CN1256351C - Catalyst for polymerization and copolymerization of olefine and its synthesis and use - Google Patents

Catalyst for polymerization and copolymerization of olefine and its synthesis and use Download PDF

Info

Publication number
CN1256351C
CN1256351C CN 01126323 CN01126323A CN1256351C CN 1256351 C CN1256351 C CN 1256351C CN 01126323 CN01126323 CN 01126323 CN 01126323 A CN01126323 A CN 01126323A CN 1256351 C CN1256351 C CN 1256351C
Authority
CN
China
Prior art keywords
refer
alkyl
group
linkage
covalent linkage
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
CN 01126323
Other languages
Chinese (zh)
Other versions
CN1332182A (en
Inventor
唐勇
孙秀丽
胡蔚秋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Institute of Organic Chemistry of CAS
Original Assignee
Shanghai Institute of Organic Chemistry of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Institute of Organic Chemistry of CAS filed Critical Shanghai Institute of Organic Chemistry of CAS
Priority to CN 01126323 priority Critical patent/CN1256351C/en
Publication of CN1332182A publication Critical patent/CN1332182A/en
Priority to EP02754132A priority patent/EP1426385B1/en
Priority to PCT/CN2002/000425 priority patent/WO2003010207A1/en
Priority to US10/761,827 priority patent/US7253133B2/en
Application granted granted Critical
Publication of CN1256351C publication Critical patent/CN1256351C/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Landscapes

  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

The present invention relates to a catalyst for the polymerization and the copolymerization of olefin, a synthetic method thereof and application in the catalysis of olefinic polymerization. The catalyst is a transition metal compound from the first group to the thirteenth group of a kind of novel three-tooth ligand, and the structure of the catalyst is disclosed in the right formula.

Description

Olefinic polymerization and copolymerization catalyst, preparation method and use
Technical field
The present invention relates to olefinic polymerization and copolymerization catalyst, synthetic method and be used for catalysis in olefine polymerization, this catalyzer is three races's to the 13 group 4 transition metal complexes of a class new tridentate ligand.
Background technology
Since having found Ziegler-Natta catalyst from 1850s, highly active MgCl 2The catalyzer of the titanium of load has shown good catalytic performance, thus this Application of Catalyst simplified production process and saved the energy and starting material, improved polymer properties (K.Ziegler, etc., Angew.Chem.1995,67,424; K.Ziegler etc., Angew.Chem.1995,67,541; N.Kashiwa etc., USP-3642746,1968).Industrial, this catalyzer has been used for high density polyethylene(HDPE) (HDPE), linear low density polyethylene (LLDPE), the production of the polymkeric substance of syndiotactic polypropylene (i-PP).Yet the solid catalyst in this many active centre can't well come the structure and the performance of controlling polymers at present by the adjusting catalyst structure.The discovery of the 4th family's metallocene catalyst has then solved this problem preferably, owing to have single active center, make people can obtain polymkeric substance (W.Kaminsky etc., the Adv.Organomet.Chem.1980 of expected structure as required by the structure that changes catalyzer, 18,99; W.Kaminsky etc., Angew.Chem., Int.Ed.Engl.1980,19,390; H.H.Brintzinger etc., Angew.Chem.Int.Ed.Engl.1995,34,1143).After having found metallocene catalyst, late transition metal complex is also flourish as the research of olefin polymerization catalysis recently, this class catalyzer is collectively referred to as " luxuriant rear catalyst ", since nineteen ninety-five, there are some new outstanding catalyzer to be synthesized out gradually, shown in the following array structure formula:
Figure C0112632300141
Structural formula
Nineteen ninety-five, Brookhart has reported that the nickel catalyst of diimine structure (a) can highly actively make vinyl polymerization obtain branched polyethylene (M.S.Brookhart etc., J.Am.Chem.Soc.1995,117,6414) under the effect of promotor.1996, Brookhart confirmed that again the palladium catalyst of same part (b) can be good at copolymerization (M.S.Brookhart etc., J.Am.Chem.Soc., 1996,118,267 of catalyzed ethylene and methyl acrylate; M.S.Brookhart etc., J.Am.Chem.Soc., 1996,118,11664; M.S.Brookhart etc., J.Am.Chern.Soc., 1998,120,888; M.S.Brookhart etc., WO 9623010; M.S.Brookhart etc., US 5,866,663 1999; M.S.Brookhart etc., US 5,880,241 1999; M.S.Brookhart etc., US 5,880,323 1999; M.S.Brookhart etc., US 5,891,963 1999).1998, Brookhart and Gibson found independently separately that respectively the iron of a series of pyridine diimines is complex compound (M.S.Brookhart etc., J.Am.Chem.Soc., 1998,120,4049; Polym.Prepr. (Am.Chem.Soc., Div.Polym.Chem.), 1998,39,213; WO 98/30612; WO99/02472) (V.C.Gibson etc., Chem.Commun., 1998,849; Angew.Chem., Int.Ed.Engl., 1999,38,428; WO 99/12981; WO98/27124), the complex-catalyzed vinyl polymerization of this class has very high activity, can be with metallocene catalyzed ethylene polymerization quite active.This result surprisingly because before this, people generally believe that the polymerization activity of metallocene catalyst has reached the summit, can not also have what catalyzer can surmount it.In addition, the Titanium series catalyst that contains two amine ligands (d) has shown good catalytic activity (D.H.McConville etc., Makromolekules, 1996,29,5241 for catalysis high-grade alpha-olefine polymerizing; D.H.McConville etc., Organimetallics, 1997,16,1810; D.H.McConville etc., Organimetallics, 1997,16,4415; WO2000/069922A2).Some are that the nickel catalyst of part (e) can not only highly active catalyzed ethylene polymerization but also there are good tolerance (R.H.Grubbs etc., Organometallics, 1998,17,3149 in functional group with phenol oxygen base imines; R.H.Grubbs etc., Science, 2000,287,460; WO98/42664; WO 98/42665).1999, the salicylic alidehyde imine titanium (IV) of T.Fujita group report, the title complex (f) of zirconium (IV) (shown in the following array structure formula) can highly active catalyzed ethylene polymerization under the effect of promotor (MAO), its activity is considerably beyond other non-luxuriant class the 4th group 4 transition metal catalyzer (Terunori Fujita etc., Chemistry Letters 1999,1065-1066; Terunori Fujita etc., Chemistry Letters 1999,1263-1264; Terunori Fujita etc., Chemistry Letters 2000,554-555; Terunori Fujita etc., Chemistry Letters 2000,1270-1271:WO 99/54364).
Figure C0112632300151
Some tridentate ligands of existing report are as containing [N -1NN -1], [N -1ON -1] the title complex of zirconium vinyl polymerization is had medium catalytic activity (Horton AD etc., Orgaometallics, 1996,15,2657; M.Bochmann etc., J.Cheem.Soc.Dalton.Trans, 1997,2487, J.Am.Chem.Soc.1997 such as Baumann R, 119,3830), and contain the tridentate ligand [N of pyridine electron-donating group -1NN -1] zirconium (IV) title complex then has very high activity (McConcille D.H., Orgaometallics, 1996,15,5586), but when the center atom is titanium, because it is very low easily to be reduced to titanium (III) catalytic activity.Up to the present, a lot (K.Hakala etc., Macromol.Chem.Rapid.Commun.1997,18,635 of the report of relevant this luxuriant rear catalyst; D.W.Stephan etc., J.Chem.Soc., Dalton.Trans.1998,255; N.J.Nicholas etc., Organometallics 1999,18, and 2731; M.D.Ransch, Organometallics 1995,14, and 1827).
Not a lot of for report on the compound document of the titanous chloride (IV) of non-luxuriant class single anion ligand and tri-chlorination zirconium (IV) in the document, the title complex of reports such as Terunori Fujita (g) has shown medium activity (Terunori Fujita etc. to vinyl polymerization, WO99/54346), Nagy S, the title complex that contains the titanium (IV) of oxine negative ion Deng people's synthetic has very high catalytic activity to vinyl polymerization, (EthertonB P.PCT Int Appl such as Nagy S, 1996,96/34021) people (Organometallics such as .A.Otero, 2001,20,2428-2430) reported following compound:
Figure C0112632300161
Vinyl polymerization has been shown high activity, and the resulting polymers molecular weight is very high, but the molecular weight distribution broad.
People such as Joanthan Parr once reported and had synthesized a series of following structural coordination compound nickel (II), palladium (II), platinum (II), the title complex of ruthenium (Joanthan Parr etc., J.Chem.Soc., Dalton.1998,3609; Joanthan Parr etc., J.Chem.Soc., Dalton.1999,2917; Inorganica Chimica Acta 2000,303,116), still these compounds all are not useful on the report of olefinic polymerization.These title complex statements are not protected among the present invention.
Figure C0112632300162
Summary of the invention
The object of the invention provides a class olefinic polymerization and a copolymerization catalyst, promptly is three races's to the 13 group 4 transition metal complexes catalyst system of the class tridentate ligand that is used for olefinic polymerization.
The object of the invention also provides the synthetic method of above-mentioned catalyzer, i.e. the synthetic method of three races's to the 13 group 4 transition metal complexes of tridentate ligand.
Another purpose of the present invention provides the purposes of above-mentioned catalyzer, and this catalyst system can be used for catalyzed ethylene, alpha-olefin, contains the homopolymerization and the copolymerization of the alkene of functional groups.This catalyzer still keeps high reactivity under the very low situation of promotor consumption, and can adapt to wide temperature range and active not obviously decline.
Alkene provided by the invention and copolymerization polymerizing catalyst are the described title complex (I) of following structural formula:
Figure C0112632300171
Wherein:
M:1,2 or 3;
Q:0 or 1;
M: transition metal atoms, the especially titanium of ten gangs of three races to the, zirconium, hafnium, iron, chromium, cobalt, nickel;
N:1,2 or 3;
X: be to comprise halogen atom, hydrogen atom, C 1-C 30Alkyl, oxy radical, nitrogen-containing group, sulfur-containing group, boron-containing group, contain aluminium base group, phosphorus-containing groups, silicon-containing group, germanic group or contain tin group at interior anion ligand, several X can be identical, also can be different, can also be each other in key Cheng Huan;
The halogen atom here comprises fluorine, chlorine, bromine or iodine;
In the structural formula all parts electronegative sum absolute value should with metal M in the structural formula the absolute value of positively charged sum identical, all parts comprise X and tridentate ligand;
A: Sauerstoffatom, sulphur atom, selenium atom, R 21N or R 21P;
B: refer to nitrogen-containing group or C 1-C 30Alkyl;
D: refer to nitrogen-atoms, Sauerstoffatom, sulphur atom, selenium atom, phosphorus atom, C 1-C 30The nitrogenous or C of alkyl 1-C 30The phosphorus-containing groups of alkyl, wherein N, O, S, Se, P are ligating atom:
E: refer to nitrogen-containing group, oxy radical, sulfur-containing group, contain seleno group, phosphorus-containing groups, wherein N, O, S, Se, P are ligating atom;
→: refer to singly-bound or two key;
: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage;
R 1, R 2, R 3, R 21: hydrogen, C 1-C 30Alkyl, halogen atom, C 1-C 30Substituted hydrocarbon radical be meant halogenated alkyl especially, as-CH 2Cl ,-CH 2CH 2Cl or safing function group, R 1, R 2, R 3, R 21Can be the same or different wherein adjacent R 1, R 2, R 3Part can be each other in key Cheng Huan.Condition is that related part is not
Figure C0112632300181
To further be elaborated to catalyst system of the present invention below, this catalyzer also can be divided into following two big classes:
(1) catalyzer (IA)
Wherein:
M, M, n, X, A, B, E, R 1, R 2, R 3, q is with identical described in the aforementioned structural formula (I);
: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage.
(IA-1～IA-6) will help to more clearly understand this catalyst system:
Wherein:
R 4: hydrogen, C 1-C 30Alkyl, halogen atom, C 1-C 30The alkyl of replacement be meant C especially 1-C 30Halogenated alkyl, as-CH 2Cl ,-CH 2CH 2Cl or safing function group, wherein adjacent R 4With R 1Can be each other in key Cheng Huan;
: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage;
Q, m, M, n, X, A, E, R 1, R 2, R 3With identical described in the aforementioned structural formula (I).
Wherein: q, m, M, n, X, A, E, R 3, R 4With identical described in the aforementioned structural formula (IA-1);
: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage;
R 6, R 7, R 8, R 9: hydrogen, C 1-C 30Alkyl, halogen atom, C 1-C 30The alkyl of replacement be meant C especially 1-C 30Halogenated alkyl, as-CH 2Cl ,-CH 2CH 2Cl or safing function group; R 3, R 4, R 6, R 7, R 8, R 9Can be the same or different, can be each other in key Cheng Huan.
Figure C0112632300192
Wherein:
: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage;
Q, m, M, n, X, A, E, R 3, R 6, R 7, R 8, R 9With identical described in the aforementioned structural formula (IA-2).
Figure C0112632300201
Wherein:
: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage;
M, M, n, X, A, E, R 1, R 2, R 4With identical described in the aforementioned structural formula (I).
Figure C0112632300202
Wherein:
: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage; M, M, n, X, A, E, R 4, R 6, R 7, R 8, R 9With identical described in the aforementioned structural formula (IA-2).
Figure C0112632300211
Wherein:
: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage;
M, M, n, X, A, E, R 6, R 7, R 8, R 9With identical described in the aforementioned structural formula (IA-2).
(2) catalyzer (IB)
Figure C0112632300212
Wherein:
: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage;
Q, m, M, n, X, A, B, E, R 1, R 2, R 3With identical described in the aforementioned structural formula (I);
F: refer to nitrogen-containing group, oxy radical, sulfur-containing group, contain seleno group, phosphorus-containing groups, wherein N, O, S, Se, P are ligating atom.
(IB-1～IB-6) also will help to more clearly understand this catalyst system:
Wherein:
: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage;
Q, m, M, n, X, A, E, F, R 1, R 2, R 3With identical described in the aforementioned structural formula (IB);
R 10, R 11: hydrogen, C 1-C 30Alkyl, halogen atom, C 1-C 30The alkyl of replacement be meant C especially 1-C 30Halogenated alkyl, as-CH 2Cl ,-CH 2CH 2Cl or safing function group, wherein R 10, R 11, R 1Can be the same or different, can be each other in key Cheng Huan.
Wherein:
: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage;
Q, m, M, n, X, A, E, F, R 3, R 10, R 11With identical described in the aforementioned structural formula (IB-1);
R 6, R 7, R 8, R 9: hydrogen, C 1-C 30Alkyl, halogen atom, C 1-C 30The alkyl of replacement be meant C especially 1-C 30Halogenated alkyl, as-CH 2Cl ,-CH 2CH 2Cl or safing function group.R 6, R 7, R 8, R 9, R 10, R 11Can be the same or different, can be each other in key Cheng Huan.
Figure C0112632300231
Wherein:
: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage;
Q, m, M, n, X, A, E, F, R 3, R 6, R 7, R 8, R 9: with identical described in the aforementioned structural formula (IB-2);
R 12: hydrogen, C 1-C 30Alkyl, halogen atom, C 1-C 30The alkyl of replacement be meant C especially 1-C 30Halogenated alkyl, as-CH 2Cl ,-CH 2CH 2Cl or safing function group.R 6, R 12Can be the same or different, can be each other in key Cheng Huan.
Wherein:
: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage;
M, M, n, X, A, E, F, R 1, R 2, R 10, R 11With identical described in the aforementioned structural formula (IB-1).
Figure C0112632300241
Wherein:
: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage;
M, M, n, X, A, E, F, R 6, R 7, R 8, R 9, R 10, R 11With identical described in the aforementioned structural formula (IB-2).
Figure C0112632300242
Wherein:
: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage;
M, M, n, X, A, E, F, R 6, R 7, R 8, R 9, R 12: with identical described in the aforementioned structural formula (IB-3).
Catalyzer of the present invention also can have following structure:
Figure C0112632300251
Wherein: R 13, R 14, R 15, R 16, R 17, R 18, R 19, R 20, R 31Be C 1-C 30Alkyl, can be the same or different to each other, also can be each other in key Cheng Huan; Z=N, P; M=Ti, Zr, Hf, Fe or Co; X=F, Cl, Br, I, C 1-C 30Alkyl, weak coordinate negatively charged ion comprise (R 32) 3AlX -, (R 32) 2AlX 2 -, (R 32) AlX 3 -, SbF 6 -, PF 6 -, BF 4 -, (C 6F 5) 4B -, R f(SO 2) 2, N -, CF 3SO 3 -, ((3,5-(CF 3) 2) C 6H 3) 4B -Y=O, S; N is 1,2 or 3, and negatively charged ion negative charge sum should be identical with the burning attitude in the structural formula;
R 32Refer to hydrogen, C 1-C 30Alkyl, halogen atom, C 1-C 30The alkyl of replacement be meant halogenated alkyl especially, as-CH 2Cl ,-CH 2CH 2Cl or safing function group;
R fRefer to C 1-C 30Fluorine-containing alkyl;
: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage.
Figure C0112632300252
R 13, R 14, R 15, R 16, R 17, R 18, R 19, R 20, R 31, R 33Be C 1-C 30Alkyl can be the same or different, also can be each other in key Cheng Huan: Z=N, P to each other; M=Ti, Zr, Hf, Fe or Co; X=F, Cl, Br, I, C 1-C 30Alkyl, weak coordinate negatively charged ion comprise (R 32) 3AlX -, (R 32) 2AlX 2 -, (R 32) AlX 3 -, SbF 6 -, PF 6 -, BF 4 -, (C 6F 5) 4B -, R f(SO 2) 2, N -, CF 3SO 3 -, ((3,5-(CF 3) 2) C 6H 3) 4B -Y=O, S; N is 1,2 or 3, and negatively charged ion negative charge sum should be identical with the burning attitude in the structural formula;
R 32Refer to hydrogen, C 1-C 30Alkyl, halogen atom, C 1-C 30The alkyl of replacement be meant halogenated alkyl especially, as-CH 2Cl ,-CH 2CH 2Cl or safing function group;
R fRefer to C 1-C 30Fluorine-containing alkyl;
: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage.
To the part term that foregoing partly uses be described as follows below, these explanations will help clearer understanding content of the present invention.
Alkyl refers to contain C 1-C 30Alkyl, C 1-C 30Cyclic hydrocarbon group, C 1-C 30-C 30Group, the C of carbon-carbon double bonds 2-C 30Carbon containing carbon triple-linked group, C 6-C 30Aryl radical, C 8-C 30Condensed ring alkyl or C 4-C 30Heterogeneous ring compound;
The alkyl that replaces refers to contain on the alkyl one or more substituted radical, under the employed process condition of the compound that contains substituted hydrocarbon radical, these substituting groups are inert, and these substituting groups do not have substantial interference to related process yet, in other words, these substituting groups generally not with metal-complexing.As non-specified otherwise, refer generally to contain the group of 1～30 carbon atom, and substituting group also comprises C 6-C 30Aryl radical, C 8-C 30Condensed ring alkyl or C 4-C 30Heterocyclic compound;
The safing function group is different from other functional groups of alkyl and substituted hydrocarbon radical at this patent middle finger, this functional group to the compound that contains this functional groups all do not have substantially in the reaction that may participate in and disturb, here the indication functional groups comprises halogen (fluorine, chlorine, bromine, iodine), ether is (as-OR 22Or-CH 2TOR 22, T, R 22Be C 1-C 30Alkyl or C 1-C 30Substituted hydrocarbon radical), C 1-6Ester group, C 1-6Amido, C 1-6Alkoxyl group, oxy radicals such as nitro, nitrogen-containing group, silicon-containing group, germanic group, sulfur-containing group or contain tin group is when functional groups during near atoms metal, the coordination ability of itself and metal is not better than A, E, the F group that contains ligating atom, and promptly these functional groups should not replace desirable coordinating group;
Oxy radical refers to hydroxyl, alkoxyl group-OR 22, the alkyl that has an ehter bond is as-CH 2-T-OR 22
Sulfur-containing group refers to-SH ,-SR 23,-CH 2-T-OR 23
R 23Be C 1-C 30Alkyl or C 1-C 30Substituted hydrocarbon radical;
Boron-containing group refers to BF 4 -, (C 6F 5) 4B -, (R 24BAr 3) -
R 24Be meant C 1-C 30Alkyl or C 1-C 30Substituted hydrocarbon radical;
Alkylaluminium cpd refers to have at least an alkyl to link to each other with the aluminium atom, and other groups also link to each other with the aluminium atom.
As methylaluminoxane (MAO), AlEt 3, AlMe 3, Al (i-Bu) 3
Contain aluminium base group and refer to alkylaluminium cpd, AlPh 4 -, AlF 4 -, AlCl 4 -, AlBr 4 -, AlI 4 -
Phosphorus-containing groups refers to-CH 2-T-PR 25
R 25Be C 1-C 30Alkyl or C 1-C 30Substituted hydrocarbon radical, T=-CH 2-C nH 2n-,-CH 2-C nH 2n-2-,-CH 2-C nH 2n-4, n=1～30);
Nitrogen-containing group refers to-NR 2,-NH 2,-NHR reaches-CH 2-T-NR 26(R 26Be C 1-C 30Alkyl or C 1-C 30Substituted hydrocarbon radical, T=-CH 2-C nH 2n-,-CH 2-C nH 2n-2-,-CH 2-C nH 2n-4, n=1～30);
Silicon-containing group refers to-CH 2-T-SiR 27(R 27Be C 1-C 30Alkyl or C 1-C 30Substituted hydrocarbon radical, T=-CH 2-C nH 2n-,-CH 2-C nH 2n-2-,-CH 2-C nH 2n-4, n=1～30);
Germanic group-CH 2-T-GeR 28(R 28Be C 1-C 30Alkyl or C 1-C 30Substituted hydrocarbon radical, T=-CH 2-C nH 2n-,-CH 2-C nH 2n-2-,-CH 2-C nH 2n-4, n=1～30);
Contain tin group and refer to-CH 2-T-SnR 29(R 29Be C 1-C 30Alkyl or C 1-C 30Substituted hydrocarbon radical, T=-CH 2-C nH 2n-,-CH 2-C nH 2n-2-,-CH 2-C nH 2n-4, n=1～30);
Weak coordinate negatively charged ion is meant relatively not coordinate negatively charged ion, and its coordination situation can be referring to document (W.Beck., et al., Chem.Rev., vol.88, p1405-1421 (1988), and S.H.Stares, Chem.Rev., vol.93, p927-942 (1993)) and internal reference document, for example (R 32) 3AlX -, (R 32) 2AlX 2 -, (R 32) AlX 3 -, SbF 6 -, PF 6 -, BF 4 -, (C 6F 5) 4B -, (R fSO 2) 2, N -, CF 3SO 3 -, ((3,5-(CF 3) 2) C 6H 3) 4B -Deng.
Synthesizing of catalyzer of the present invention
Among the present invention, catalyzer is to be mixed with mol ratio 1: 0.1～6 by the part of following structural formula or the negative ion metallizing thing of part in organic solvent, obtain to the temperature range internal reaction that refluxes at-78 ℃, organic solvent refers to tetrahydrofuran (THF), sherwood oil, toluene, methylene dichloride, CCl 4, ether, 2,4-dioxane or 1,2-ethylene dichloride etc.
Figure C0112632300271
Wherein:
A: Sauerstoffatom, sulphur atom, selenium atom, R 21N or R 21P;
B: refer to nitrogen-containing group or C 1-C 30Alkyl;
D: refer to nitrogen-atoms, Sauerstoffatom, sulphur atom, selenium atom, phosphorus atom, C 1-C 30The nitrogenous or C of alkyl 1-C 30The phosphorus-containing groups of alkyl, wherein N, O, S, Se, P are ligating atom;
E: refer to nitrogen-containing group, oxy radical, sulfur-containing group, contain seleno group, phosphorus-containing groups, wherein N, O, S, Se, P are ligating atom;
→: refer to singly-bound or two key;
-: refer to covalent linkage or ionic linkage;
R 1, R 2, R, R 21: hydrogen, C 1-C 30Alkyl, halogen atom, C 1-C 30Substituted hydrocarbon radical be meant halogenated alkyl especially, as-CH 2Cl ,-CH 2CH 2Cl or safing function group, R 1, R 2, R can be the same or different wherein adjacent R 1, R 2, R part can be each other in key Cheng Huan.
The part part that catalyzer of the present invention adopted is as follows:
Part catalyzer code description of the present invention
(L1) m-MCl n(the negatively charged ion that forms after the body of the L1 assignment herein L1 dehydrogenation
Figure C0112632300291
Table 1 ligand L 1 forms the part complex compound
The catalyzer code name M m n
A-1 B-1 C-1 D-1 F-1 G-1 Ti Ti Zr Zr Fe Fe 1 2 1 2 1 1 3 2 3 2 2 1
(L2) m-MCl n(negatively charged ion that forms after the body of the L2 assignment herein L2 dehydrogenation)
Table 2 ligand L 2 forms the part complex compound
The catalyzer code name M m n
A-2 B-2 C-2 D-2 F-2 G-2 Ti Ti Zr Zr Fe Fe 1 2 1 2 1 1 3 2 3 2 2 1
L3 forms the part complex compound
(L3) m-MCl n(negatively charged ion that forms after the body of the L3 assignment herein L3 dehydrogenation)
Table 3 part
The catalyzer code name M m n
A-3 B-3 C-3 D-3 F-3 G-3 Ti Ti Zr Zr Fe Fe 1 2 1 2 1 1 3 2 3 2 2 1
Table 4 ligand L 4 forms the part complex compound
(L4) m-MCl n(negatively charged ion that forms after the body of the L4 assignment herein L4 dehydrogenation)
The catalyzer code name M m n
A-4 B-4 C-4 D-4 F-4 G-4 Ti Ti Zr Zr Fe Fe 1 2 1 2 1 1 3 2 3 2 2 1
(L5) m-MCl n(negatively charged ion that forms after the body of the L5 assignment herein L5 dehydrogenation)
Table 5 ligand L 5 forms the part complex compound
The catalyzer code name M m n
A-5 B-5 C-5 D-5 F-5 G-5 Ti Ti Zr Zr Fe Fe 1 2 1 2 1 1 3 2 3 2 2 1
Table 6 ligand L 6 forms the part complex compound
(L6) m-MCl n(negatively charged ion that forms after the body of the L6 assignment herein L6 dehydrogenation)
The catalyzer code name M m n
A-6 B-6 C-6 D-6 F-6 G-6 Ti Ti Zr Zr Fe Fe 1 2 1 2 1 1 3 2 3 2 2 1
(Ln) NiPh (PPh 3) (negatively charged ion that forms after the body of the Ln assignment herein Ln dehydrogenation)
Example:
Figure C0112632300311
Purposes-the reactant of catalyzer, polymerization and polymerisate
Table 7 ligand L 1～6 forms part metals Ni complex compound
The catalyzer code name n
E-1 E-2 E-3 E-4 E-5 E-6 1 2 3 4 5 6
Catalyzer of the present invention can be used for olefinic polymerization, comprises homopolymerization or copolymerization, usually can with promotor directly use or load after use.
The present invention relates to following olefin polymerization process, promptly the following substances interaction is comprised 1. catalyzer shown in the structural formula (I) at-100～200 ℃
2. alkene
3. promotor W, a kind of neutral Lewis acid (Lewis acid) can take out X from metal M -Form (WX) -, and as (WX) -When being weak coordinate negatively charged ion, W can be with alkyl or hydrogen transference on metal M, as the methylaluminoxane MMAO of alkylaluminium cpd especially methylaluminoxane (MAO) or modification; Two kinds of compounds of use perhaps also capable of being combined, wherein a kind of can with alkyl or hydrogen transference on the metal M as alkylaluminium cpd especially AlEt 3, AlMe 3, Al (i-Bu) 3, another kind can take out X from metal M -, as sodium salt or silver salt: Na[B (3,5-(CF 3) 2C 6H 3) 4], AgOSO 2CF 3, alkylaluminium cpd or borine B (C 6F 5) 3Form weakly coordinating anion.
Above-mentioned catalyzer of the present invention can be used for catalysis in olefine polymerization under the effect of promotor, alkene comprises ethene, alpha-olefin, vinylbenzene, methyl methacrylate etc., and alpha-olefin is meant C 3-C 8Alkene, for example propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, 4-methyl-1-pentene and its mixture etc., polymerization comprises above-mentioned monomeric homopolymerization and copolymerization, if polymerisate is the multipolymer of ethene and alpha-olefin, then recommend to use 1-hexene, 4-methyl-1-pentene as comonomer to reach maximum polymer strength.
Slurry polymerization, endless tube polymerization or other special shapes are adopted in the monomeric together polymerization of monomer.Wherein slurry polymerization is easy to operate, and polymerisate is convenient to reclaim, this polymerization technique known by people and document in have and report, for example can be referring to U.S.Pat.No.3,248,179.
Polymerization is generally carried out in inert solvent, for example hydro carbons, cyclic hydrocar-bons or aromatic hydrocarbons.For helping reactor operation and polymerisate, inert solvent can use the hydro carbons less than 12 carbon, is exemplified below but is not limited in this propane, Trimethylmethane, Skellysolve A, 2-methylbutane, hexane, toluene, chlorobenzene and composition thereof.Especially the 2-methylbutane, toluene is cheap and easy to use.
Polymerization temperature maintains-50～150 ℃, for reaching good catalytic activity and throughput, can maintain 0～70 ℃.
Polymerization pressure can change in 0.1～10MPa, and operation can obtain reactor operating parameters and polymkeric substance preferably in 0.1～3MPa.
Catalyst concn can be 10 -6～10 -3M is recommended in 10 -5～10 -4Use in the M.
Promotor is MAO (methylaluminoxane), mMAO (methylaluminoxane of modification), EAO (ethyl aikyiaiurnirsoxan beta), BAO (butyl aikyiaiurnirsoxan beta), LiR (R=C 1-4Alkyl), AlR 3(R=C 1-4Alkyl), Lewis acid (Lewis acid), LiR/Lewis acid (R=C 1-4Alkyl) AlR 3/ Lewis acid (R=C 1-4Alkyl), borine such as B (C 6F 5) 3Deng.
Catalyzer and promotor can any order adding system all can make polymerization carry out.For example, catalyzer elder generation adding system adds partial solvent and MAO subsequently, adds remaining solvent again, and last ethene feeds.But as previously mentioned, this order of addition(of ingredients) can be looked the feasibility of operation and desirable product property and be changed.Catalyzer had better not mix before adding polymerization system with promotor, in order to avoid cause unnecessary decay of activity.
The amount of employed catalyzer of polymerization and promotor is variable.Usually the mol ratio of catalyzer and promotor is 1: 1～5000, generally can be 1: 10～2000 so that make catalytic activity, polymer property and production cost all maintain scope preferably.
Polyreaction can be used round-bottomed flask, autoclave or annular-pipe reactor, can single still use also can be used in combination with the multiple reactor series, parallel or with certain form, and wherein each reactor condition can be the same or different.
Resulting polymers of the present invention has narrower molecular weight distribution (Mw/Mn) and is generally 1～3.
Brief summary:
The invention provides a kind of olefinic polymerization and copolymerization catalyst, preparation method and use.This catalyzer is three races's to the 13 group 4 transition metal complexes of tridentate ligand, is to be reacted in organic solvent such as tetrahydrofuran (THF) by above-mentioned part metallizing thing to obtain.This catalyzer provided by the invention can be used for catalyzed ethylene, alpha-olefin, contains the homopolymerization and the copolymerization of functionalization group alkene under the effect of promotor.This catalyzer has shown following several respects distinguishing feature in the process of catalysis in olefine polymerization and copolymerization:
Under the situation of promotor consumption very low (Al/M=10～50), still keep high catalytic activity; Can adapt to wide temperature range and active unobvious decline; Method with this catalyst ethylene homo and alkene, methyl methacrylate homopolymerization also is provided in the present invention, has realized the homopolymerization and the copolymerization of catalyzed ethylene or alpha-olefin, obtained high molecular, the polymkeric substance of narrow molecular weight distributions.
Specific implementation method
The following examples will better illustrate the present invention, but what need emphasize is that the present invention only limits to never that these are several
Content that embodiment explains.
Following example has shown not ipsilateral of the present invention.Given data comprise synthetic, metal complex synthetic of part, converging operation, polymerizing condition and polymerisate.All operations comprises reaction, preparation and stores and all carries out under the exsiccant inert atmosphere, adopts the Schlenk of standard to operate.In 140 ℃ of mensuration, orthodichlorobenzene is made eluent at Waters model 150GPC (differential refraction detector) for molecular weight and molecular weight distribution, and polystyrene is the reference standard specimen.
Synthesizing of embodiment one ligand L 1
In the reaction flask of 100ml, add 8.2g (34.4mmol) 3, the 5-di-tert-butyl salicylaldehyde, 9.6g (34.6mmol) (o-amino-phenyl-) diphenylphosphine, 50ml dehydrated alcohol, the Glacial acetic acid of molecular sieve and catalytic amount, after being heated to backflow 24h, stopped reaction is removed molecular sieve, concentrate, make to be chilled to room temperature, promptly obtain crude product, with ethanol/ether recrystallization, obtain pale yellow crystals L1,11.8g (69.4%).
Figure C0112632300341
Ultimate analysis: actual measurement (calculated value): C:80.39 (80.29) H:7.59 (7.35) N:2.77 (2.84)
1HNMr(300MHz CDCl 3)：δ8.4(s CH＝N)；7.4-6.8(m，Aryl H)1.4，1.3(s，st-Bu-H)
δ( 31P)-5.52(s)
Synthesizing of embodiment two ligand L 2
In the reaction flask of 50ml, add 750mg (3.2mmol) 3, the 5-di-tert-butyl salicylaldehyde, 440mg (3.2mmol) neighbour-dimethylamino-aniline, 25ml dehydrated alcohol, the Glacial acetic acid of molecular sieve and catalytic amount, after being heated to backflow 20h, stopped reaction is removed molecular sieve, concentrates, make and be chilled to room temperature, promptly obtain crude product,, obtain pale yellow crystals L2 352mg (31%) with ethyl alcohol recrystallization.
Figure C0112632300351
Ultimate analysis: actual measurement (calculated value): C 78.20 (78.37) H 8.86 (9.17) N 7.86 (7.86) 1HNMR (300MHz CDCl 3): δ (ppm) 13.9 (s, O-H) 8.6-8.7 (s CH=N) 7.6-6.9 (m, Aryl6H) 2.9 (s, CH 36H) 1.5,1.3 (s, s t-Bu-H, 9H, 9H)
MS 352(M+100.00)
IR (KBr compressing tablet) υ C=N(cm -1) 1614
Synthesizing of embodiment three ligand L 3
In reaction flask, add 1.17g (5.25mmol) 3, the 5-di-tert-butyl salicylaldehyde, (5.25mmol) 0.64g (N-methyl-o-phenylenediamine), the 15ml dehydrated alcohol, the Glacial acetic acid of molecular sieve and catalytic amount, be heated to backflow 2h after, stopped reaction, remove molecular sieve, cooling promptly obtains crude product, with ethyl alcohol recrystallization, obtain pale yellow crystals L3 1.67g (98%).
Ultimate analysis: actual measurement (calculated value): C 77.85 (78.06) is (8.98) N 8.30 (8.28) H.86: 1HNMR (300MHz CDCl 3): δ (ppm) 13.4-13.2 (s, O-H) 8.3 (s CH=N); 7.6-6.6 (m, 6HAryl-H) 3.1 (s, N-CH 3) 1.5,1.4 (s, s 9H, 9H t-Bu-H).
MS(M+)338
IR(KBr)υ C＝N(cm -1)1613.3
Figure C0112632300352
Synthesizing of embodiment four ligand L 4
In reaction flask, add 2.0g (8.5mmol) 3, the 5-di-tert-butyl salicylaldehyde, 0.92g (8.5mmol) 2-aminomethyl-pyridine, the 25ml methylene dichloride, stopped reaction behind an amount of sal epsom stirring at room 20h filters, remove sal epsom, remove and desolvate, the crude product column chromatography obtains ligand L 41.21g (44.4%).
Figure C0112632300361
Ultimate analysis: actual measurement (calculated value): C 77.70 (77.57) H 8.85 (8.98) N 8.59 (8.60) 1HNMR (300MHz CDCl 3): δ (ppm) 13.6 (s O-H) 8.6 (m 2H); (7.69-7.14 m 5HAryl H) 4.93 (s-CH 2-) 1.45,1.32 (s, s t-Bu-H)
MS(M +)324
IR(KBr)υ C＝N(cm -1)1629.0
Synthesizing of embodiment five ligand L 5
With 468mg (2mmol) 3, the 5-di-tert-butyl salicylaldehyde, 236mg (2mmol) neighbour-itrile group aniline is dissolved in the 15ml dehydrated alcohol, and the Glacial acetic acid that adds catalytic amount is as catalyzer, be heated to backflow, behind the reaction 24h, stopped reaction removes and desolvates, promptly obtain crude product, column chromatography for separation is ligand L 5,253mg (35.9%).
Ultimate analysis: actual measurement (calculated value): C:78.85 (79.00) H:7.85 (7.84) N:8.33 (8.38)
IR (KBr compressing tablet) υ C=N(cm -1) 1614
Embodiment sexadentate L6's is synthetic
With 500mg (2.99mmol) right-nitro 3-tertiary butyl salicylic aldehyde, 900mg (3.25mmol) neighbour-aminocarbonyl phenyl phenylbenzene is seen and is dissolved in the 25ml dehydrated alcohol, the Glacial acetic acid that adds catalytic amount is heated to backflow as catalyzer, behind the reaction 4h, stopped reaction, make to be chilled to room temperature, promptly separate out crude product, with ethyl alcohol recrystallization, obtain ligand L 6,730mg (57.3%).
Figure C0112632300371
Ultimate analysis: actual measurement (calculated value): C 70.70 (70.42) H 4.56 (4.49) N 7.01 (6.57)
1H NMR(300MHz CDCl 3)：δ(ppm)7.98(s 1H)；7.75-6.66(m 17H Aryl H)
Synthesizing of embodiment seven ligand L 7
Above-mentioned part obtains corresponding amine according to usual method reduction or alkylation.Be the synthesis step of ligand L 7 below, the reduction of other part is all according to synthetic with the L7 similar methods.
Under nitrogen protection, in the 15ml tetrahydrofuran solution of 0.49g (1.0mmol) ligand L 1, drip 0.2g (1.0mmol) n-Bu 2SnH 2And 0.32g (1.0mmol) n-Bu 2SnCl 2Mixture, mixture stirred after 20 minutes, added 0.35ml (2.0mmol) hexamethylphosphoramide (HMPA) and 0.13ml (2.0mmol) methyl iodide in this mixing solutions, remained on 60 ℃ of stirring 3h then.Adding methyl alcohol crosses the reaction solution collection back of going out silicagel column and purifies and obtain L7 331mg (65%)
Figure C0112632300372
FID-MS：(M+)509
Ultimate analysis: actual measurement (calculating): C:80.25 (80.13); H:7.88 (7.91); N:2.75 (2.73) 1HNMR (CDCl 3): 7.76-6.83 (m, 16H), 4.33 (s, 2H), 2.75 (s, 3H), 1.50,1.43 (s, s 9H, 9H)
Synthesizing of embodiment eight ligand L 8
The 5ml methanol suspension that adds 0.14g (4.0mmol) sodium borohydride under nitrogen protection in the 10ml methanol solution of 0.98g (2.0mmol) ligand L 1 slowly continued to stir after 30 minutes, and reaction solution goes out with the frozen water collection.Silicagel column is purified and is obtained L8 940mg (94.8%).
Figure C0112632300381
FID-MS：(M+)495
Ultimate analysis: actual measurement (calculating): C:79.87 (79.97); H:7.89 (7.73); N:2.81 (2.82) 1HNMR (CDCl 3): 7.74-6.78 (m, 16H), 4.15 (s, 2H), 1.40,1.38 (s, s 9H, 9H)
Synthesizing of embodiment nine ligand L 9
In the reaction flask, add 15ml ethanol, the adjacent diphenylphosphine aniline of 2.77g (10.0mmol) and (12.0mmol) add molecular sieve and small amount of acetic acid, reflux 3h in the compound system of following structural formula (h), remove and desolvate, the silicagel column separation obtains ligand L 9 2.72g (51%) ..
Figure C0112632300382
Ultimate analysis: actual measurement (calculating): C:81.00 (81.02); H:7.43 (7.55); N:2.51 (2.62) 1HNMR (CDCl 3): 7.6-6.9 (m 17H); (5.36 s 1H); (2.10 s 3H); 1.44,1.38 (s, s9H, 9H)
Synthesizing of embodiment ten ligand L 10
In the 100ml reaction flask, add the adjacent diphenylphosphine aniline of 2.77g (10.0mmol), concentrated hydrochloric acid 3.1g (30.0mmol) and 5ml water, vigorous stirring.Under keeping 0 ℃, the 2.5ml aqueous solution with 0.65g (10.0mmol) Sodium Nitrite adds in the above-mentioned system while stirring,, keep 0 ℃ to stir 1h down, obtain diazonium salt.In another reaction flask, to 2.07g (10.0mmol) 2, the 4-DI-tert-butylphenol compounds is dissolved in the 20ml aqueous solution that adds 2.0g (50.0mmol) sodium hydroxide in the 5ml tetrahydrofuran solution, under keeping 0 ℃, above-mentioned gained diazonium salt is added drop-wise in this negative solution, continues to stir 1.5h down at 0 ℃, system is risen to room temperature, use the 30ml extracted with diethyl ether, organic phase is washed with dilute hydrochloric acid, anhydrous Na 2SO 4Drying, the rear pillar chromatography that goes out to desolvate obtains ligand L 10 3.57g (72.3%)
Ultimate analysis: actual measurement (calculating): C:77.70 (77.71); H:7.11 (7.13); N:5.56 (5.66) 1HNMR (CDCl 3): 7.9-6.9 (m 16H); 1.42,1.35 (s, s 9H, 9H)
Synthesizing of embodiment 11 ligand L 11
In the reaction flask of 100ml, add 2.48g (10.0mmol) 3,5-di-t-butyl-o-hydroxyacetophenone, 2.77g (10.0mmol) (o-amino-phenyl-) diphenylphosphine, 50ml dehydrated alcohol, the Glacial acetic acid of molecular sieve and catalytic amount, after being heated to backflow 30h, stopped reaction is removed molecular sieve, concentrate, make to be chilled to room temperature, promptly obtain crude product, with methylene dichloride/ether recrystallization, obtain ligand L 1,3.0g (59.3%).
Ultimate analysis: actual measurement (calculated value): C:80.24 (80.44) H:7.01 (7.54) N:2.53 (2.76) 1HNMR (300MHz CDCl 3):; (7.4-6.8 m, Aryl H), δ 2.1 (s CH 3), 1.4,1.3 (s, s t-Bu-H)
Embodiment 12 title complex A-1's is synthetic
10ml tetrahydrofuran solution with 740.5mg (1.5mmol) ligand L 1 under 0 ℃ is added dropwise in the 10ml tetrahydrofuran (THF) of 60mg (1.5mmol) KH, continues under the room temperature to stir the 1h. vacuum and desolventize, and adds 30ml toluene, under the room temperature with TiCl 40.20ml 10ml toluene solution (0.18mmol) drips so far in the negative solution, dropwise, continue at and stir the 3h. solvent removed in vacuo under the room temperature, add the 40ml methylene dichloride and make dissolving, centrifugal, the supernatant liquor solvent removed in vacuo promptly obtains orange red thick product, washes, obtains orange red solid 760mg (78.3%) with hexane, toluene/hexane.
Figure C0112632300401
Ultimate analysis: actual measurement (calculating) C:60.36 (61.27) H; 6.01 (5.45) N:2.01 (2.16) 1HNMR (300MHz CDCl 3): δ 8.2 (s CH=N); (7.8-7.0 m, Aryl H); (A) (B) 1.14,1.09 (s, s t-Bu-H) of 1.51,1.34 (s, s t-Bu-H), B/A=6
δ( 31P，CDCl 3)δ：15.81
Embodiment 13
Obtain other title complex A-7 (56.3%) with the experimental technique identical with title complex A-1; A-8 (31.3%); A-9 (53.2%); A-10 (21.5%); A-11 (56.4%)
FID-MS(M +)661
Ultimate analysis: actual measurement (calculating): C:79.69 (79.97); H:7.60 (7.73); N:2.65 (2.75)
FID-MS(M +)611
Ultimate analysis: actual measurement (calculating): C:64.21 (64.72); H:5.88 (5.93); N:2.17 (2.29) Cl:11.42 (11.58)
Figure C0112632300413
FID-MS(M +)685
Ultimate analysis: actual measurement (calculating): C:62.33 (62.95); H:5.60 (5.72); N:2.41 (2.04) Cl:15.83 (15.48)
Figure C0112632300421
FID-MS(M +)646
Ultimate analysis: actual measurement (calculating): C:60.98 (59.33); H:5.39 (5.29); N:4.55 (4.32) Cl:16.76 (16.42)
Figure C0112632300422
FID-MS(M +)659
Ultimate analysis: actual measurement (calculating): C:60.90 (61.79); H:5.23 (5.64); N:1.99 (2.12) Cl:16.71 (16.09)
Synthesizing of embodiment 14 complex B-1
The 20ml tetrahydrofuran solution that adds 800mg (1.62mmol) ligand 1 in the 100ml Schlenk bottle is added dropwise among the NaH in 0 ℃, obtains the xanchromatic negative solution, continues under the room temperature and stirs under the 1h. room temperature TiCl 40.09ml 5ml tetrahydrofuran solution (0.8mmol) drips so far in the negative solution, dropwise, continue at and stir the 3h. solvent removed in vacuo under the room temperature, add the 20ml methylene dichloride and make dissolving, centrifugal, tell supernatant liquor, vacuum concentration, freezing obtains yellow thick product, with the toluene recrystallization, obtain orange-yellow crystallite 550mg (62.3%).
Figure C0112632300431
Ultimate analysis: actual measurement (calculating) C:70.91 (71.81) H; 6.64 (6.39) N:2.21 (2.54) 1HNMR (300MHz CDCl 3): δ 8.1 (s CH=N); (7.6-7.0 m, Aryl H); 1.2,1.1 (s, s t-Bu-H)
Embodiment 15 title complex C-1's is synthetic
Under 0 ℃, the 10ml tetrahydrofuran solution of 300mg (0.6mmol) ligand L 1 is added dropwise in the 10ml tetrahydrofuran (THF) of 0.6mmolNaH, continues under the room temperature and stir 1h, this negative solution is transferred to 261.7mg (0.6mmol) ZrCl under 0 ℃ 4In the 15ml tetrahydrofuran (THF) of 2T HF, dropwise, keep 0 ℃ of 0.5h, backflow 7h, vacuum desolventizes, and adds the 20ml methylene dichloride and makes dissolving, centrifugal, and is freezing, obtains faint yellow thick product, with the dichloromethane/hexane recrystallization, obtains C-1 97.8mg (23.6%).
Figure C0112632300432
FID-MS(M +)687
Ultimate analysis: actual measurement (calculating) C:56.91 (57.43); H; 5.24 (5.11); N:2.23 (2.03); Cl:15.62 (15.41)
With the experimental technique synthetic compound C-7 identical with title complex C-1 (productive rate: 23.1%), C-8 (15.6%), C-11 (20.7%)
Figure C0112632300441
FID-MS(M +)703
Ultimate analysis: actual measurement (calculating): C:58.72 (57.82); H:5.34 (5.57); N:1.74 (1.98) Cl:15.57 (15.06)
Figure C0112632300442
FID-MS(M +)653
Ultimate analysis: actual measurement (calculating): C:61.03 (60.44); H:5.64 (5.53); N:2.28 (2.14) Cl:10.33 (10.81)
Figure C0112632300443
FID-MS(M +)701
Ultimate analysis: actual measurement (calculating): C:57.07 (57.99); H:5.03 (5.30); N:1.53 (1.99) Cl:16.07 (15.10)
Embodiment 16 title complex D-1's is synthetic
Under 0 ℃, the 10ml tetrahydrofuran solution of 300mg (0.6mmol) ligand L 1 is added dropwise in the 10ml tetrahydrofuran (THF) of 0.6mmolNaH, continues under the room temperature and stir 1h, this negative solution is transferred to 0.3mmolZrCl under 0 ℃ 4In the 3ml tetrahydrofuran (THF) of 2THF, dropwise, keep 0 ℃ of 0.5h, backflow 5.5h, vacuum desolventizes, and adds the 20ml methylene dichloride and makes dissolving, centrifugal, and is freezing, obtains faint yellow thick product, with the dichloromethane/hexane recrystallization, obtains D-1 94mg (27.3%).
Figure C0112632300451
Ultimate analysis: actual measurement (calculating) C:68.98 (69.09) H:6.17 (6.15) N:2.49 (2.44)
FID-MS(M +)：1148
Embodiment 17 title complex H-1's is synthetic
Under 0 ℃, the 10ml tetrahydrofuran solution of 148mg (0.44mmol) ligand L 3 is added dropwise in the 10ml tetrahydrofuran (THF) of 35mg (0.88mmol) KH, continues under the room temperature and stir 1h, after the solvent removed in vacuo, with 10ml toluene, with 0.07ml (0.6mmol) TiCl 4The 10ml toluene solution join in this negative solution, dropwise, continue under the room temperature and to stir the 5.5h. vacuum and desolventize, add the 20ml methylene dichloride and make dissolving, centrifugal, supernatant liquor obtains H-1 135mg (67.4%) except that desolvating.
Figure C0112632300452
Ultimate analysis: actual measurement (calculating) C:58.34 (58.04) H:6.19 (6.20) N:6.32 (6.15) Cl:16.99 (15.58)
FID-MS(M +)454
Synthesizing of embodiment 18 compound Hs-2
Under 0 ℃, the 10ml tetrahydrofuran solution of 148mg (0.44mmol) ligand L 3 is added dropwise in the 10ml tetrahydrofuran (THF) of 35mg (0.88mmol) KH, continues under the room temperature and stir 1h, 144mg (0.4mmol) ZrCl 4The suspension of the 10ml tetrahydrofuran (THF) of 2THF is transferred in this negative solution, continues backflow 5h. vacuum and desolventize after stirring 26h under the room temperature, adds methylene dichloride 20ml and makes dissolving, obtains yellow clear liquid after the filtration, obtains H-2 44.6mg (22.4%) after concentrating.
Figure C0112632300461
FID-MS(M +)496
Ultimate analysis: actual measurement (calculating) C:53.41 (53.00) H:5.84 (5.66) N:5.87 (5.62) Cl:14.87 (14.22)
Embodiment 19 title complex A-4's is synthetic
Under 0 ℃, the 10ml tetrahydrofuran solution of 233mg (0.72mmol) ligand L 4 is added dropwise in the 10ml tetrahydrofuran (THF) of 30mg (0.75mmol) KH, continues under the room temperature and stir 1h, after the solvent removed in vacuo, add 20ml toluene, 0.09ml (0.8mmol) TiCl 4The 10ml toluene solution be added drop-wise in this negative solution, dropwise, continue under the room temperature and to stir the 3.5h. vacuum and desolventize, obtain A-4 308mg (89.6%)
FID-MS(M +)476
Ultimate analysis: actual measurement (calculating) C:53.38 (52.80) H:5.84 (5.70) N:5.73 (5.86) Cl:22.51 (22.27)
Embodiment 20 title complex E-2 are synthetic
Under 0 ℃, the 10ml tetrahydrofuran solution of 420mg (1.2mmol) ligand L 2 is added dropwise in the 10ml tetrahydrofuran (THF) of 1.2mmolNaH, continues under the room temperature and stir 1h, under 0 ℃, 780mg (1.1mmol) (Ph 3P) 2The 10ml tetrahydrofuran solution of PhCl is transferred in this negative solution, stirs under room temperature and spends the night, and continues backflow 1h, make cooling gradually, after the filtration, vacuum desolventizes, add the 20ml hexane and make dissolving, obtain yellow clear liquid after the filtration, the E-2253mg (46.3%) that obtains after concentrating
Figure C0112632300472
Ultimate analysis: actual measurement (calculating) C:70.80 (71.48) H; 7.46 (7.45) N 5.49 (5.75)
Embodiment 21 title complex F-1's is synthetic
Under 0 ℃, the 10ml tetrahydrofuran solution of 300mg (0.6mmol) ligand L 1 is added dropwise in the 10ml tetrahydrofuran (THF) of 0.6mmolNaH, continues under the room temperature and stir 1h, solvent removed in vacuo, add acetonitrile 25ml, under 0 ℃, this negative solution is added to 97mg (0.6mmol) FeCl 3Acetonitrile solution in, under room temperature, stir and spend the night, be heated to 80 ℃ and continue down to stir 1h, make cooling gradually, after the filtration, the vacuum concentration solvent obtains F-1296mg (79.65%).
Figure C0112632300481
Ultimate analysis: actual measurement (calculating) C:70.80 (71.48) H; 7.46 (7.45) N 5.49 (5.75)
FID-MS(M+)618
Embodiment 22 title complex G-1's is synthetic
Under 0 ℃, the 10ml tetrahydrofuran solution of 300mg (0.6mmol) ligand L 1 is added dropwise in the 10ml tetrahydrofuran (THF) of 0.6mmolNaH, continues at and this negative solution is added to 76mg (0.6mmol) FeCl after stirring 1h under the room temperature 2The 10ml tetrahydrofuran (THF) in, under room temperature, stir 40h, vacuum desolventizes, and adds the 20ml methylene dichloride and makes dissolving, obtains green clear liquid after the filtration, obtains G-1 135mg (38.5%) after concentrating
Figure C0112632300482
FID-MS(M+)583
Embodiment 23 title complex F-6's is synthetic
Under 0 ℃, the 15ml tetrahydrofuran solution of 200mg (0.47mmol) ligand L 6 is added dropwise in the 5ml tetrahydrofuran (THF) of 18.8mg (0.47mmol) KH, continue at after dropwising under the room temperature and stir 1h, solvent removed in vacuo, add acetonitrile 25ml, under 0 ℃, this negative solution is added to 76.2mg (0.47mmol) FeCl 3The 5ml acetonitrile solution in, under room temperature, stir and spend the night, be heated to 80 ℃ and continue down to stir 1h, make cooling gradually, after the filtration, the vacuum concentration solvent obtains F-6 191mg (73.8%)
Figure C0112632300491
FID-MS(M+)551
Embodiment 24 title complex G-6's is synthetic
Under 0 ℃, the 10ml tetrahydrofuran solution of 200mg (0.47mmol) ligand L 6 is added dropwise in the 5ml tetrahydrofuran (THF) of 18.8mg (0.47) mmol KH, continues at and this negative solution is added to 60mg (0.47mmol) FeCl after stirring 1h under the room temperature 2The 10ml tetrahydrofuran (THF) in, under room temperature, stir 40h, vacuum desolventizes, and adds the 20ml methylene dichloride and makes dissolving, obtains green clear liquid after the filtration, obtains G-6 81.8mg (33.7%) after concentrating
Figure C0112632300501
FID-MS(M+)516
Embodiment 24～embodiment 33 has shown that (A-1) catalyst system shows special catalytic characteristics in catalyzed ethylene polymerization, be under the normal pressure, (Al: Cat=10: 1～3000: 1) all have good catalytic activity in the amount ranges of quite wide temperature range (30 ℃～70 ℃), promotor, especially at low Al: the Cat ratio, for example less than 100: 1 even less than 10: still have 1.6 * 10 during l 5The excellent activity of g PE/molTi hratm, and polymerization temperature (40～80 ℃) in the acceptable scope of commerce; Resulting polymers has molecular weight height, narrow molecular weight distribution, and the low characteristics such as (1-5/1000C) of the degree of branching are expected to be used for industrial application.
Above characteristics are not limited in (A-1) catalyst system, also occur in relevant other systems.
Embodiment 25
Under the ethene atmosphere of 1atm, catalyzer (A-1) (2 μ mol), toluene 20ml are added in the round-bottomed flask through taking out roasting 100ml successively, vigorous stirring, place 50 ℃ of oil baths then, the constant temperature certain hour, add mMAO (Al/Ti=1500) again, react after 0.5 hour, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polyethylene 1.80g in 50 ℃ of vacuum-dryings after precipitation, filtration, washing.Catalytic activity is 1.8 * 10 6G PE/molTi hr atm.Resulting polymers molecular weight M w=630,000g/mol, molecular weight distribution is 1.22, T mIt is 136.1 ℃.
Embodiment 26
Under the ethene atmosphere of 1atm, catalyzer (A-1) (2 μ mol), toluene 20ml are added in the round-bottomed flask through taking out roasting 100ml successively, vigorous stirring, place 50 ℃ of oil baths then, the constant temperature certain hour, add mMAO (Al/Ti=100) again, react after 0.5 hour, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polyethylene 0.9422g in 50 ℃ of vacuum-dryings after precipitation, filtration, washing.Catalytic activity is 0.94 * 10 6G PE/molTi hr atm.Resulting polymers molecular weight M w=720,000g/mol, molecular weight distribution is 1.08, T mBe 135.8 ℃, degree of crystallinity 80%.
Embodiment 27
Under the ethene atmosphere of 1atm, catalyzer (A-1) (2 μ mol), toluene 20ml are added in the round-bottomed flask through taking out roasting 100ml successively, vigorous stirring, place 50 ℃ of oil baths then, the constant temperature certain hour, add mMAO (Al/Ti=10) again, react after 0.5 hour, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polyethylene 0.1573g in 50 ℃ of vacuum-dryings after precipitation, filtration, washing.Catalytic activity is 1.6 * 10 5G PE/molTi hr atm.Resulting polymers molecular weight M w=800,000g/mol, molecular weight distribution is 1.05, T mBe 140.5 ℃, degree of crystallinity 82%.
Embodiment 28
Under the ethene atmosphere of 1atm, catalyzer (A-1) (2 μ mol), toluene 20ml are added in the round-bottomed flask through taking out roasting 100ml successively, vigorous stirring, place 50 ℃ of oil baths then, the constant temperature certain hour, add mMAO (Al/Ti=500) again, react after 0.5 hour, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polyethylene 0.538g in 70 ℃ of vacuum-dryings after precipitation, filtration, washing.Catalytic activity is 5.4 * 10 5G PE/molTi hr atm.Resulting polymers molecular weight M w=580,000g/mol, molecular weight distribution is 1.18, T mIt is 132.4 ℃.
Embodiment 29
Under the ethene atmosphere of 1atm, catalyzer (A-1) (2 μ mol), toluene 20ml are added in the round-bottomed flask through taking out roasting 100ml successively, vigorous stirring, place 50 ℃ of oil baths then, the constant temperature certain hour, add mMAO (Al/Ti=500) again, react after 0.5 hour, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polyethylene 1.1g in 60 ℃ of vacuum-dryings after precipitation, filtration, washing.Catalytic activity is 1.1 * 10 6G PE/molTi hr atm.Resulting polymers molecular weight M w=620,000g/mol, molecular weight distribution is 1.16, T mBe 134.1 ℃, degree of crystallinity 68%.
Embodiment 30
Under the ethene atmosphere of 1atm, catalyzer (A-1) (2 μ mol), toluene 20ml are added in the round-bottomed flask through taking out roasting 100ml successively, vigorous stirring, place 50 ℃ of oil baths then, the constant temperature certain hour, add mMAO (Al/Ti=500) again, react after 0.5 hour, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polyethylene 0.7371g in 0 ℃ of vacuum-drying after precipitation, filtration, washing.Catalytic activity is 7.4 * 10 5G PE/molTi hr atm.Resulting polymers molecular weight M w=770,000g/mol, molecular weight distribution is 1.10.
The embodiment hentriaconta-
Under the ethene atmosphere of 1atm, catalyzer (A-1) (2 μ mol), toluene 20ml are added in the round-bottomed flask through taking out roasting 100ml successively, vigorous stirring, place 50 ℃ of oil baths then, the constant temperature certain hour, add mMAO (Al/Ti=500) again, react after 0.5 hour, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polyethylene 0.4224g in 50 ℃ of vacuum-dryings after precipitation, filtration, washing.Catalytic activity is 4.2 * 10 5G PE/molTi hr atm.Resulting polymers molecular weight M w=910,000g/mol, molecular weight distribution is 1.06, T mBe 141.5 ℃, degree of crystallinity 62%.
Embodiment 32
In the autoclave of 500ml, under the ethene atmosphere, add 240ml toluene, 0.1mlAl (i-Bu) successively 3, stirred one hour under the room temperature, add the toluene solution that mMAO (Al/Ti=500), 10ml contain 4 μ mol (A-1) more successively, under vigorous stirring, ethylene pressure is risen to 6 * 10 5MPa reacted after 0.5 hour, and the emptying ethylene gas is with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance is done 50 ℃ of vacuum-dryings to constant weight after precipitation, filtration, washing, get polyethylene 28.1g.Catalytic activity is 1.16 * 10 6, E/molTi hr atm.Resulting polymers molecular weight M w=88,000g/mol, molecular weight distribution is 1.17.
Embodiment 33
Under the ethene atmosphere of 1atm, catalyzer (A-1) (2 μ mol), toluene 20ml are added in the round-bottomed flask through taking out roasting 100ml successively, vigorous stirring, place 50 ℃ of oil baths then, the constant temperature certain hour, add mMAO (Al/Ti=500) again, react after 0.5 hour, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polyethylene 1.22g in 50 ℃ of vacuum-dryings after precipitation, filtration, washing.Catalytic activity is 1.2 * 10 6G PE/molTi hr atm.Resulting polymers molecular weight M w=700,000g/mol, molecular weight distribution is 1.16, T mBe 134.5 ℃, degree of crystallinity 78%.
The embodiment 34～embodiment 46 explanation parts (polymerization result of the early transition metal complex compound of L1～L6) and part (polymerization result of L1～L6) and the different coordination mode gained complex compounds of early transition metal.
Embodiment 34
Under the ethene atmosphere of 1atm, toluene 20ml, mMAO (Al/Ti=1100) are added in the round-bottomed flask through taking out roasting 100ml successively, vigorous stirring, place 50 ℃ of oil baths then, the constant temperature certain hour, add catalyzer (B-3) (1.5 μ mol) reaction again after 0.5 hour, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polyethylene 0.0022g in 50 ℃ of vacuum-dryings after precipitation, filtration, washing.Catalytic activity is 2.9 * 10 3G PE/molTi hr atm.Resulting polymers molecular weight M w=23,000g/mol, molecular weight distribution is 2.10.
Embodiment 35
Under the ethene atmosphere of 1atm, toluene 20ml, mMAO (Al/Ti=500) are added in the round-bottomed flask through taking out roasting 100ml successively, vigorous stirring, place 50 ℃ of oil baths then, the constant temperature certain hour, add catalyzer (A-3) (1.5 μ mol) reaction again after 0.5 hour, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polyethylene 0.0022g in 50 ℃ of vacuum-dryings after precipitation, filtration, washing.Catalytic activity is 2.9 * 10 3G PE/molTi hr atm.Resulting polymers molecular weight M w=403,000g/mol, molecular weight distribution is 2.10.
Embodiment 36
Under the ethene atmosphere of 1atm, toluene 20ml, mMAO (Al/Ti=300) are added in the round-bottomed flask through taking out roasting 100ml successively, vigorous stirring, place 50 ℃ of oil baths then, the constant temperature certain hour, add catalyzer (B-5) (5.4 μ mol) reaction again after 0.5 hour, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polyethylene 0.0248g in 50 ℃ of vacuum-dryings after precipitation, filtration, washing.Catalytic activity is 0.9 * 10 3G PE/molTi hr atm.Resulting polymers molecular weight M w=33,000g/mol, molecular weight distribution is 2.21.
Embodiment 37
Under the ethene atmosphere of 1atm, toluene 20ml, mMAO (Al/Ti=300) are added in the round-bottomed flask through taking out roasting 100ml successively, vigorous stirring, place 50 ℃ of oil baths then, the constant temperature certain hour, add catalyzer (A-5) (5.4 μ mol) reaction again after 0.5 hour, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polyethylene 0.338g in 50 ℃ of vacuum-dryings after precipitation, filtration, washing.Catalytic activity is 1.2 * 10 5G PE/molTi hr atm.Resulting polymers molecular weight M w=530,000g/mol, molecular weight distribution is 2.21.
Embodiment 38
Under the ethene atmosphere of 1atm, toluene 20ml, mMAO (Al/Ti=1000) are added in the round-bottomed flask through taking out roasting 100ml successively, vigorous stirring, place 50 ℃ of oil baths then, the constant temperature certain hour, add catalyzer (B-1) (1.9 μ mol) reaction again after 1 hour, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polyethylene 0.104g in 50 ℃ of vacuum-dryings after precipitation, filtration, washing.Catalytic activity is 5.5 * 10 4G PE/molTi hr atm.Resulting polymers molecular weight M w=32,000g/mol, molecular weight distribution is 2.03.
Embodiment 39
Under the ethene atmosphere of 1atm, toluene 20ml, mMAO (Al/Ti=1000) are added in the round-bottomed flask through taking out roasting 100ml successively, vigorous stirring, place 50 ℃ of oil baths then, the constant temperature certain hour, add catalyzer (B-2) (2.06 μ mol) reaction again after 1 hour, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polyethylene 0.026g in 50 ℃ of vacuum-dryings after precipitation, filtration, washing.Catalytic activity is 1.3 * 10 4G PE/molTi hr atm.Resulting polymers molecular weight M w=35,000g/mol, molecular weight distribution is 1.56.
Embodiment 40
Under the ethene atmosphere of 1atm, toluene 20ml, mMAO (Al/Ti=1000) are added in the round-bottomed flask through taking out roasting 100ml successively, vigorous stirring, place 50 ℃ of oil baths then, the constant temperature certain hour, add catalyzer (A-2) (2.77 μ mol) reaction again after 1 hour, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polyethylene 0.16g in 50 ℃ of vacuum-dryings after precipitation, filtration, washing.Catalytic activity is 0.58 * 10 5G PE/molTi hr atm.Resulting polymers molecular weight M w=430,000g/mol, molecular weight distribution is 1.32.
Embodiment 41
Under the ethene atmosphere of 1atm, toluene 20ml, mMAO (Al/Ti=1000) are added in the round-bottomed flask through taking out roasting 100ml successively, vigorous stirring, place 50 ℃ of oil baths then, the constant temperature certain hour, add catalyzer C-1 (2.06 μ mol) reaction again after 0.5 hour, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polyethylene 0.52g in 50 ℃ of vacuum-dryings after precipitation, filtration, washing.Catalytic activity is 5.0 * 10 5G PE/molTi hr atm.Resulting polymers molecular weight M w=530,000g/mol, molecular weight distribution is 1.21.
Embodiment 42
Under the ethene atmosphere of 1atm, toluene 20ml, mMAO (Al/Ti=1000) are added in the round-bottomed flask through taking out roasting 100ml successively, vigorous stirring, place 50 ℃ of oil baths then, the constant temperature certain hour, add catalyzer C-3 (2.2mol) reaction again after 0.5 hour, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polyethylene 0.26g in 50 ℃ of vacuum-dryings after precipitation, filtration, washing.Catalytic activity is 2.36 * 10 5G PE/molTi hr atm.Resulting polymers molecular weight M w=620,000g/mol, molecular weight distribution is 1.31.
Embodiment 43
Under the ethene atmosphere of 1atm, toluene 20ml, mMAO (Al/Ti=1000) are added in the round-bottomed flask through taking out roasting 100ml successively, vigorous stirring, place 50 ℃ of oil baths then, the constant temperature certain hour, add catalyzer C-2 (3.5 μ mol) reaction again after 0.5 hour, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polyethylene 0.64g in 50 ℃ of vacuum-dryings after precipitation, filtration, washing.Catalytic activity is 3.6 * 10 5G PE/molTi hr atm.Resulting polymers molecular weight M w=480,000g/mol, molecular weight distribution is 1.12.
Embodiment 44
Under the ethene atmosphere of 1atm, toluene 20ml, mMAO (Al/Ti=1000) are added in the round-bottomed flask through taking out roasting 100ml successively, vigorous stirring, place 50 ℃ of oil baths then, the constant temperature certain hour, add catalyzer C-5 (2.3 μ mol) reaction again after 0.5 hour, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polyethylene 0.13g in 50 ℃ of vacuum-dryings after precipitation, filtration, washing.Catalytic activity is 1.13 * 10 5G PE/molTi hr atm.Resulting polymers molecular weight M w=530,000g/mol, molecular weight distribution is 1.13.
Embodiment 45
Under the ethene atmosphere of 1atm, toluene 20ml, mMAO (Al/Ti=300) are added in the round-bottomed flask through taking out roasting 100ml successively, vigorous stirring, place 50 ℃ of oil baths then, the constant temperature certain hour, add catalyzer C-4 (1.6 μ mol) reaction again after 0.5 hour, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polyethylene 0.47g in 50 ℃ of vacuum-dryings after precipitation, filtration, washing.Catalytic activity is 5.9 * 10 5G PE/molTi hr atm.Resulting polymers molecular weight M w=670,000g/mol, molecular weight distribution is 1.17.
Embodiment 46
Under the ethene atmosphere of 1atm, toluene 20ml, mMAO (Al/Ti=300) are added in the round-bottomed flask through taking out roasting 100ml successively, vigorous stirring, place 50 ℃ of oil baths then, the constant temperature certain hour, add catalyst A-4 (5.2 μ mol) reaction again after 0.5 hour, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polyethylene 0.77g in 50 ℃ of vacuum-dryings after precipitation, filtration, washing.Catalytic activity is 3.0 * 10 5G PE/molTi hr atm.Resulting polymers molecular weight M w=640,000g/mol, molecular weight distribution is 1.15.
Embodiment 47 explanation parts (the late transition metal complex catalysis in olefine polymerization result of L1～L6)
Embodiment 47
Under the ethene atmosphere of 1atm, toluene 20ml, mMAO (Al/Ti=1000) are added in the round-bottomed flask through taking out roasting 100ml successively, vigorous stirring, place 0 ℃ of ice bath then, the constant temperature certain hour, add catalyzer (G-1) (13 μ mol) reaction again after 1 hour, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polyethylene 0.0051g in 50 ℃ of vacuum-dryings after precipitation, filtration, washing.Catalytic activity is 3.9 * 10 2G PE/molTi hr atm.Resulting polymers molecular weight M w=21,000g/mol, molecular weight distribution is 2.21.
The polymerization result of other alkene of embodiment 48～embodiment 49 explanation catalysis except that ethene.
Embodiment 48
With catalyzer (A-1) (16 μ mol, 7.2 * 10 -3The toluene solution of M), AlEt 3(Al/Ti=20) add successively in the ampere bottle through taking out roasting 15ml, vigorous stirring places 50 ℃ of oil baths then, and the constant temperature certain hour adds the hexene of 1ml, react after 1 hour, and usefulness contains the ethanol termination reaction of 5% hydrochloric acid.Polymkeric substance to constant weight, gets polyhexene 0.12g in 50 ℃ of vacuum-dryings after precipitation, filtration, washing.Catalytic activity is 0.75 * 10 4G PE/molTi hr.Resulting polymers molecular weight M w=18,000g/mol, molecular weight distribution is 1.7.
Embodiment 49
Under the ethene atmosphere of 1atm, with catalyzer (A-1) (18 μ mol, 7.2 * 10 -3The toluene solution of M), AlEt 3(Al/Ti=20) add successively in the ampere bottle through taking out roasting 15ml, vigorous stirring places 50 ℃ of oil baths then, and the constant temperature certain hour adds the methyl methacrylate of 1ml, react after 12 hours, and usefulness contains the ethanol termination reaction of 5% hydrochloric acid.Polymkeric substance to constant weight, gets polymethylmethacrylate 0.1721g in 50 ℃ of vacuum-dryings after precipitation, filtration, washing.Catalytic activity is 0.96 * 10 4G PE/molTi.Resulting polymers molecular weight M w=220,000g/mol, molecular weight distribution is 2.1.

Claims (23)

1. olefinic polymerization and copolymerization catalyst, its structural formula is as follows:
Wherein:
M:1,2 or 3;
Q:0 or 1;
M: the transition metal atoms of ten gangs of three races to the;
N:1,2 or 3;
X: be to comprise halogen atom, hydrogen atom, C 1-C 30Alkyl, oxy radical, nitrogen-containing group, sulfur-containing group, boron-containing group, contain aluminium base group, phosphorus-containing groups, silicon-containing group, germanic group or contain tin group at interior anion ligand, several X can be identical, also can be different, can also be each other in key Cheng Huan; In the structural formula all parts electronegative sum absolute value should with metal M in the structural formula the absolute value of positively charged sum identical, all parts comprise X and tridentate ligand;
A: Sauerstoffatom, sulphur atom, selenium atom, R 21N or R 21P;
B: refer to nitrogen-containing group or C 1-C 30Alkyl;
D: refer to nitrogen-atoms, Sauerstoffatom, sulphur atom, selenium atom, phosphorus atom, C 1-C 30The nitrogenous or C of alkyl 1-C 30The phosphorus-containing groups of alkyl, wherein N, O, S, Se, P are ligating atom;
E: refer to nitrogen-containing group, oxy radical, sulfur-containing group, contain seleno group or phosphorus-containing groups, wherein N, O, S, Se, P are ligating atom;
→: refer to singly-bound or two key;
: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage;
R 1, R 2, R 3, R 21: hydrogen, C 1-C 30Alkyl, halogen atom, C 1-C 30Substituted hydrocarbon radical or safing function group, R 1, R 2, R 3, R 21Can be the same or different wherein adjacent R 1, R 2, R 3Part can be each other in key Cheng Huan, and works as R 1With R 2When becoming ring, except A and B, also has a hydrogen at least on the phenyl ring by C 1-C 30Alkyl, halogen atom, C 1-C 30Substituted hydrocarbon radical or safing function group replace;
Alkyl refers to contain C 1-C 30Alkyl, C 1-C 30Cyclic hydrocarbon group, C 2-C 30Group, the C of carbon-carbon double bonds 2-C 30Carbon containing carbon triple-linked group, C 6-C 30Aryl radical or C 8-C 30The condensed ring alkyl;
The alkyl that replaces refers to contain on the alkyl one or more substituted radical, under the employed process condition of the compound that contains substituted hydrocarbon radical, these substituting groups are inert, and these substituting groups do not have substantial interference to related process yet, in other words, these substituting groups generally not with metal-complexing;
The safing function group refers to be different from other functional groups of alkyl and substituted hydrocarbon radical, this functional group to the catalyzer that contains this functional groups all do not have substantially in the reaction that may participate in and disturb, described functional groups comprises C 1-6Ester group, C 1-6Amido, C 1-6Alkoxyl group, nitro, oxy radical, nitrogen-containing group, silicon-containing group, germanic group, sulfur-containing group or contain tin group, when functional groups when the atoms metal, the coordination ability of itself and metal is not better than A, E, the D group that contains ligating atom, and promptly these functional groups should not replace desirable coordinating group;
Halogen refers to fluorine, chlorine, bromine, or iodine;
Oxy radical refers to hydroxyl, alkoxyl group or has the alkyl of ehter bond;
Sulfur-containing group refers to-SH ,-SR 23Or-CH 2-T-OR 23
R 23Be C 1-C 30Alkyl or C 1-C 30Substituted hydrocarbon radical;
Boron-containing group refers to BF 4 -, (C 6F 5) 4B -Or (R 24BAr 3) -
R 24Be meant C 1-C 30Alkyl or C 1-C 30Substituted hydrocarbon radical;
Contain aluminium base group and refer to alkylaluminium cpd, AlPh 4 -, AlF 4 -, AlCl 4 -, AlBr 4 -Or AlI 4 -
Phosphorus-containing groups refers to-CH 2-T-PR 25
R 25Be C 1-C 30Alkyl or C 1-C 30Substituted hydrocarbon radical;
Nitrogen-containing group refers to-NR 2,-NH 2,-NHR or-CH 2-T-NR 26
R 26Be C 1-C 30Alkyl or C 1-C 30Substituted hydrocarbon radical;
Silicon-containing group refers to-CH 2-T-SiR 27
R 27Be C 1-C 30Alkyl or C 1-C 30Substituted hydrocarbon radical;
Germanic group-CH 2-T-GeR 28
R 28Be C 1-C 30Alkyl or C 1-C 30Substituted hydrocarbon radical;
Contain tin group and refer to-CH 2-T-SnR 29
R 29Be C 1-C 30Alkyl or C 1-C 30Substituted hydrocarbon radical;
T is C 1-C 30Alkylene or C 1-C 30The alkylene of replacement;
Condition is that related part is not
2. a kind of olefinic polymerization as claimed in claim 1 and copolymerization catalyst, its feature structure formula is as follows:
Wherein:
: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage;
Q, m, M, n, X, A, B, E, R 1, R 2, R 3With identical described in the aforementioned claim 1.
3. a kind of olefinic polymerization as claimed in claim 2 and copolymerization catalyst, its feature structure formula is as follows:
Figure C011263230005C1
Wherein:
: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage;
R 4: hydrogen, C 1-C 30Alkyl, halogen atom, C 1-C 30The alkyl or the safing function group of replacement, wherein adjacent R 4With R 1Can be each other in key Cheng Huan;
Q, m, M, n, X, A, E, R 1, R 2, R 3With identical described in the aforementioned claim 1.
4. a kind of olefinic polymerization as claimed in claim 2 and copolymerization catalyst, its feature structure formula is as follows:
Figure C011263230005C2
Wherein:
: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage;
R 6, R 7, R 8, R 9: hydrogen, C 1-C 30Alkyl, halogen atom, C 1-C 30The alkyl or the safing function group of replacement, R 3, R 4, R 6, R 7, R 8, R 9Can be the same or different, can be each other in key Cheng Huan;
Q, m, M, n, X, A, E, R 3, R 4With identical described in the aforementioned claim 3.
5, a kind of olefinic polymerization as claimed in claim 2 and copolymerization catalyst, its feature structure formula is as follows:
Wherein:
: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage;
Q, m, M, n, X, A, E, R 3, R 6, R 7, R 8, R 9With identical described in the aforementioned claim 4.
6, a kind of olefinic polymerization as claimed in claim 2 and copolymerization catalyst, its feature structure formula is as follows:
Wherein:
: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage;
M, M, n, X, A, E, R 1, R 2, R 4With identical described in the aforementioned claim 3.
7, a kind of olefinic polymerization as claimed in claim 2 and copolymerization catalyst, its feature structure formula is as follows:
Wherein:
: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage;
M, M, n, X, A, E, R 4, R 6, R 7, R 8, R 9With identical described in the aforementioned claim 4.
8. a kind of olefinic polymerization as claimed in claim 2 and copolymerization catalyst, its feature structure formula is as follows:
Wherein:
: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage;
M, M, n, X, A, E, R 6, R 7, R 8, R 9With identical described in the aforementioned claim 5.
9. a kind of olefinic polymerization as claimed in claim 1 and copolymerization catalyst, its feature structure formula is as follows:
Figure C011263230007C2
Wherein:
: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage;
Q, m, M, n, X, A, B, E, R 1, R 2, R 3With identical described in the aforementioned claim 1;
F: refer to nitrogen-containing group, oxy radical, sulfur-containing group, contain seleno group or phosphorus-containing groups, described nitrogen-containing group, oxy radical, sulfur-containing group, contain seleno group or phosphorus-containing groups with identical described in the aforementioned claim 1, wherein N, O, S, Se, P are ligating atom.
10, a kind of olefinic polymerization as claimed in claim 1 and copolymerization catalyst, its feature structure formula is as follows:
Wherein:
: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage;
R 10, R 11: hydrogen, C 1-C 30Alkyl, halogen atom, C 1-C 30The alkyl or the safing function group of replacement, R 10, R 11, R 1Can be the same or different, can be each other in key Cheng Huan;
Q, m, M, n, X, A, E, F, R 1, R 2, R 3With identical described in the aforementioned claim 9.
11, a kind of olefinic polymerization as claimed in claim 1 and copolymerization catalyst, its feature is as follows:
Figure C011263230008C2
Wherein:
: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage;
R 6, R 7, R 8, R 9: hydrogen, C 1-C 30Alkyl, halogen atom, C 1-C 30The alkyl or the safing function group of replacement, R 6, R 7, R 8, R 9, R 10, R 11Can be the same or different, can be each other in key Cheng Huan;
Q, m, M, n, X, A, E, F, R 3, R 10, R 11With identical described in the aforementioned claim 10.
12, a kind of olefinic polymerization as claimed in claim 1 and copolymerization catalyst, its feature structure formula is as follows:
Figure C011263230009C1
Wherein:
: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage;
M, M, n, X, A, E, F, R 1, R 2, R 10, R 11With identical described in the aforementioned claim 10.
13, a kind of olefinic polymerization as claimed in claim 1 and copolymerization catalyst, its feature structure formula is as follows:
Figure C011263230009C2
Wherein:
: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage;
M, M, n, X, A, E, F, R 6, R 7, R 8, R 9, R 10, R 11With identical described in the aforementioned claim 11.
14, a kind of olefinic polymerization as claimed in claim 1 and copolymerization catalyst, its feature structure formula is as follows:
Wherein:
R 13, R 14, R 15, R 16, R 17, R 18, R 19, R 20, R 31Be C 1-C 30Alkyl, can be the same or different to each other, also can be each other in key Cheng Huan; Z=N or P; M=Ti, Zr, Hf, Fe or Co; X=F, Cl, Br, I, C 1-30Alkyl or weak coordinate negatively charged ion; Y=O or S; N is 1,2 or 3, and negatively charged ion negative charge sum should be identical with the burning attitude in the structural formula;
: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage.
15. a kind of olefinic polymerization as claimed in claim 2 and copolymerization catalyst, its feature structure formula is as follows:
Figure C011263230010C2
Wherein:
R 13, R 14, R 15, R 16, R 17, R 18, R 19, R 20, R 31, R 33Be C 1-C 30Alkyl, can be the same or different to each other, also can be each other in key Cheng Huan; Z=N or P; M=Ti, Zr, Hf, Fe or Co; X=F, Cl, Br, I, C 1-C 30Alkyl or weak coordinate negatively charged ion; Y=O or S; N is 1,2 or 3, and negatively charged ion negative charge sum should be identical with the burning attitude in the structural formula;
: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage;
16. equal polymerization of alkene as claimed in claim 1 and copolymerization catalyst synthetic method, it is characterized in that in organic solvent mixing with mol ratio 1: 0.1～6, react under the temperature of backflow at-78 ℃ and obtain by the part of following structural formula or the negative ion metallizing thing of part.
Described ligand structure formula is as follows:
Figure C011263230011C1
Wherein:
A: Sauerstoffatom, sulphur atom, selenium atom, R 21N or R 21P;
B: refer to nitrogen-containing group or C 1-C 30Alkyl;
D: refer to nitrogen-atoms, Sauerstoffatom, sulphur atom, selenium atom, phosphorus atom, C 1-C 30The nitrogenous or C of alkyl 1-C 30The phosphorus-containing groups of alkyl, wherein N, O, S, Se, P are ligating atom;
E: refer to nitrogen-containing group, oxy radical, sulfur-containing group, contain seleno group or phosphorus-containing groups, wherein N, O, S, Se, P are ligating atom;
→: refer to singly-bound or two key;
-: refer to covalent linkage or ionic linkage;
R 1, R 2, R, R 21: hydrogen, C 1-C 30Alkyl, halogen atom, replacement C 1-C 30Alkyl or safing function group, R 1, R 2, R can be the same or different wherein adjacent R 1, R 2, R part can be each other in key Cheng Huan.
17. the purposes of a kind of olefinic polymerization as claimed in claim 1 and copolymerization catalyst is characterized in that with equal polymerization of promotor catalyzed alkene or copolymerization.
18. the purposes of a kind of olefinic polymerization as claimed in claim 17 and copolymerization catalyst is characterized in that described alkene is the alkene of ethene, alpha-olefin and band functional groups.
19. the purposes of a kind of olefinic polymerization as claimed in claim 18 and copolymerization catalyst is characterized in that alpha-olefin is C 3-C 8Alkene; The alkene of band functional groups is vinylbenzene, methacrylic ester, acrylate, vinyl acetate, norbornylene or acrylamide.
20. the purposes of a kind of olefinic polymerization as claimed in claim 17 and copolymerization catalyst is characterized in that copolymerization comprises the copolymerization and the alpha-olefin copolymerization to each other of alkene of copolymerization, alpha-olefin and band functional groups of alkene of copolymerization, ethene and the band functional groups of ethene and alpha-olefin.
21. the purposes of a kind of olefinic polymerization as claimed in claim 17 and copolymerization catalyst is characterized in that the polymerization pressure scope is 0.1～10MPa.
22. the purposes of a kind of olefinic polymerization as claimed in claim 17 and copolymerization catalyst is characterized in that the polymerization temperature scope is-50～150C.
23. the purposes of a kind of olefinic polymerization as claimed in claim 17 and copolymerization catalyst, the mol ratio that it is characterized in that catalyzer and promotor are 1: 1～5000.
CN 01126323 2001-07-23 2001-07-23 Catalyst for polymerization and copolymerization of olefine and its synthesis and use Expired - Lifetime CN1256351C (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN 01126323 CN1256351C (en) 2001-07-23 2001-07-23 Catalyst for polymerization and copolymerization of olefine and its synthesis and use
EP02754132A EP1426385B1 (en) 2001-07-23 2002-06-17 Catalyst for polymerization or copolymerization of olefins, preparation and use of the same
PCT/CN2002/000425 WO2003010207A1 (en) 2001-07-23 2002-06-17 Catalyst for polymerization or copolymerization of olefins, preparation and use of the same
US10/761,827 US7253133B2 (en) 2001-07-23 2004-01-21 Catalyst for polymerization or copolymerization of olefins, preparation and use of the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 01126323 CN1256351C (en) 2001-07-23 2001-07-23 Catalyst for polymerization and copolymerization of olefine and its synthesis and use

Publications (2)

Publication Number Publication Date
CN1332182A CN1332182A (en) 2002-01-23
CN1256351C true CN1256351C (en) 2006-05-17

Family

ID=4666344

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 01126323 Expired - Lifetime CN1256351C (en) 2001-07-23 2001-07-23 Catalyst for polymerization and copolymerization of olefine and its synthesis and use

Country Status (1)

Country Link
CN (1) CN1256351C (en)

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100516093C (en) * 2006-04-21 2009-07-22 中国科学院上海有机化学研究所 Catalyst for olefin polymerization
CN100482697C (en) * 2006-05-22 2009-04-29 中国科学院上海有机化学研究所 Mono-active center Ziegler-Natta catalyst for olefinic polymerization
CN101600723A (en) * 2006-12-22 2009-12-09 国际壳牌研究有限公司 The part and the catalyst system thereof that are used for catalytic oligomerization of olefinic monomers
JP5480148B2 (en) 2007-10-16 2014-04-23 中国石化揚子石油化工有限公司 Magnesium compound-supported nonmetallocene catalyst and production thereof
JP5523572B2 (en) 2009-10-26 2014-06-18 中国石油化工股▲ふん▼有限公司 Supported nonmetallocene catalyst, process for its production and use thereof
JP5670460B2 (en) 2009-10-26 2015-02-18 中国石油化工股▲ふん▼有限公司 Supported nonmetallocene catalyst, process for its production and use thereof
EP2493934A4 (en) * 2009-10-28 2013-07-10 Exxonmobil Chem Patents Inc Catalyst compounds and use thereof
EP2493932A4 (en) * 2009-10-28 2013-06-12 Exxonmobil Chem Patents Inc Catalyst compounds and use thereof
EP2500364B1 (en) 2009-11-13 2020-03-04 China Petroleum & Chemical Corporation Supported non-metallocene catalyst preparation method and application thereof
WO2011057469A1 (en) 2009-11-13 2011-05-19 中国石油化工股份有限公司 Supported non-metallocene catalyst and preparation method and uses thereof
CN102030844B (en) * 2010-09-14 2014-07-23 中国科学院上海有机化学研究所 Olefin polymerization catalyst and polyethylene with ultralow branching coefficient and ultrahigh molecular weight
CN102964472B (en) * 2011-08-31 2015-07-01 中国石油化工股份有限公司 Supported non-metallocene catalyst, preparation method and application
CN102964489B (en) * 2011-08-31 2015-06-03 中国石油化工股份有限公司 Supported non-metallocene catalyst, preparation method and application
CN102964481B (en) * 2011-08-31 2015-04-22 中国石油化工股份有限公司 Supported non-metallocene catalyst, preparation method and application
CN102964471B (en) * 2011-08-31 2015-07-01 中国石油化工股份有限公司 Supported non-metallocene catalyst, preparation method and application
CN102964490B (en) * 2011-08-31 2015-07-01 中国石油化工股份有限公司 Supported non-metallocene catalyst, preparation method and application
CN102964480B (en) * 2011-08-31 2015-07-29 中国石油化工股份有限公司 Load type non-metallocene catalyst, its preparation method and application thereof
CN103183624B (en) * 2011-12-30 2017-04-19 中国科学院上海有机化学研究所 Catalyst used for olefine polymerization or copolymerization and preparation method thereof
JP5902210B2 (en) 2013-06-08 2016-04-13 中国石油化工股▲ふん▼有限公司 Supported nonmetallocene catalyst, process for its production and use thereof
CN105884664B (en) * 2014-09-05 2019-07-02 中国石油化工股份有限公司 A kind of Nonmetallocene ligand, its manufacturing method and its application

Also Published As

Publication number Publication date
CN1332182A (en) 2002-01-23

Similar Documents

Publication Publication Date Title
CN1256351C (en) Catalyst for polymerization and copolymerization of olefine and its synthesis and use
CN1203076C (en) Organometallic compound useful as cocatalyst for polymerizing olefins
CN1146593C (en) Catalyst and process for olefin polymerization
CN1093543C (en) Fused ring substituted indenyl metal complexes and polymerization process
CN1218970C (en) New olefine polymerization catalyst
CN1110467C (en) Manufacture of alpha-olefins
CN1120168C (en) Catalyst activators comprising expanded anions
CN1208357C (en) Olefin polymerization catalyst component and catalyst system and polymerization process using such catalyst system
CN1274701C (en) Metallocenes with bridged 4-phenyl-indenyl-ligand for olefin polymerization
CN1137148C (en) Catalyst system
CN1050135C (en) Olefin polymerization catalyst and process for olefin polymerization
CN1240455A (en) Polymerization of ethylene with specific iron or cobalt complexes, novel pyridinebis (imines) and novel complexes of pyridinebis (imines) with iron and cobalt
CN1784431A (en) High activity olefin polymerization catalyst and process
CN1612881A (en) Polymerization catalyst activator and its use in a polymerization process
CN1835978A (en) Catalytic system for the production of conjugated diene/mono-olefin copolymers and copolymers thereof
CN1842544A (en) Activated catalyst systems from substituted dialuminoxane complexes
CN100339403C (en) Halogen substituted catalyst system for olefin polymerization
CN1643004A (en) Substituted indenyl metal complexes and polymerization process
CN1320130A (en) Polymerization of olefins
CN1589284A (en) Imino-amide catalyst compositions for the polymerization of olefins
CN1058601A (en) Be used to prepare and have poly novel vanadium impregnated-Zr catalyst altogether wide or that bimodal Mw distributes
CN1537873A (en) Polyaddition catalyst component, polyaddition catalyst and process for preparing addition polymer
CN1168745C (en) Method for polymerising olefins
CN1169736A (en) Olefin polymerization catalyst
CN1226312C (en) Process for producing olefin polymer

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CX01 Expiry of patent term
CX01 Expiry of patent term

Granted publication date: 20060517