
N represents nitrogen; O represents oxygen; S represents sulphur; With
X
-Be a kind of weakly coordinating anion.
49. the method for claim 48, wherein said catalyzer are the catalyzer of formula I.
50. the method for claim 48, wherein said catalyzer are the catalyzer of formula IV.
51. the method for claim 48, wherein said catalyzer are the catalyzer of formula VII.
52. the method for claim 48, wherein said catalyzer are the catalyzer of formula XIII.
53. the method for claim 48, wherein said catalyzer are the catalyzer of formula XIV.
54. the method for claim 49, wherein M is Ni (II).
55. the method for claim 50, wherein M is Ni (II).
56. the method for claim 51, wherein M is Ni (II).
57. the method for claim 52, wherein M is Ni (II).
58. the method for claim 53, wherein M is Ni (II).
59. the method for claim 48, wherein M is Ni (II).
60. the method for claim 48, wherein M is Co (II).
61. the method for claim 48, wherein M is Pd (II).
62. the method for claim 48, wherein M is Fe (II).
63. the method for claim 59, its Chinese style RCH=CHR
8Monomer be selected from ethene, propylene, 1-butylene, 1-hexene and 1-octene.
64. the method for claim 59, wherein R
1And R
6Be 2, the 6-3,5-dimethylphenyl.
65. the method for claim 59, wherein R
1And R
6Be 2, the 6-diisopropyl phenyl.
66. the method for claim 59, wherein said being aggregated in a kind of inert solvent carried out.
67. the method for claim 66, wherein said inert solvent are selected from linearity or ramose hydro carbons, toluene or its mixture.
68. the method for claim 59, wherein said catalyzer is attached on a kind of solid carrier.
69. the method for claim 59, wherein temperature is between about 150 ℃ of about 25-, and pressure is between about 1000 normal atmosphere of about 1-.
70. the method for claim 33, the catalyzer of wherein said formula XII is selected from:
Wherein R and R
8Each represents hydrogen, alkyl or fluoro-alkyl independently, and can be connected to form cycloolefin;
R
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently;
R
2, R
3, R
4And R
5Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently; In addition, R
2, R
3, R
4Or R
5Any two can form an abutment jointly, prerequisite is for when described catalyzer is the catalyzer of formula V or VIII, described abutment is not the sulphur atom of a replacement or the phosphorus atom of replacement;
Q representation hydrocarbyl, chlorine, iodine or bromine;
W representation hydrocarbyl, chlorine, iodine or bromine;
M represents Ni (II), Pd (II), Co (II) or Fe (II); With
N represents nitrogen.
71. the method for claim 70, wherein said catalyzer are the catalyzer of formula II.
72. the method for claim 70, wherein said catalyzer are the catalyzer of formula V.
73. the method for claim 70, wherein said catalyzer are the catalyzer of formula VIII.
74. the method for claim 70, wherein said catalyzer are the catalyzer of formula XV.
75. the method for claim 70, wherein said catalyzer are the catalyzer of formula XVI.
76. the method for claim 71, wherein M is Ni (II).
77. the method for claim 72, wherein M is Ni (II).
78. the method for claim 73, wherein M is Ni (II).
79. the method for claim 74, wherein M is Ni (II).
80. the method for claim 75, wherein M is Ni (II).
81. the method for claim 70, wherein M is Ni (II).
82. the method for claim 70, wherein M is Co (II).
83. the method for claim 70, wherein M is Pd (II).
84. the method for claim 70, wherein M is Fe (II).
85. the method for claim 81, its Chinese style RCH=CHR
8Monomer be selected from ethene, propylene, 1-butylene, 1-hexene and 1-octene.
86. the method for claim 83, wherein said monomer also comprises methyl acrylate.
87. the method for claim 83, wherein said monomer also comprises vinyl-acetic ester.
88. the method for claim 81, wherein R
1And R
6Be 2, the 6-3,5-dimethylphenyl.
89. the method for claim 81, wherein R
1And R
6Be 2, the 6-diisopropyl phenyl.
90. the method for claim 81, wherein said being aggregated in a kind of inert solvent carried out.
91. the method for claim 90, wherein said inert solvent are selected from linearity or ramose hydro carbons, toluene or its mixture.
92. the method for claim 81, wherein said catalyzer is attached on a kind of solid carrier.
93. the method for claim 81, wherein temperature is between about 150 ℃ of about 25-, and pressure is between about 1000 normal atmosphere of about 1-.
94. the process of claim 1 wherein that the ligand that described suitable metal carrier body is nickel (O) compound and formula X is selected from:
And the Bronsted acid that is a kind of weakly coordinating anion with a kind of its conjugate base combines,
R wherein
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently;
R
2, R
3, R
4And R
5Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently; In addition, R
2, R
3, R
4And R
5Any two can form an abutment jointly, prerequisite is for when described ligand is the ligand of formula VI or IX, described abutment is not the sulphur atom of a replacement or the phosphorus atom of replacement.
95. the method for claim 94, its Chinese style RCH=CHR
8Monomer be selected from ethene, propylene, 1-butylene, 1-hexene and 1-octene.
96. the method for claim 94, wherein R
1And R
6Be 2, the 6-3,5-dimethylphenyl.
97. the method for claim 94, wherein R
1And R
6Be 2, the 6-diisopropyl phenyl.
98. the method for claim 94, wherein said being aggregated in a kind of inert solvent carried out.
99. the method for claim 98, wherein said inert solvent are selected from linearity or ramose hydro carbons, toluene or its mixture.
100. the method for claim 94, wherein temperature is between about 150 ℃ of about 25-, and pressure is between about 1000 normal atmosphere of about 1-.
101. a method in batches or continuously that is used for olefinic polymerization comprises one or more formulas RCH=CHR
8Monomer contact with a kind of catalyzer of following formula:
Wherein R and R
8Each represents hydrogen, alkyl or fluoro-alkyl independently, and can be connected to form cycloolefin;
R
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently;
R
2, R
3, R
4And R
5Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently; In addition, R
2, R
3, R
4And R
5Any two can form an abutment jointly, prerequisite is for when described catalyzer is the catalyzer of formula XX or XXI, described abutment is not the sulphur atom of a replacement or the phosphorus atom of replacement;
G is a π-allyl group or π-benzyl;
M represents Ni (II) or Pd (II);
N represent nitrogen and
X
-Be a kind of weakly coordinating anion.
102. the method for claim 101, wherein said catalyzer are the catalyzer of formula XIX.
103. the method for claim 101, wherein said catalyzer are the catalyzer of formula XX.
104. the method for claim 101, wherein said catalyzer are the catalyzer of formula XXI.
105. the method for claim 101, wherein said catalyzer are the catalyzer of formula XXII.
106. the method for claim 101, wherein said catalyzer are the catalyzer of formula XXIII.
107. the method for claim 101, wherein M is Ni (II).
108. the method for claim 102, wherein M is Ni (II).
109. the method for claim 103, wherein M is Ni (II).
110. the method for claim 104, wherein M is Ni (II).
111. the method for claim 105, wherein M is Ni (II).
112. the method for claim 106, wherein M is Ni (II).
113. the method for claim 101, wherein X
-Be BF
4 -
114. the method for claim 101, wherein M is Pd (II).
115. the method for claim 101, wherein X
-Be PF
6 -
116. the method for claim 107, its Chinese style RCH=CHR
8Monomer be selected from ethene, propylene, 1-butylene, 1-hexene and 1-octene.
117. the method for claim 114, wherein said monomer also comprises methyl acrylate.
118. the method for claim 114, wherein said monomer also comprises vinyl-acetic ester.
119. the method for claim 107, wherein R
1And R
6Be 2, the 6-3,5-dimethylphenyl.
120. the method for claim 107, wherein R
1And R
6Be 2, the 6-diisopropyl phenyl.
121. the method for claim 107, wherein said being aggregated in a kind of inert solvent carried out.
122. the method for claim 121, wherein said inert solvent are selected from linearity or ramose hydro carbons, toluene or its mixture.
123. the method for claim 107, wherein said catalyzer is attached on a kind of solid carrier.
124. the method for claim 107, wherein temperature is between about 150 ℃ of about 25-, and pressure is between about 1000 normal atmosphere of about 1-.
125. a method for preparing linear alpha-alkene comprises with ethene and (a) a kind of suitable nickel parent (b) a kind of compound of following formula:
Contact with optional (c) a kind of Bronsted acid or Lewis acid, wherein
R
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently;
R
2, R
3, R
4And R
5Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently; In addition, R
2, R
3, R
4And R
5Any two can form an abutment jointly, prerequisite is for when described compound is the compound of formula VI or IX, described abutment is not the sulphur atom of a replacement or the phosphorus atom of replacement;
N represents nitrogen; O represents oxygen; S represents sulphur.
126. the method for claim 125, wherein said compound are the compounds of formula III.
127. the method for claim 125, wherein said compound are the compounds of formula VI.
128. the method for claim 125, wherein said compound are the compounds of formula IX.
129. the method for claim 125, wherein said compound are the compounds of formula XVII.
130. the method for claim 125, wherein said compound are the compounds of formula XVIII.
131. the method for claim 125, wherein R
1And R
6It is phenyl.
132. the method for claim 125, wherein said method is carried out in a kind of inert solvent.
133. the method for claim 132, wherein said inert solvent are selected from linearity or ramose hydro carbons, toluene or its mixture.
134. the method for claim 125, wherein temperature is between about 150 ℃ of about 25-, and pressure is between about 1000 normal atmosphere of about 1-.
135. a method for preparing linear alpha-alkene comprises ethene is contacted with a kind of compound of following formula:
R
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently;
R
2, R
3, R
4And R
5Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently; In addition, R
2, R
3, R
4And R
5Any two can form an abutment jointly, prerequisite is for when described compound is the compound of formula IV or VII, described abutment is not the sulphur atom of a replacement or the phosphorus atom of replacement;
T represents hydrogen or alkyl;
L represents monoolefine or neutral Lewis base, and wherein said ligating atom is nitrogen, oxygen or sulphur;
M represents Ni (II);
N represents nitrogen; O represents oxygen; S represents sulphur; With
X
-Be a kind of weakly coordinating anion.
136. the method for claim 135, wherein said compound are the compound of formula I.
137. the method for claim 135, wherein said compound are the compound of formula IV.
138. the method for claim 135, wherein said compound are the compound of formula VII.
139. the method for claim 135, wherein said compound are the compound of formula XIII.
140. the method for claim 135, wherein said compound are the compound of formula XIV.
141. the method for claim 135, wherein R
1And R
6It is phenyl.
142. the method for claim 135, wherein said method is carried out in a kind of inert solvent.
143. the method for claim 142, wherein said inert solvent are selected from linearity or ramose hydro carbons, toluene or its mixture.
144. the method for claim 135, wherein temperature is between about 150 ℃ of about 25-, and pressure is between about 1000 normal atmosphere of about 1-.
145. a method for preparing alpha-olefin comprises ethene is contacted with a kind of catalyzer, described catalyzer is by the title complex of following formula:
Combine with compound Y and to form,
R wherein
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently;
R
2, R
3, R
4And R
5Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently; In addition, R
2, R
3, R
4And R
5Any two can form an abutment together, prerequisite is when described title complex is the title complex of formula V or VIII, described abutment is not to replace sulphur atom or replace phosphorus atom;
Q representation hydrocarbyl, chlorine, iodine or bromine;
W representation hydrocarbyl, chlorine, iodine or bromine;
M represents Ni (II);
N represents nitrogen; O represents oxygen; S represents sulphur;
Be selected from Y and can capture Q
-Or W
-The Bronsted acid that to form a kind of neutral lewis acid of weakly coordinating anion, positively charged ion Lewis acid that its gegenion is weakly coordinating anion or a kind of its conjugate base be weakly coordinating anion.
146. the method for claim 145, wherein said title complex are the title complexs of formula II.
147. the method for claim 145, wherein said title complex are the title complexs of formula V.
148. the method for claim 145, wherein said title complex are the title complexs of formula VIII.
149. the method for claim 145, wherein said title complex are the title complexs of formula XV.
150. the method for claim 145, wherein said title complex are the title complexs of formula XVI.
151. the method for claim 145, wherein R
1And R
6It is phenyl.
152. the method for claim 145, wherein said method is carried out in a kind of inert solvent.
153. the method for claim 152, wherein said inert solvent are selected from linearity or ramose hydro carbons, toluene or its mixture.
154. the method for claim 145, wherein temperature is between about 150 ℃ of about 25-, and pressure is between about 1000 normal atmosphere of about 1-.
155. ethene and formula CH
2=CH (CH
2)
nCO
2R
1The copolymerization process of comonomer, comprise ethene and a kind of formula CH
2=CH (CH
2)
nCO
2R
1Comonomer with (it is selected from and can captures Q by making first kind of compound Y
-Or W
-The Bronsted acid that to form a kind of neutral lewis acid of weakly coordinating anion, positively charged ion Lewis acid that its gegenion is weakly coordinating anion or a kind of its conjugate base be weakly coordinating anion) contact in conjunction with formed title complex with second kind of compound of formula XXIV:
R wherein
1Be hydrogen, alkyl, substituted hydrocarbon radical, fluoro-alkyl or silyl;
N is an integer greater than 3;
R
2And R
3Each is hydrogen, alkyl, substituted hydrocarbon radical or silyl independently, or can form a bridging alkyl, bridging substituted hydrocarbon radical or a replacement Siliciumatom jointly;
Q is alkyl, chlorine, iodine or bromine;
W is alkyl, chlorine, iodine or bromine;
N is a nitrogen;
Z is sulphur or oxygen; With
M is Ni (II).
156. ethene and formula CH
2=CH (CH
2)
nCO
2R
1The polymerization process of comonomer, comprise ethene and a kind of formula CH
2=CH (CH
2)
nCO
2R
1Comonomer and compound by (a) a kind of formula XLII; (b) a kind of suitable nickel (O) parent, the title complex that forms with the reaction product of (c) a kind of its conjugate base Bronsted acid that is weakly coordinating anion contacts,
R wherein
1Be hydrogen, alkyl, substituted hydrocarbon radical, fluoro-alkyl or silyl;
N is an integer greater than 3;
R
2And R
3Each is hydrogen, alkyl, substituted hydrocarbon radical or silyl independently, or can form a bridging alkyl, bridging substituted hydrocarbon radical or a replacement Siliciumatom jointly;
N is a nitrogen; With
Z is sulphur or oxygen.
157. the method for an olefinic polymerization comprises one or more formulas RCH=CHR
8Monomer be coupled to a double-coreization or a multinucleation ligand on the 8-10 group 4 transition metal M and contact with one or more Lewis acids, wherein said Lewis acid is incorporated on one or more heteroatomss, described heteroatoms pi-conjugated to described transition metal M bonded donor atom on; R and R
8Each represents hydrogen, alkyl or fluoro-alkyl independently, and can be connected to form cycloolefin.
158. the method for claim 157, wherein said double-coreization or multinucleation ligand are selected from:
And M is Ni (II), Pd (II), Co (II) or Fe (II), wherein R
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently;
R
2, R
3, R
4And R
5Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently; In addition, R
2, R
3, R
4And R
5Any two can form an abutment together, prerequisite is when described ligand is the ligand of formula VI or IX, described abutment is not to replace sulphur atom or replace phosphorus atom; With
N represents nitrogen; O represents oxygen; Represent sulphur with S.
159. the method for claim 157, wherein said Lewis acid are the Lewis acids of a kind of boracic or aluminium.
160. the method for claim 158, wherein said Lewis acid are the Lewis acids of a kind of boracic or aluminium.
161. a composition, it comprises (a) 8-10 group 4 transition metal M, (b) one or more Lewis acids and (c) double-coreization or the multinucleation compound of a kind of formula X:
Wherein said Lewis acid combines with one or more heteroatomss, and described heteroatoms is pi-conjugated with the described donor atom that is attached on the described transition metal M;
R
1And R
6Each represents sterically hindered aryl independently;
N represents nitrogen;
Respectively being one independently is connected heteroatomic single group for A and B, and the heteroatoms of wherein said connection is selected from the 15th or 16 families; In addition, A can link to each other by an abutment with B.
162. according to the composition of claim 161, wherein said transition metal is that Ni (II), described Lewis acid are the Lewis acids of boracic or aluminium, the double-coreization of described formula X or multinucleation compound are selected from:
R wherein
1And R
6Each represents sterically hindered aryl independently;
R
2, R
3, R
4And R
5Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently; In addition, R
2, R
3, R
4And R
5Any two can form an abutment together, prerequisite is when described compound is the compound of formula VI or IX, described abutment is not to replace sulphur atom or replace phosphorus atom;
N represents nitrogen; O represents oxygen; Represent sulphur with S.
163. the compound of a formula I:
R wherein
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently;
R
2, R
3, R
4And R
5Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently; In addition, R
2, R
3, R
4And R
5Any two can form an abutment together;
T represents hydrogen or alkyl;
L represents a kind of monoolefine or neutral Lewis base, and wherein said ligating atom is nitrogen, oxygen or sulphur;
M represents Ni (II), Pd (II), Co (II) or Fe (II);
N represents nitrogen; With
X
-Be weakly coordinating anion.
164. the compound of a formula II:
R wherein
1And R
6Each represents a kind of sterically hindered aryl independently;
R
2, R
3, R
4And R
5Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently; In addition, R
2, R
3, R
4And R
5Any two can form an abutment together;
Q representation hydrocarbyl, chlorine, iodine or bromine;
W representation hydrocarbyl, chlorine, iodine or bromine;
N represents nitrogen; With
M represents Ni (II), Pd (II), Co (II) or Fe (II).
165. the compound of a formula IV:
R wherein
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently;
R
2And R
3Each represents hydrogen, alkyl substituted hydrocarbon radical or silyl independently, in addition, can form bridging alkyl, bridging substituted hydrocarbon radical together or replace Siliciumatom;
T represents hydrogen or alkyl;
L represents monoolefine or neutral Lewis base, and wherein said ligating atom is nitrogen, oxygen or sulphur;
M represents Ni (II), Pd (II), Co (II) or Fe (II);
N represents nitrogen; With
X
-Be a kind of weakly coordinating anion.
166. the compound of a formula V:
R wherein
1And R
6Each represents sterically hindered aryl independently;
R
2And R
3Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently, in addition, can form bridging alkyl, bridging substituted hydrocarbon radical together or replace Siliciumatom;
Q representation hydrocarbyl, chlorine, iodine or bromine;
W representation hydrocarbyl, chlorine, iodine or bromine;
N represents nitrogen; With
M represents Ni (II), Pd (II), Co (II) or Fe (II).
167. the compound of a formula VI
R wherein
1And R
6Each represents sterically hindered aryl independently; With
R
2And R
3Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently, in addition, can form bridging alkyl, bridging substituted hydrocarbon radical together or replace Siliciumatom.
168. the compound of a formula VII:
R wherein
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently;
R
2And R
3Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently, in addition, can form bridging alkyl, bridging substituted hydrocarbon radical together or replace Siliciumatom;
T represents hydrogen or alkyl;
L represents monoolefine or neutral Lewis base, and wherein said ligating atom is nitrogen, oxygen or sulphur;
M represents Ni (II), Pd (II), Co (II) or Fe (II);
N represents nitrogen; With
X
-Be a kind of weakly coordinating anion.
169. formula VIII compound:
R wherein
1And R
6Each represents sterically hindered aryl independently;
R
2And R
3Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently, in addition, can form bridging alkyl, bridging substituted hydrocarbon radical together or replace Siliciumatom;
Q representation hydrocarbyl, chlorine, iodine or bromine;
W representation hydrocarbyl, chlorine, iodine or bromine;
N represents nitrogen; With
M represents Ni (II), Pd (II), Co (II) or Fe (II).
170. the compound of a formula IX:
R wherein
1And R
6Each represents sterically hindered aryl independently; With
R
2And R
3Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently, in addition, can form bridging alkyl, bridging substituted hydrocarbon radical together or replace Siliciumatom.
171. the compound of a formula XIII:
R wherein
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently;
R
2, R
3And R
4Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently, in addition, and R
2, R
3And R
4Any two can form abutment together;
T represents hydrogen or alkyl;
L represents monoolefine or neutral Lewis base, and wherein said ligating atom is nitrogen, oxygen or sulphur;
M represents Ni (II), Pd (II), Co (II) or Fe (II);
N represents nitrogen; With
X
-Be a kind of weakly coordinating anion.
172. the compound of a formula XV:
R wherein
1And R
6Each represents sterically hindered aryl independently;
R
2, R
3And R
4Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently, in addition, and R
2, R
3And R
4Any two can form abutment together;
Q representation hydrocarbyl, chlorine, iodine or bromine;
W representation hydrocarbyl, chlorine, iodine or bromine;
N represents nitrogen; With
M represents Ni (II), Pd (II), Co (II) or Fe (II).
173. the compound of a formula XVII:
R wherein
1And R
6Each represents sterically hindered aryl independently; With
R
2, R
3And R
4Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently, in addition, and R
2, R
3And R
4Any two can form abutment together.
174. the compound of a formula XIV:
R wherein
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently;
R
2And R
5Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently;
T represents hydrogen or alkyl;
L represents monoolefine or neutral Lewis base, and wherein said ligating atom is nitrogen, oxygen or sulphur;
M represents Ni (II), Pd (II), Co (II) or Fe (II);
N represents nitrogen; With
X
-Be a kind of weakly coordinating anion.
175. the compound of a formula XVI:
R wherein
1And R
6Each represents sterically hindered aryl independently;
R
2And R
5Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently;
Q representation hydrocarbyl, chlorine, iodine or bromine;
W representation hydrocarbyl, chlorine, iodine or bromine;
N represents nitrogen; With
M represents Ni (II), Pd (II), Co (II) or Fe (II).
176. the compound of a formula XVIII:
R wherein
1And R
6Each represents sterically hindered aryl independently;
R
2And R
5Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently.
177. the compound of a formula XIX:
R wherein
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently;
R
2, R
3, R
4And R
5Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently, in addition, and R
2, R
3, R
4And R
5Any two can form abutment together;
G is a π-allyl group or π-benzyl group;
M represents Ni (II) or Pd (II);
N represents nitrogen; With
X
-Be a kind of weakly coordinating anion.
178. the compound of a formula XX:
R wherein
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently;
R
2And R
3Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently, in addition, can form bridging alkyl, bridging substituted hydrocarbon radical together or replace Siliciumatom;
G is a π-allyl group or π-benzyl group;
M represents Ni (II), Pd (II);
N represents nitrogen; With
X
-Be a kind of weakly coordinating anion.
179. the compound of a formula XXI:
R wherein
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently;
R
2And R
3Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently, in addition, can form bridging alkyl, bridging substituted hydrocarbon radical together or replace Siliciumatom;
G is a π-allyl group or π-benzyl group;
M represents Ni (II), Pd (II);
N represents nitrogen; With
X
-Be a kind of weakly coordinating anion.
180. the compound of a formula XXII:
R wherein
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently;
R
2, R
3And R
4Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently, in addition, can form abutment together;
G is a π-allyl group or π-benzyl group;
M represents Ni (II) or Pd (II);
N represents nitrogen; With
X
-Be a kind of weakly coordinating anion.
181. the compound of a formula XXIII:
R wherein
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently;
R
2And R
5Each represents hydrogen, alkyl, substituted hydrocarbon radical or silyl independently;
G is a π-allyl group or π-benzyl group;
M represents Ni (II), Pd (II);
N represents nitrogen; With
X
-Be a kind of weakly coordinating anion.
182. the compound of a formula XXIV:
R wherein
1And R
6Each is representation hydrocarbyl, substituted hydrocarbon radical or silyl independently;
A and B are respectively independently for being connected heteroatomic single group, and the heteroatoms of wherein said connection is selected from the 15th or 16 families, and A can be connected by an abutment with B in addition;
T represents hydrogen or alkyl;
L represents monoolefine or neutral Lewis base, and wherein said ligating atom is nitrogen, oxygen or sulphur;
M represents Ni (II) or Pd (II);
N represents nitrogen; With
X
-Be a kind of weakly coordinating anion.
183. the compound of a formula XXIX:
R wherein
1And R
6Each represents sterically hindered aryl independently;
A and B are respectively independently for being connected heteroatomic single group, and the heteroatoms of wherein said connection is selected from the 15th or 16 families, and A can be connected by an abutment with B in addition;
Q representation hydrocarbyl, chlorine, iodine or bromine;
W representation hydrocarbyl, chlorine, iodine or bromine;
M represents Ni (II) or Pd (II); With
N represents nitrogen.
184. have the compound of the claim 165 of formula XXV:
R wherein
1And R
6Be 2, the 6-3,5-dimethylphenyl;
And X
-Be a kind of weakly coordinating anion.
185. have the compound of the claim 165 of formula XXVI:
R wherein
1And R
6Be 2, the 6-diisopropyl phenyl;
And X
-Be a kind of weakly coordinating anion.
186. have the compound of the claim 166 of formula XXVII:
R wherein
1And R
6Be 2, the 6-3,5-dimethylphenyl.
187. have the compound of the claim 166 of formula XXVIII:
R wherein
1And R
6Be 2, the 6-diisopropyl phenyl.
188. have the compound of the claim 168 of formula XXX;
R wherein
1And R
6Be 2, the 6-3,5-dimethylphenyl;
And X
-Be a kind of weakly coordinating anion.
189. have the compound of the claim 168 of formula XXXI:
R wherein
1And R
6Be 2, the 6-diisopropyl phenyl;
And X
-Be a kind of weakly coordinating anion.
190. have the compound of the claim 169 of formula XXXII:
R wherein
1And R
6Be 2, the 6-3,5-dimethylphenyl.
191. have the compound of the claim 169 of formula XXXIII:
R wherein
1And R
6Be 2, the 6-diisopropyl phenyl.
192. have the compound of the claim 168 of formula XXXIV:
R wherein
1And R
6Be 2, the 6-diisopropyl phenyl;
And X
-Be a kind of weakly coordinating anion.
193. have the compound of the claim 165 of formula XXXV:
R wherein
1And R
6Be 2, the 6-diisopropyl phenyl;
And X
-Be a kind of weakly coordinating anion.
194. have the compound of the claim 171 of formula XXXVI:
R wherein
1And R
6Be 2, the 6-3,5-dimethylphenyl;
And X
-Be a kind of weakly coordinating anion.
195. have the compound of the claim 171 of formula XXXVII:
R wherein
1And R
6Be 2, the 6-diisopropyl phenyl;
And X
-Be a kind of weakly coordinating anion.
196. have the compound of the claim 172 of formula XXXVIII:
R wherein
1And R
6Be 2, the 6-3,5-dimethylphenyl.
197. have the compound of the claim 172 of formula XXXIX:
R wherein
1And R
6Be 2, the 6-diisopropyl phenyl.
198. have the compound of the claim 174 of formula XL:
R wherein
1, R
2, R
5And R
6Be 2,6-dimethyl-4-p-methoxy-phenyl;
And X
-Be a kind of weakly coordinating anion.
199. have the compound of the claim 175 of formula XLI:
R wherein
1, R
2, R
5And R
6Be 2,6-dimethyl-4-p-methoxy-phenyl.
200. the composition of a polymkeric substance comprises the formula CH that comes from ethene and come from 0.1-50% (weight)
2=CH (CH
2)
nCO
2R
1The monomeric unit of comonomer, R wherein
1For hydrogen, alkyl, substituted hydrocarbon radical, fluoro-alkyl or silyl and n are a integer between 3 to 18; Except branch be since described comonomer sneak into caused, alkyl branch is present in the described polymer composition, wherein per 1000 carbon atoms exist 5 to 50 alkyl branches and most of alkyl to branch into methyl branch.
201. one kind comprises and contains the composition that per 1000 carbon atoms have the ester of 5-30 alkyl ramose hemicrystalline copolymerization of ethylene, wherein most of alkyl branches into methyl branch and on average about 1-50 the end capped branch of ester of each chain comes from sneaking into of ester comonomer.
202. one kind comprises and contains the composition that per 1000 carbon atoms have the alkene of 5-30 alkyl ramose hemicrystalline copolymerization of ethylene, wherein most of alkyl branches into methyl branch and on average about 1-50 the end capped branch of alkene of each chain comes from sneaking into of linear diene comonomer.
203. the compound of claim 164, wherein M is Ni (II).
204. one kind comprises that per 1000 carbon atoms have the composition of 125 above alkyl ramose Alathons.
Applications Claiming Priority (12)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US4036397P | 1997-03-10 | 1997-03-10 | |
| US60/040,363 | 1997-03-10 | ||
| US4154297P | 1997-03-25 | 1997-03-25 | |
| US4340697P | 1997-04-04 | 1997-04-04 | |
| US4292597P | 1997-04-04 | 1997-04-04 | |
| US4469197P | 1997-04-18 | 1997-04-18 | |
| US60/044,691 | 1997-05-06 | ||
| US5937297P | 1997-09-18 | 1997-09-18 | |
| US60/059,372 | 1997-09-18 | ||
| US60/041,542 | 1997-09-18 | ||
| US60/043,406 | 1997-09-18 | ||
| US60/042,925 | 1997-09-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1258292A true CN1258292A (en) | 2000-06-28 |
Family
ID=27556377
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 98804802 Pending CN1258292A (en) | 1997-03-10 | 1998-02-24 | Olefin polymerization catalysts contg. group 8-10 transition metals, bidentate ligands, processes employing such catalysts and polymers obtained therefrom |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN1258292A (en) |
| CA (1) | CA2283223A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106243254A (en) * | 2011-03-04 | 2016-12-21 | 奥特拉斯技术有限责任公司 | Comprise the goods of the functional polymeric phase change materials of exact branch |
-
1998
- 1998-02-24 CA CA002283223A patent/CA2283223A1/en not_active Abandoned
- 1998-02-24 CN CN 98804802 patent/CN1258292A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106243254A (en) * | 2011-03-04 | 2016-12-21 | 奥特拉斯技术有限责任公司 | Comprise the goods of the functional polymeric phase change materials of exact branch |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2283223A1 (en) | 1998-09-17 |
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