CN1218970C - New olefine polymerization catalyst - Google Patents

New olefine polymerization catalyst Download PDF

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CN1218970C
CN1218970C CN 02110844 CN02110844A CN1218970C CN 1218970 C CN1218970 C CN 1218970C CN 02110844 CN02110844 CN 02110844 CN 02110844 A CN02110844 A CN 02110844A CN 1218970 C CN1218970 C CN 1218970C
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CN1364818A (en
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唐勇
胡蔚秋
孙秀丽
王聪
张玉良
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Shanghai Institute of Organic Chemistry of CAS
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Shanghai Institute of Organic Chemistry of CAS
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Priority to PCT/CN2002/000425 priority patent/WO2003010207A1/en
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Abstract

The present invention relates to olefinic polymerization, a catalyst or a catalytic system for copolymerization, a synthetic method of the catalyst and application of the catalyst for catalyzing the olefinic polymerization. The catalyst is the complex of the transition metal in third group to eleventh group of a multi-dentate ligand, and the structural formula of the catalyst is disclosed in the specification.

Description

New olefine polymerization catalyst
Technical field
The present invention relates to olefinic polymerization and copolymerization catalyst (catalyst system), synthetic method and as the applied research of homogeneous phase (not load is directly used) or heterogeneous (using) system catalysis in olefine polymerization with carrier loaded back such as silicon oxide, aluminum oxide, magnesium chloride.This catalyzer relates to three races's to the 11 group 4 transition metal complexes of a class novel multidentate part.
Background technology
Since having found Ziegler-Natta catalyst from nineteen fifties, highly active MgCl 2The catalyzer of the titanium of load has shown good catalytic performance, (K.Ziegler, etc., Angew.Chem.1995,67,424; K.Ziegler etc., Angew.Chem.1995,67,541; N.Kashiwa etc., USP-3642746,1968) industrial at present, 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 controlling polymers structure, performance by regulating catalyst structure at present.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).In recent ten years, also flourish with the metal complexes that the part that contains ligating atoms such as N, O, P replaces cyclopentadiene and transition-metal coordination to obtain as the research of olefin polymerization catalysis, 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 C0211084400091
Report is not a lot of on the compound document of titanous chloride of non-luxuriant class single anion ligand (IV) and tri-chlorination zirconium (IV), 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, (Nagy S etc., WO9634021).People such as A.Otero have reported that compound h has shown high activity to vinyl polymerization, and the resulting polymers molecular weight is very high, but the molecular weight distribution broad (Organometallics, 2001,20,2428-2430).People such as Tang Yong have reported olefinic polymerization and copolymerization catalyst, preparation method and use, this catalyst structure formula (CN01126323.7) shown in i.
Summary of the invention
The invention provides a class olefinic polymerization and copolymerization catalyst (catalyst system), promptly relate to the catalyst system of three races's to the 11 group 4 transition metal complexes that a class is used for the polydentate ligand of olefinic polymerization.
The present invention also provides the synthetic method of above-mentioned catalyzer, comprises polydentate ligand and generates the synthetic method of metal complexes with three races to the 11 group 4 transition metals.
Catalyst system provided by the invention can be used as homogeneous phase (not load is directly used) or heterogeneous (using with carrier loaded back such as silicon oxide, aluminum oxide, magnesium chloride) system catalysis in olefine polymerization.
The present invention also provides the purposes of above-mentioned catalyzer, this catalyst system can be used for catalyzed ethylene, alpha-olefin, contain functional groups alkene comprise oligomerisation homopolymerization and copolymerization.
Olefinic polymerization provided by the invention and copolymerization catalyst are the described title complex of following structural formula (I):
Figure C0211084400101
To further be elaborated below to above-mentioned catalyzer:
Catalyst I mainly comprises the catalyst I A and the IB of following structure
Figure C0211084400102
IA-1～IA-7 will help to more clearly understand catalyst I A:
Figure C0211084400111
IB-1～IB-7 will help to more clearly understand catalyst system IB:
Figure C0211084400112
In above-mentioned all structures:
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:1,2,3 or 4;
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 group, 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 positively charged absolute value identical;
A: Sauerstoffatom, sulphur atom, selenium atom, R 23N-or-PR 24,-PR 24R 25,
-(PO) R 24(OR 25), sulfuryl, sulfoxide group ,-N (O) R 23R 24
B: refer to nitrogen-containing group, phosphorus-containing groups or C 1-C 30Alkyl;
D: refer to Sauerstoffatom, sulphur atom, selenium atom, C 1-C 30The nitrogen-containing group of alkyl, C 1-C 30The phosphorus-containing groups of alkyl, sulfuryl, sulfoxide group ,-P (O) R 24R 25,-P (O) R 24(OR 25) ,-N (O) R 23R 24, 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;
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;
G: be inertia group, comprise C 1-C 30Alkyl, C 1-C 30Substituted hydrocarbon radical or safing function group;
Y, Z: nitrogen-containing group, sulfur-containing group, oxy radical, phosphorus-containing groups, contain seleno group, as-NR 23R 24,-PR 24R 25,-SR 30,-OR 31, R 24R 25P (O)-, R 30S (O)-,-SeR 30,-SeOR 31
→: 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 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18, R 19, R 20, R 21, R 23, R 24, R 25, R 30, R 31: 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, above-mentioned group can be the same or different to each other, wherein adjacent group such as R 1With R 2, R 3, R 3With R 4, R 6, R 7, R 8, R 9And R 23With R 24Deng can be each other in key Cheng Huan.
R 26Refer to lone-pair electron, hydrogen, C on the nitrogen 1-C 30Alkyl, C 1-C 30Alkyl, the oxy radical of replacement comprise hydroxyl, alkoxyl group-OR 31, the alkyl that has ehter bond comprises-T-OR 31, sulfur-containing group comprises-SR 30,-T-SR 30, nitrogen-containing group comprises-NR 23R 24,-T-NR 23R 24, phosphorus-containing groups comprises-PR 24R 25,-T-PR 24R 25,-T-P (O) R 24R 25Work as R 26During for oxy radical, sulfur-containing group, nitrogen-containing group, contain seleno group, phosphorus-containing groups, N, O, S, P can participate in the coordination with metal.
T: be C 1-C 30Alkyl or C 1-C 30Substituted hydrocarbon radical or safing function group;
Catalytic body of the present invention means the system that contains above-mentioned catalyzer, can be by 1. or 1. being carried on 2. back or 1. and 3. in the following substances, or 1. and 3. be carried on the 2. formed four kinds of systems in back:
1. catalyzer shown in the structural formula (I);
2. carrier comprises silicon oxide, aluminum oxide, magnesium chloride, titanium oxide or their mixture etc.;
3. promotor W.
Synthesizing of catalyzer of the present invention
Among the present invention, arrive in the temperature range that refluxes at-78 ℃, catalyzer is to be respectively reaction in 1: 0.1～6 o'clock by the negative ion metallizing thing of the part of following structural formula or part with mol ratio to obtain in 0.5～40 hour in organic solvent, prolongs the reaction times to not influence of reaction.Organic solvent can be tetrahydrofuran (THF), sherwood oil, toluene, methylene dichloride, CCl 4, ether, 2,4-dioxane or 1,2-ethylene dichloride etc.
Wherein:
A:A: Sauerstoffatom, sulphur atom, selenium atom, R 23N-or-PR 24,-PR 24R 25,
-(PO) R 24(OR 25), sulfuryl, sulfoxide group ,-N (O) R 23R 24
B: refer to nitrogen-containing group, phosphorus-containing groups or C 1-C 30Alkyl;
D: refer to Sauerstoffatom, sulphur atom, selenium atom, C 1-C 30The nitrogen-containing group of alkyl, C 1-C 30The phosphorus-containing groups of alkyl, sulfuryl, sulfoxide group ,-P (O) R 24R 25,-P (O) R 24(OR 25) ,-N (O) R 23R 24, 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;
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;
G: be inertia group, comprise C 1-C 30Alkyl, C 1-C 30Substituted hydrocarbon radical or safing function group;
Y, Z: nitrogen-containing group, sulfur-containing group, oxy radical, phosphorus-containing groups, contain seleno group, as-NR 23R 24,-PR 24R 25,-SR 30,-OR 31, R 24R 25P (O)-, R 30S (O)-,-SeR 30,-SeOR 31
→: 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 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18, R 19, R 20, R 21, R 23, R 24, R 25, R 30, R 31: 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, above-mentioned group can be the same or different to each other, wherein adjacent group such as R 1With R 2, R 3, R 3With R 4, R 6, R 7, R 8, R 9And R 23With R 24Deng can be each other in key Cheng Huan.
R 26Refer to lone-pair electron, hydrogen, C on the nitrogen 1-C 30Alkyl, C 1-C 30Alkyl, the oxy radical of replacement comprise hydroxyl, alkoxyl group-OR 31, the alkyl that has ehter bond comprises-T-OR 31, sulfur-containing group comprises-SR 30,-T-SR 30, nitrogen-containing group comprises-NR 23R 24,-T-NR 23R 24, phosphorus-containing groups comprises-PR 24R 25,-T-PR 24R 25,-T-P (O) R 24R 25Work as R 26During for oxy radical, sulfur-containing group, nitrogen-containing group, contain seleno group, phosphorus-containing groups, N, O, S, P can participate in the coordination with metal.
T: be C 1-C 30Alkyl or C 1-C 30Substituted hydrocarbon radical or safing function group; Catalyst applications-reaction, polymerization and polymerisate
Catalyzer of the present invention (catalyst system) is as homogeneous phase (not load is directly used) or heterogeneous (using with carrier loaded back such as silicon oxide, aluminum oxide, magnesium chloride) system catalysis in olefine polymerization, described olefinic polymerization is equal polymerization or the copolymerization that comprises oligomerisation, can use or use separately with promotor usually.
The present invention relates to following olefin polymerization process, promptly-100～200 ℃ will comprise at least 1. or 1. be carried on 2. in the following substances after and 4. catalyzed reaction takes place, also can add again 3. and to participate in reaction:
1. catalyzer shown in the structural formula (I);
2. carrier;
3. promotor W;
4. alkene.
Above-mentioned catalyst system of the present invention can be used for catalysis in olefine polymerization, and alkene comprises ethene, alpha-olefin, vinylbenzene, various olefin(e) acid and derivative, enol and derivative thereof, diolefine, cycloolefin etc., and alpha-olefin is meant C 3~ C 16Alkene, for example propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, 4-methyl-1-pentene and its mixture etc., the main finger ring amylene of cycloolefin, tetrahydrobenzene, norbornylene etc. and derivative thereof; Polymerization comprises the above-mentioned monomeric equal polymerization of the oligomerisation polymerization together that comprises.
Slurry polymerization, endless tube polymerization, vapour phase polymerization or other forms of polymerization technique are adopted in polymerization.
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.
Polymerization temperature maintains-50～150 ℃, for reaching good catalytic activity and throughput, can maintain 0～120 ℃.
Polymerization pressure can change in 0.1～10MPa, and operation can obtain reactor operating parameters and polymkeric substance preferably in 0.1～3MPa.
Described promotor W is MAO (methylaluminoxane), MMAO (methylaluminoxane of modification), EAO (ethyl aikyiaiurnirsoxan beta), BAO (butyl aikyiaiurnirsoxan beta), LiR (R=C 1-C 10Alkyl), AlR 3(R=C 1-C 10Alkyl), Lewis acid (Lewis acid), LiR/Lewis acid (R=C 1-C 10Alkyl), AlR 3/ Lewis acid (R=C 1-C 10Alkyl), borine such as B (C 6F 5) 3Deng.
Catalyzer and promotor can any order adding system carry out polymerization.The variable-scale of employed catalyzer of polymerization and promotor.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.
To the part term that foregoing partly uses be described as follows below, these explanations will help clearer understanding content of the present invention.
Catalytic body means and 1. or 1. is carried on 2. back or 1. and 3. in the following substances, or 1. and 3. is carried on the 2. formed system in back:
4. catalyzer shown in the structural formula (I);
5. carrier comprises silicon oxide, aluminum oxide, magnesium chloride, titanium oxide or their mixture etc.;
6. promotor W.
Promotor W is meant a kind of neutral Lewis acid (Lewis acid), can take out X from metal M -Form (WX) -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;
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, p 1405-1421 (1988), and S.H.Stares, Chem.Rev., vol.93, p927-942 (1993)) and reference, 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 -
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, 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, contain in the process of compound of substituted hydrocarbon radical in use, these substituting groups are inert, and promptly these substituting groups do not have substantial interference to related process, 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 carbon containing functional groups of alkyl and substituted hydrocarbon radical at this patent middle finger, this functional group is not to all there being substantive the interference in the reaction that may participate at the compound that contains this functional groups, here the indication functional groups comprises halogen (fluorine, chlorine, bromine, iodine), ether is (as-OR 31Or-TOR 31), C 1-C 10Ester group, C 1-C 10Amido, C 1-C 10Alkoxyl 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, D, E, F, Y, the Z group that contains ligating atom, and promptly these functional groups should not replace desirable coordinating group;
Oxy radical refers to hydroxyl, alkoxyl group-OR 31, the alkyl that has an ehter bond is as-T-OR 31
Sulfur-containing group refers to-SR 30,-T-SR 26,-SOR 30,-T-SO 2R 26
Boron-containing group refers to BF 4 -, (C 6F 5) 4B -, (R 27BAr 3) -Deng;
Contain aluminium base group and refer to alkylaluminium cpd, AlPh 4 -, AlF 4 -, AlCl 4 -, AlBr 4 -, AlI 4 -, R 32AlAr 3 -
Phosphorus-containing groups refers to-PR 24R 25,-P (O) R 24R 25,-P (O) R 24(OR 25);
Nitrogen-containing group refers to-NR 23R 24And-T-NR 23R 24,-N (O) R 23R 24
Silicon-containing group refers to-T-SiR 28
Germanic group-T-GeR 28
Contain tin group and refer to-T-SnR 29
Containing seleno group refers to-T-SeR 29
T: be C 1-C 30Alkyl or C 1-C 30Substituted hydrocarbon radical or safing function group;
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
R 24, R 25, R 27, R 28, R 29, R 30, R 31, R 32Be hydrogen, C 1-C 30Alkyl, halogen atom, C 1-C 30Substituted hydrocarbon radical or safing function group, above-mentioned group can be the same or different to each other, wherein adjacent group can be each other in key Cheng Huan.
In sum, the invention provides a kind of olefinic polymerization and copolymerization catalyst and catalyst system, preparation method and use.This catalyzer is three races's to the 11 group 4 transition metal complexes of polydentate ligand, is reacted in organic solvent by above-mentioned part metallizing thing to obtain.This catalyzer provided by the invention can be separately or is used for catalyzed ethylene, alpha-olefin, contains the equal polymerization polymerization together that comprises oligomerisation of functionalization group alkene etc. as homogeneous phase (not load is directly used) or heterogeneous (using with carrier loaded back such as silicon oxide, aluminum oxide, magnesium chloride) system under the effect of promotor.Wherein Aryl, Broad and pyridine represent phenyl, broad peak and pyridine respectively.
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 examples have shown not ipsilateral of the present invention.Given embodiment comprises 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 the used part of embodiment one～embodiment 16 declaratives catalyzer, synthesizing of embodiment 17～embodiment 24 declaratives catalyzer, embodiment 25～embodiment 40 declaratives catalyst vinyl polymerization results, the equal polymerization of other alkene of embodiment 41～embodiment 53 declaratives catalysts except that ethene is the polymeric result together.Wherein Aryl, Broad and pyridine represent phenyl, broad peak and pyridine respectively.
Synthesizing of embodiment one ligand L 1
In the reaction flask of 250ml, add 2.34g (10.0mmol) 3,5-di-tert-butyl salicylaldehyde, 2.3g (8.8mmol) (o-amino-phenyl-) diphenylamine, the 100ml dehydrated alcohol, after being heated to backflow 24h, stopped reaction makes to be chilled to room temperature, promptly obtain product, with cold washing with alcohol for several times, obtain yellow crystals L1 after the drying, 3.5g (81%).
Figure C0211084400161
Ultimate analysis: actual measurement (calculated value): C:83.19 (83.15) H:7.60 (7.61) N:5.87 (5.88)
1HNMR(300MHz CDCl 3)：δ13.6(s O-H)；8.6(s CH＝N)；7.5-7.0(m，Aryl H)1.5，1.3(s，st-Bu-H)
Synthesizing of embodiment two ligand L 2
In the reaction flask of 250ml, add 5.62g (24mmol) 3, the 5-di-tert-butyl salicylaldehyde, 3.68g (20mmol) phenyl neighbour-dimethylamino phenyl ether, 100ml dehydrated alcohol, after being heated to backflow 20h, stopped reaction makes to be chilled to room temperature, promptly obtains product, with absolute ethanol washing for several times, obtain yellow crystals L2 5.2g (65%) after the drying.
Figure C0211084400171
Ultimate analysis: actual measurement (calculated value): C:80.76 (80.76); H:7.77 (7.78); N:3.51 (3.49)
1HNMR(300MHz CDCl 3)：δ(ppm)13.4(s，O-H)；8.7(s CH＝N)；7.4-7.0(m，Aryl-H)；1.4，1.3(s，s t-Bu-H)
Synthesizing of embodiment three ligand L 3
In reaction flask, add 2.8g (12.0mmol) 3, the 5-di-tert-butyl salicylaldehyde, 2.01g (10.0mmol) phenyl, 2-aminocarbonyl phenyl thioether, the 25ml dehydrated alcohol, a small amount of glacial acetic acid, stopped reaction behind the stirring 2h that refluxes, separate out the yellow-green colour solid after the cooling, obtain ligand L 3 1.3g (44.4%) behind the recrystallization.
Figure C0211084400172
Ultimate analysis: actual measurement (calculated value): C:77.70 (77.65), H:7.50 (7.48), N:3.38 (3.35);
1HNMR(300MHz CDCl 3)：δ(ppm)13.3(s O-H)，8.6(s CH＝N)，7.45-7.11(m Aryl H)，1.47，1.32(s，s t-Bu-H)
The L4 of embodiment four parts is synthetic
Under 0 ℃ of-5 ℃ of condition, the 5ml dichloromethane solution of 650mg (0.31mmol) m-CBPA is dropped in the 10ml dichloromethane solution of 125mg (0.3mmol) L3, dropwise, keep continuing under 0 ℃ of-5 ℃ of condition to stir 1h, column chromatography for separation obtains ligand L 4,730mg (57.3%).
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 CH＝N)；7.75-6.66(m Aryl H)；
Synthesizing of embodiment five ligand L 5
In reaction flask, add 3.4g (14.0mmol) 3, the 5-di-tert-butyl salicylaldehyde, 2.3g (16.0mmol) 8-amido quinoline, the 100ml dehydrated alcohol, a small amount of glacial acetic acid, stopped reaction behind the stirring 24h that refluxes obtains ligand L 5 2.31g (64%) after the column chromatography for separation.
Figure C0211084400182
Ultimate analysis: actual measurement (calculating): C:80.25 (79.96); H:7.88 (7.83); N:7.75 (7.77);
1HNMR(CDCl 3)：14.0(s，O-H)；8.9(s，CH＝N)；9.0(d，pyridine-2)；8.2(d，pyridine-4)；7.6(t，pyridine-3)；7.7-7.4(m，Aryl-H)；1.5，1.4(s，s，t-Bu-H)
Embodiment sexadentate L6's is synthetic
The benzole soln of adjacent aminocarbonyl phenyl diphenylphosphine is at H 2O 2(30%) under the effect, can quantitatively obtain adjacent aminocarbonyl phenyl diphenyl phosphine oxide.Synthetic method according to similar to ligand L 1 obtains ligand L 6 560mg (64%) after the column chromatography for separation.
Ultimate analysis: actual measurement (calculating): C:77.87 (77.77); H:7.14 (7.12); N:2.71 (2.75)
1HNMR(CDCl 3)：11.7(s，O-H)；8.2(s，CH＝N)；7.75-7.0(m，Aryl-H)；1.33，1.28(s，s，t-Bu-H)
Synthesizing of embodiment seven ligand L 7
The 20ml tetrahydrofuran solution of L2 1.2g (3.0mmol) is added drop-wise to 0.45g LiAlH 4The tetrahydrofuran (THF) suspension liquid in, ice-water bath cooling makes after dropwising and returns to room temperature gradually, continues to stir, and after the TLC monitoring reaction finishes, drips less water cancellation reaction, in four times of water of gained mixture impouring, adds 30%H 2SO 4Make Al (OH) 3Dissolving is complete, CH 2Cl 2Extraction, anhydrous Na 2SO 4Drying, column chromatography for separation obtain white product L71.0g (82%).
Figure C0211084400192
Ultimate analysis: actual measurement (calculated value): C:80.58 (80.36) H:8.41 (8.24) N:3.30 (3.47);
1HNMR(300MHz CDCl 3)：δ(ppm)13.4-13.2(s，O-H)8.3(s CH＝N)；7.6-6.6(m，6H Aryl-H)3.1(s，N-CH 3)1.5，1.4(s，s 9H，9H t-Bu-H).
Embodiment eight ligand L 8, L9's is synthetic
According to the L7 similar methods, promptly obtain ligand L 8 (95%), L9 (81%).
Ligand L 8 ultimate analyses: actual measurement (calculated value): C:77.68 (77.28), H:7.85 (7.93), N:3.03 (3.34);
1HNMR(300MHz CDCl 3)：δ(ppm)13.3(s O-H)，8.6(s CH＝N)，7.45-7.11(m Aryl H)，1.47，1.32(s，s t-Bu-H)；
Ligand L 9 ultimate analyses: actual measurement (calculated value): C:79.88 (79.97), H:7.80 (7.73), N:3.03 (2.83);
1HNMR(300MHz CDCl 3)：δ(ppm)7.4-6.8(m Aryl H)；4.8(broads..NH)；4.3(s，CH 2)；1.3(s，t-Bu-H)
Synthesizing of embodiment nine ligand L 10
In the dichloromethane solution of ligand L 9 6.2g (12.5mmol), splash into 20ml H 2O 2(30%), behind the vigorous stirring 4h, separatory, organic phase is removed to desolvate and is quantitatively obtained ligand L 10.
Ultimate analysis: actual measurement (calculated value): C:77.48 (77.47), H:7.29 (7.49), N:3.03 (2.74);
1HNMR(300MHz CDCl 3)：δ(ppm)7.7-6.7(m Aryl H)；4.3(d，CH 2N)；1.28(s，s t-Bu-H)
Synthesizing of embodiment ten ligand L 11
Under-78 ℃ of conditions, 4.0mmol NaH is mixed with ligand L 10 1.018g (2.0mmol), add 30ml THF, make to return to room temperature gradually, continue to stir 2h, add 0.23ml (4.0mmol) CH 3I continues to stir 2h, and stopped reaction adds deionized water, with dichloromethane extraction, and organic phase anhydrous Na SO 4Drying is removed and is desolvated, and quantitatively obtains ligand L 11 after the column chromatography for separation.
Ultimate analysis: actual measurement (calculated value): C:77.75 (77.89) H:7.88 (7.84) N:2.69 (2.60)
1HNMR(300MHz CDCl 3)：δ(ppm)7.7-6.9(m Aryl H)；4.3(s，CH 2)；3.6(s，OMe)；2.2(s，NMe)；1.3，1.2(s，s t-Bu-H)；
Synthesizing of embodiment 11 ligand L 12
Under 0 ℃, in the 25ml toluene solvant of ligand L 11 537mg (1.0mmol), add HSiCl 30.5ml (5.0mmol), reflux to stir and spend the night, stopped reaction is to be cooled to room temperature, adds the 40ml ether, adds saturated NaHCO in system 3Solution 15ml removes by filter insolubles, removes and desolvates, and column chromatography for separation obtains ligand L 12.
Figure C0211084400211
Ultimate analysis: actual measurement (calculating) C: 80.41 (80.27); H: 8.15 (8.08); N: 2.51 (2.67);
1HNMR(300MHz CDCl 3)：δ(ppm)7.5-6.8(m Aryl H)；4.2(s，CH 2)；3.7(s，OMe)；2.5(s，NMe)；1.5，1.2(s，s t-Bu-H)；
Synthesizing of embodiment 12 ligand L 13
Under-78 ℃, the 15ml THF drips of solution of ligand L 10 509mg (1.0mmol) is added among the 5ml THF of 1mmolNaH, slowly rises to room temperature, continue to stir 2h, 0.33ml (2.5mmol) Me 3The 15ml THF solution of SiCl slowly is added drop-wise in the above-mentioned negative solution, dropwises backflow 2h, stopped reaction.Column chromatography for separation obtains ligand L 13 350mg (60%).
Figure C0211084400212
Ultimate analysis: actual measurement (calculating) C:74.33 (74.06) H:8.21 (7.94) N:2.24 (2.40)
1HNMR(300MHz CDCl 3)：δ(ppm)7.7-6.5(m Aryl H)；4.3(s，CH 2)；1.3，1.2(s，s t-Bu-H)；0.3(s，SiMe 3)
Synthesizing of embodiment 13 ligand L 14
Obtain ligand L 14 according to the synthetic method similar by 2-pyrrole aldehyde and the reaction of adjacent aminocarbonyl phenyl diphenylphosphine to ligand L 1.
Figure C0211084400213
Ultimate analysis: actual measurement (calculating) C:77.84 (77.95) H:5.31 (5.40) N:7.66 (7.90)
1HNMR(300MHz CDCl 3)：δ 8.1(s CH＝N)；7.4-6.2(m，Aryl H)；1.9(broad，s N-H)；
Synthesizing of embodiment 14 ligand L 15
Obtain ligand L 15 according to the synthetic method similar by 2-hydroxyl 5-nitrobenzaldehyde and the reaction of adjacent aminocarbonyl phenyl diphenylphosphine to ligand L 1.
Figure C0211084400221
Ultimate analysis: actual measurement (calculating) C:70.77 (70.42); H:4.50 (4.49); N:6.45 (6.57);
1HNMR(300MHz CDCl 3)：δ8.0(s CH＝N)；7.7-6.6(m，Aryl H)；
Synthesizing of embodiment 15 ligand L 16
Obtain ligand L 16 according to the synthetic method similar by 2-hydroxyl-3-(9-anthryl) phenyl aldehyde and the reaction of adjacent aminocarbonyl phenyl diphenylphosphine to ligand L 1.
Ultimate analysis: actual measurement (calculating) C:83.75 (84.00); H:5.38 (5.06); N:2.87 (2.51);
1HNMR(300MHz CDCl 3)：δ 13.5(s OH)；8.4(s CH＝N)；8.9-7.0(m，Aryl H)；
Embodiment ten sexadentate L17's is synthetic
Obtain ligand L 17 according to the synthetic method similar by 2-hydroxyl-3-(9-phenanthryl) phenyl aldehyde and the reaction of adjacent aminocarbonyl phenyl diphenylphosphine to ligand L 1.
Figure C0211084400223
Ultimate analysis: actual measurement (calculating) C:84.29 (84.00); H:5.13 (5.06); N:2.23 (2.51):
1HNMR(300MHz CDCl 3)：δδ13.3(s OH)；8.6(s CH＝N)；7.0-8.8(m，Aryl H)；
Embodiment 17 title complex A-1's is synthetic
15ml tetrahydrofuran solution with 476mg (1.0mmol) ligand L 1 under-78 ℃ is added dropwise in the 15ml tetrahydrofuran (THF) of 43mg (1.1mmol) KH, continues under the room temperature and stirs 3h.Vacuum desolventizes, and adds 40ml toluene, and 50 ℃ (drop to TiCl with this negative solution down 40.11ml in the 40ml toluene solution (1.0mmol), dropwise, continue at 50 ℃ and stir 3h down.Centrifugal, supernatant liquor removes to desolvate and promptly obtains thick product, obtains title complex A-1 380mg (60%) with the dichloromethane/hexane recrystallization.
Ultimate analysis: actual measurement (calculating) C:62.05 (62.93); H:5.03 (5.60) N:7.25 (7.60)
1HNMR(300MHz CDCl 3)：δ 8.3(s CH＝N)；7.7-6.9(m，Aryl H)；1.6，1.3(s，s t-Bu-H)；FID-MS(M +)：629
Synthesizing of embodiment 18 complex B-1
50ml tetrahydrofuran solution with 476mg (1.0mmol) ligand L 1 under-78 ℃ is added dropwise in the 15ml tetrahydrofuran (THF) of 43mg (1.1mmol) KH, continues under the room temperature and stirs 3h.Under 50 ℃ this negative solution is dropped to ZrCl 4Among the 15ml THF of 2THF g (1.0mmol), dropwise, continue to reflux to stir and spend the night.Vacuum desolventizes, and adds methylene dichloride 20ml and makes dissolving fully, and centrifugal, supernatant concentration adds a small amount of hexane, freezingly obtains thick product, obtains complex B-1215mg (32%) with the dichloromethane/hexane recrystallization.
1HNMR(300MHz CDCl 3)：δ 8.4(s CH＝N)；8.0-6.9(m，Aryl H)；1.6，1.3(s，s t-Bu-H)；FID-MS(M +)：673
Embodiment 19
Obtain other title complex A-2 (60%) with the experimental technique similar to title complex A-1; A-3 (78%); A-4 (70%); A-6 (87%); A-9 (78%); A-14 (74%); A-16 (71%); A-17 (71%).
The partial analysis data are as follows:
A-2
1H NMR(300MHz CDCl 3)：δ 8.8(s CH＝N)；7.8-6.6(m，Aryl H)；1.5，1.3(s，s t-Bu-H)A-3
1H NMR(300MHz CDCl 3)：δ 8.9(s CH＝N)；7.7-7.2(m，Aryl H)；1.5，1.3(s，s t-Bu-H)；
A-5
Ultimate analysis: actual measurement (calculating) C:56.74 (56.11); H:5.48 (5.30); N:5.26 (5.45);
1H NMR(300MHz CDCl 3)：δ9.0(s CH＝N)；9.6(d，pyridine-1H)；8.5(d，pyridine-1H)；8.0(q，Aryl-2H)；7.7(m，Aryl-3H)；7.5(d，Aryl-1H)；1.5，1.3(d，d t-Bu-H)
A-6
Ultimate analysis: actual measurement (calculating) C:59.77 (59.80); H:5.20 (5.32); N:2.43 (2.11)
1H NMR(300MHz CDCl 3)：δ 8.4(s CH＝N)；8.0-7.1(m，Aryl H)；1.6，1.3(d，d t-Bu-H)
A-9
Ultimate analysis: actual measurement (calculating) C:61.32 (61.09); H:5.78 (5.75); N:7.44 (7.38)
1H NMR(300MHz CDCl 3)：δ7.7-7.1(m，Aryl H)；4.7(d，CH 2)；1.3(d，d t-Bu-H)；
A-14
Ultimate analysis: actual measurement (calculating) C:54.99 (54.42); H:3.77 (3.57); N:5.32 (5.52)
1H NMR(300MHz CDCl 3)：δ8.0(s CH＝N)；7.4-6.1(m，Aryl H)；
A-16
1H NMR(300MHz CDCl 3)：δ 8.2(s CH＝N)；8.8-6.9(m，Aryl H)；
A-17
1H NMR(300MHz CDCl 3)：δ8.4(s CH＝N)；8.7-6.9(m，Aryl H)；
Embodiment 20
Obtain other complex B-5 (35%) with the experimental technique similar to complex B-1; B-6 (38%); B-9 (52%); B-16 (23%);
B-5
1HNMR(300MHz CDCl 3)：δ 9.1(s CH＝N)；9.6(d，pyridine-1H)；8.6(d，pyridine-1H)；7.9-7.3(m，Aryl H)；
B-6
1HNMR(300MHz CDCl 3)：δ8.4(s CH＝N)；8.1-7.0(m，Aryl H)；1.5，1.3(d，d t-Bu-H)
B-9
Ultimate analysis: actual measurement (calculating) C:58.01 (57.26); H:5.78 (5.39); N:1.77 (2.02);
1HNMR(300MHz CDCl 3)：δ7.8-6.6(m，Aryl H)；1.2(s t-Bu-H)；
B-16
1HNMR(300MHz CDCl 3)：δ8.1(s CH＝N)；8.6-6.5(m，Aryl H)；
Embodiment 21 title complex C-11's is synthetic
Add ligand L 11 162mg (0.3mmol), anhydrous FeCl in the reaction flask 237mg (0.3mmol) adds 20ml THF in mixture, stirred overnight at room temperature, and vacuum desolventizes, and thick product obtains title complex C-11 166mg (83%) with the dichloromethane/hexane recrystallization.
Figure C0211084400261
FID-MS(M +) 666
Embodiment 22 title complex C-14's is synthetic
Under-78 ℃, the 15ml THF solution of ligand L 14 417.6mg (1.2mmol) is added among the 5ml THF of KH 48mg (1.2mmol), return to room temperature gradually, stir 1h ,-78 ℃, in above-mentioned negative solution, add anhydrous FeCl 220ml THF solution, continue under the room temperature to stir and spend the night, add anhydrous diethyl ether 40ml, centrifugal, supernatant liquor removes and desolvates, thick product obtains title complex C-14 304mg (57%) with the dichloromethane/hexane recrystallization.
FID-MS(M +)：444
Embodiment 23 title complex C-15's is synthetic
Under-78 ℃, the 15ml THF solution of ligand L 15 159mg (0.37mmol) is added among the 5ml THF of KH 15mg (0.37mmol), return to room temperature gradually, stir 1h ,-78 ℃, in above-mentioned negative solution, add anhydrous FeCl 2, continue to stir and spend the night, add anhydrous diethyl ether 40ml, centrifugal, supernatant liquor removes and desolvates, and thick product obtains title complex C-15 191mg (63%) with the dichloromethane/hexane recrystallization.
FID-MS(M +)：516
Ultimate analysis: actual measurement (calculating): C:55.48 (58.11); H:4.31 (3.51); N:4.69 (5.42);
Embodiment 24 title complex D-9's is synthetic
Under-78 ℃, add n-BuLi (1.6M hexane solution) 0.5ml (0.8mmol), dropwise to the 7ml THF of ligand L 9 200mg (0.4mmol) solution, return to room temperature gradually, stir 1h, vacuum desolventizes, add 15ml toluene, will drop to TiCl in the above-mentioned negative solution 4The 20ml toluene solution in, continue to keep 30-40 ℃ to stir 3h, stirred overnight at room temperature, centrifugal, supernatant concentration, freezing, obtain thick product, the toluene recrystallization obtains title complex D-9 169mg (69%).
Ultimate analysis: actual measurement (calculating): C:63.99 (64.72); H:6.35 (5.93); N:2.07 (2.29)
1HNMR(300MHz CDCl 3)：δ7.7-7.1(m，Aryl H)；1.2(s t-Bu-H)；
Embodiment 25
Under the ethene atmosphere of 0.1Mpa, successively with in the few polymerization bottle that adds through taking out roasting 100ml of toluene 20ml, MMAO (mol ratio of MMAO and catalyzer is 400), vigorous stirring, place 50 ℃ of oil baths then, the constant temperature certain hour, catalyst A-18 (2 μ mol) is added, react after 15 minutes, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polyethylene 1.4g in 40 ℃ of vacuum-dryings after precipitation, filtration, washing.
Embodiment 26
In 2 liters autoclave, under the ethene atmosphere, add the MAO of 600ml toluene, 4.3ml 15% successively, stirred 15 minutes under the room temperature, 10ml contains the hexane solution of 23 μ mol A-18, under vigorous stirring, ethylene pressure is risen to 6 * 10 5MPa reacted after 0.5 hour, and emptying ethylene gas, polymkeric substance to constant weight, get polyethylene 31.5g in 50 ℃ of vacuum-dryings after precipitation, filtration, washing.Resulting polymers molecular weight M w=1700,000g/mol.
Embodiment 27
Under the ethene atmosphere of 0.1Mpa, successively with toluene 20ml, Et 3Al (Et 3The mol ratio of Al and catalyzer is 1000) the few adding, in the polymerization bottle through taking out roasting 100ml, vigorous stirring, place 40 ℃ of oil baths then, the constant temperature certain hour adds catalyst A-18 (2 μ mol), react after 15 minutes, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polyethylene 0.14g in 40 ℃ of vacuum-dryings after precipitation, filtration, washing.
Embodiment 28
Under the ethene atmosphere of 0.1Mpa, successively toluene 20ml, MMAO (mol ratio of MMAO and catalyzer is 500) are added, in the polymerization bottle through taking out roasting 100ml, vigorous stirring, place 50 ℃ of oil baths then, the constant temperature certain hour adds catalyzer (A-9) (2 μ mol), react after 3 minutes, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polyethylene 0.55g in 40 ℃ of vacuum-dryings after precipitation, filtration, washing.
Embodiment 29
Under the ethene atmosphere of 0.1Mpa, successively toluene 15ml, MMAO (mol ratio of MMAO and catalyzer is 500) are added in the polymerization bottle through taking out roasting 100ml, vigorous stirring, place 50 ℃ of oil baths then, the constant temperature certain hour, add catalyzer toluene solution (D-9) (3 μ mol), react after 3 minutes, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polyethylene 0.412g in 40 ℃ of vacuum-dryings after precipitation, filtration, washing.
Embodiment 30
Under the ethene atmosphere of 0.1Mpa, successively toluene 10ml, MMAO (mol ratio of MMAO and catalyzer is 500) are added in the polymerization bottle through taking out roasting 100ml, vigorous stirring, place 50 ℃ of oil baths then, the constant temperature certain hour, add catalyzer toluene solution (B-9) (6 μ mol), behind the reaction 1hr, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polyethylene 0.064g in 40 ℃ of vacuum-dryings after precipitation, filtration, washing.
The embodiment hentriaconta-
Under the ethene atmosphere of 0.1Mpa, successively toluene 15ml, MMAO (mol ratio of MMAO and catalyzer is 500) are added in the polymerization bottle through taking out roasting 100ml, vigorous stirring, place 50 ℃ of oil baths then, the constant temperature certain hour, add catalyzer toluene solution (A-5) (8 μ mol), react after 3 hours, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polyethylene 0.37g in 40 ℃ of vacuum-dryings after precipitation, filtration, washing.
Embodiment 32
Under the ethene atmosphere of 0.1Mpa, successively toluene 15ml, MMAO (mol ratio of MMAO and catalyzer is 500) are added in the polymerization bottle through taking out roasting 100ml, vigorous stirring, place 50 ℃ of oil baths then, the constant temperature certain hour, add catalyzer (A-3) toluene solution (8 μ mol), after reaction half an hour, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polyethylene 0.91g in 40 ℃ of vacuum-dryings after precipitation, filtration, washing.
Embodiment 33
Under the ethene atmosphere of 0.1Mpa, under the room temperature toluene 15ml, MMAO (mol ratio of MMAO and catalyzer is 500) are added in the polymerization bottle through taking out roasting 100ml successively, vigorous stirring, place 50 ℃ of oil baths then, the constant temperature certain hour, add catalyzer (A-2) (9 μ mol) reaction again after 3 hours, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polymkeric substance 0.45g in 50 ℃ of vacuum-dryings after precipitation, filtration, washing.
Embodiment 34
Under the ethene atmosphere of 0.1Mpa, under the room temperature toluene 10ml, MMAO (mol ratio of MMAO and catalyzer is 500) are added in the polymerization bottle through taking out roasting 100ml successively, vigorous stirring, place 50 ℃ of oil baths then, the constant temperature certain hour, add catalyzer (A-6) (30 μ mol) reaction again after 20 minutes, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polymkeric substance 0.70g in 50 ℃ of vacuum-dryings after precipitation, filtration, washing.
Embodiment 35
Under the ethene atmosphere of 0.1Mpa, under the room temperature toluene 10ml, MMAO (mol ratio of MMAO and catalyzer is 500) are added in the polymerization bottle through taking out roasting 100ml successively, vigorous stirring, place 50 ℃ of (oil baths then, the constant temperature certain hour, add catalyzer (A-1) (3 μ mol) reaction again after 1 hour, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polymkeric substance 0.34g in 50 ℃ of vacuum-dryings after precipitation, filtration, washing.
Embodiment 36
Under the ethene atmosphere of 0.1Mpa, under the room temperature toluene 10ml, MMAO (mol ratio of MMAO and catalyzer is 500) are added in the polymerization bottle through taking out roasting 100ml successively, vigorous stirring, place 50 ℃ of oil baths then, the constant temperature certain hour, add catalyzer (B-1) (5 μ mol) reaction again after 1 hour, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polymkeric substance 0.4g in 50 ℃ of vacuum-dryings after precipitation, filtration, washing.
Embodiment 37
Under the ethene atmosphere of 0.1Mpa, toluene 20ml, MMAO (mol ratio of MMAO and catalyzer is 1000) are added in the polymerization bottle through taking out roasting 100ml successively, vigorous stirring, place 0 ℃ of ice bath then, the constant temperature certain hour, add catalyzer (C-18) (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.
Embodiment 38
Under the ethene atmosphere of 0.1Mpa, under the room temperature toluene 20ml, MMAO (mol ratio of MMAO and catalyzer is 1000) are added in the polymerization bottle through taking out roasting 100ml successively, vigorous stirring, add catalyzer (C-15) (16 μ mol) reaction again after 1 hour, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets ethylene oligomer 0.7g in 50 ℃ of vacuum-dryings after precipitation, filtration, washing.
Embodiment 39
Under the ethene atmosphere of 0.1Mpa, under the room temperature toluene 20ml, MMAO (mol ratio of MMAO and catalyzer is 1000) are added in the polymerization bottle through taking out roasting 100ml successively, vigorous stirring, add catalyzer (C-14 again, Fe) (22 μ mol) reaction is after 3 hours, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polymkeric substance 0.003g in 50 ℃ of vacuum-dryings after precipitation, filtration, washing.
Embodiment 40
Under the ethene atmosphere of 0.1Mpa, under the room temperature toluene 20ml, MMAO (mol ratio of MMAO and catalyzer is 1000) are added in the polymerization bottle through taking out roasting 100ml successively, vigorous stirring, add catalyzer (C-11) (15 μ mol) reaction again after 3 hours, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polymkeric substance 0.005g in 50 ℃ of vacuum-dryings after precipitation, filtration, washing.
Embodiment 41
In 2 liters autoclave, under the nitrogen atmosphere, add the MAO of 400ml toluene, 6ml 15% successively, stirred 15 minutes under the room temperature, 10ml contains the toluene solution of 29 μ mol catalyst A-18, under vigorous stirring, propylene is added, and pressure remains on 18 * 10 5MPa reacted after 0.5 hour, the emptying propylene gas, and polymkeric substance to constant weight, gets polyethylene 5.3g in 50 ℃ of vacuum-dryings after precipitation, filtration, washing.
Embodiment 42
Under the ethene atmosphere of 0.1Mpa, successively with 1-hexene 0.5ml, in the polymerization bottle of toluene 5ml, MMAO (mol ratio of MMAO and catalyzer is 500) adding through taking out roasting 100ml, vigorous stirring places 50 ℃ of oil baths, the constant temperature certain hour then, catalyst A-18 (9 μ mol) is added, adding toluene to cumulative volume is 15ml, reacts after 10 minutes, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polymkeric substance 1.49g in 40 ℃ of vacuum-dryings after precipitation, filtration, washing, wherein the content of hexene is 5%.
Embodiment 43
Under the ethene atmosphere of 0.1Mpa, successively with 1-hexene 10ml, in the polymerization bottle of MMAO (mol ratio of MMAO and catalyzer is 500) adding through taking out roasting 100ml, vigorous stirring places 50 ℃ of oil baths, the constant temperature certain hour then, catalyst A-18 (9 μ mol) is added, adding toluene to cumulative volume is 15ml, reacts after 10 minutes, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polymkeric substance 2.9g in 40 ℃ of vacuum-dryings after precipitation, filtration, washing, wherein the content of hexene is 5%.
Embodiment 44
Under the ethene atmosphere of 0.1Mpa, successively with norbornylene toluene solution 2ml (norbornylene mass content 67%), toluene 15ml, MMAO (mol ratio of MMAO and catalyzer is 500), in the polymerization bottle of adding through taking out roasting 100ml, vigorous stirring places 50 ℃ of oil baths then, the constant temperature certain hour, catalyst A-18 (9 μ mol) is added, react after 20 minutes, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polymkeric substance 0.89g in 40 ℃ of vacuum-dryings after precipitation, filtration, washing, wherein the content of norbornylene is 15%.
Embodiment 45
Under the ethene atmosphere of 0.1Mpa, successively with norbornylene toluene solution 25ml (norbornylene mass content 67%), toluene 15ml, MMAO (mol ratio of MMAO and catalyzer is 500), in the polymerization bottle of adding through taking out roasting 100ml, vigorous stirring places 50 ℃ of oil baths then, the constant temperature certain hour, catalyst A-18 (9 μ mol) is added, react after 20 minutes, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polymkeric substance 0.42g in 40 ℃ of vacuum-dryings after precipitation, filtration, washing, wherein the content of norbornylene is 40%.
Embodiment 46
Under the nitrogen atmosphere of 0.1Mpa, successively with hexene 2ml, a certain amount of toluene, MMAO (mol ratio of MMAO and catalyzer is 200) adds in the reaction flask through taking out roasting 25ml, vigorous stirring, place 50 ℃ of oil baths then, the constant temperature certain hour adds catalyst A-18 (18 μ mol), react after 1 hour termination reaction.Handle from now on polymkeric substance 0.32g.
Embodiment 47
Under the nitrogen atmosphere of 0.1Mpa, successively with norbornylene toluene solution 2ml (norbornylene mass content 67%), a certain amount of toluene, MMAO (mol ratio of MMAO and catalyzer is 500) adds in the reaction flask through taking out roasting 25ml, vigorous stirring, place 50 ℃ of oil baths then, the constant temperature certain hour adds catalyst A-18 (15 μ mol), react after 1 hour termination reaction.Get polymkeric substance 0.052g through aftertreatment.
Embodiment 48
Under the nitrogen atmosphere of 0.1Mpa, successively with methyl methacrylate 1ml, a certain amount of toluene, in the reaction flask of MMAO (mol ratio of MMAO and catalyzer is 20) adding through taking out roasting 20ml, vigorous stirring places 50 ℃ of oil baths then, the constant temperature certain hour, catalyst A-18 (18 μ mol) is added, react after 12 hours termination reaction.Get polymkeric substance 0.18g through aftertreatment.
Embodiment 49
Under the ethene atmosphere of 0.1Mpa, successively with norbornylene toluene solution 2ml (norbornylene mass content 67%), in the polymerization bottle of toluene 5ml, mMAO (Al/Ti=500 mol ratio) adding through taking out roasting 100ml, vigorous stirring, place 50 ℃ of oil baths then, the constant temperature certain hour adds catalyzer (A-9) (12 μ mol), react after 10 minutes, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polymkeric substance 0.72g in 40 ℃ of vacuum-dryings after precipitation, filtration, washing, wherein the content of norbornylene is 21%.
Embodiment 50
Under the ethene atmosphere of 0.1Mpa, successively with 1-hexene 2ml, in the polymerization bottle of toluene 5ml, MMAO (mol ratio of MMAO and catalyzer is 500) adding through taking out roasting 100ml, vigorous stirring, place 50 ℃ of oil baths then, the constant temperature certain hour adds catalyst A-9 (9 μ mol), react after 20 minutes, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polymkeric substance 1.51g in 40 ℃ of vacuum-dryings after precipitation, filtration, washing, wherein the content of hexene is 22%.
Embodiment 51
Under the ethene atmosphere of 0.1Mpa, successively with 1-hexene 1ml, in the polymerization bottle of toluene 15ml, MMAO (mol ratio of MMAO and catalyzer is 500) adding through taking out roasting 100ml, vigorous stirring, place 50 ℃ of oil baths then, the constant temperature certain hour adds catalyzer D-9 (4.5 μ mol), react after 15 minutes, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polymkeric substance 0.85g in 40 ℃ of vacuum-dryings after precipitation, filtration, washing, wherein the content of hexene is 4.5%.
Embodiment 52
Under the ethene atmosphere of 0.1Mpa, successively with norbornylene toluene solution 1.5ml (norbornylene mass content 67%), in the polymerization bottle of toluene 5ml, MMAO (mol ratio of MMAO and catalyzer is 500) adding through taking out roasting 100ml, vigorous stirring, place 50 ℃ of oil baths then, the constant temperature certain hour adds catalyzer D-9 (4.5 μ mol), react after 10 minutes, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polymkeric substance 0.47g in 40 ℃ of vacuum-dryings after precipitation, filtration, washing.
Embodiment 53
Under the ethene atmosphere of 0.1Mpa, successively toluene 15ml, MMAO (mol ratio of MMAO and catalyzer is 500) are added, in the polymerization bottle through taking out roasting 100ml, vigorous stirring, place 50 ℃ of oil baths then, the constant temperature certain hour adds catalyzer toluene solution (A-3) (10.5 μ mol), react after 73 minutes, with the ethanol termination reaction that contains 5% hydrochloric acid.Polymkeric substance to constant weight, gets polyethylene 1.37g in 40 ℃ of vacuum-dryings after precipitation, filtration, washing, wherein hexene content is 11%.

Claims (9)

1, the catalyzer of a kind of olefinic polymerization and copolymerization or catalyst system is characterized in that the structural formula of described catalyzer 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:1,2,3 or 4;
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 group, 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 positively charged absolute value identical, all parts comprise X and polydentate ligand;
A: Sauerstoffatom, sulphur atom, selenium atom, R 23N-or R 24P-,-P (O) R 24R 25,-P (O) R 24(OR 25), sulfuryl, sulfoxide group ,-N (O) R 23R 24
B: refer to nitrogen-containing group, phosphorus-containing groups or C 1-C 30Alkyl;
D: refer to Sauerstoffatom, sulphur atom, selenium atom, C 1-C 30The nitrogen-containing group of alkyl, C 1-C 30The phosphorus-containing groups of alkyl, sulfuryl, sulfoxide group ,-P (O) R 24R 25,-P (O) R 24(OR 25) ,-N (O) R 23R 24, 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;
G: be inertia group, comprise C 1-C 30Alkyl, C 1-C 30Substituted hydrocarbon radical or safing function group;
→: refer to singly-bound or two key;
: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage;
Described 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, C 8-C 30Condensed ring alkyl or C 4-C 30Heterogeneous ring compound;
The alkyl of described replacement refers to contain on the alkyl one or more substituted radical, contain in the process of compound of substituted hydrocarbon radical in use, these substituting groups are inert, be that these substituting groups do not have substantial interference to related process, 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 30Heterogeneous ring compound;
The safing function group refers to be different from other carbon containing functional groups of alkyl and substituted hydrocarbon radical, and this functional group is not to all there being substantive the interference in the reaction that may participate at the compound that contains this functional groups, and the indication functional groups comprises halogen here, ether (as-OR 31Or-TOR 31), C 1-C 10Ester group, C 1-C 10Amido, C 1-C 10Alkoxyl group, the oxy radical of 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, D, E, F, Y, the Z group that contains ligating atom, and promptly these functional groups should not replace desirable coordinating group;
Described halogen refers to fluorine, chlorine, bromine, iodine;
Ether is meant-OR 31Or-TOR 31
Oxy radical refers to hydroxyl, alkoxyl group-OR 31, have an alkyl of ehter bond;
Sulfur-containing group refers to-SR 30,-T-SR 26,-S (O) R 30Or-T-S (O) 2R 26
Boron-containing group refers to BF 1 -, (C 6F 5) 1B -Or (R 27BAr 3) -
Contain aluminium base group and refer to alkylaluminium cpd, AlPh 4 -, AlF 4 -, AlCl 4 -, AlBr 4 -, AlI 4 -Or R 32AlAr 3 -
Phosphorus-containing groups refers to PR 24R 25,-P (O) R 24R 25Or-P (O) R 24(OR 25);
Nitrogen-containing group refers to-NR 23R 24And-T-NR 23R 24Or-N (O) R 23R 24
Silicon-containing group refers to-T-SiR 28
Germanic group refers to-T-GeR 28
Contain tin group and refer to-T-SnR 2
Containing seleno group refers to-T-SeR 2
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; Nail base aikyiaiurnirsoxan beta (MAO) particularly, AlEt 3, AlMe 3Or Al (i-Bu) 3
R 1, R 2, R 3, R 23, R 24, R 25, R 27, R 28, R 29, R 30, R 31Or R 32Be meant hydrogen, C 1-C 30Alkyl, halogen atom, C 1-C 30Substituted hydrocarbon radical or safing function group, above-mentioned group can be the same or different to each other, wherein adjacent group can be each other in key Cheng Huan;
T: be C 1-C 30Alkyl or C 1-C 30Substituted hydrocarbon radical or safing function group;
Described catalytic body mean above-mentioned catalyzer or above-mentioned catalyst cupport on carrier or catalyzer and cocatalyst W or above-mentioned catalyzer and promotor W be carried on the formed system of carrier:
Carrier is silicon oxide, aluminum oxide, magnesium chloride, titanium oxide or their mixture;
Promotor W is meant a kind of neutral Lewis acid, and the neutral Lewis acid is to take out X from metal M -Form (WX) -, and as (WX) -When being weak coordinate negatively charged ion, W can with alkyl or hydrogen transference on the metal M alkylaluminium cpd or the alkylaluminoxane of modification; Perhaps be used in combination following two kinds of compounds, a kind of can be with alkyl or the hydrogen transference AlMe on the metal M 3, Al (i-Bu) 3Alkylaluminium cpd, and another kind can take out X from metal M -Na or Ag[B (3,5-(CF 3) 2C 6H 3) 4], Na or Ag OSO 2CF 3, alkylaluminium cpd or borine B (C 6F 5) 3The weakly coordinating anion that forms;
Weak coordinate negatively charged ion is to be selected from (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 -Or ((3,5-(CF 3) 2) C 6H 3) 4B -Coordinate negatively charged ion not relatively.
2, a kind of olefinic polymerization as claimed in claim 1 and copolymerization catalyst or catalyst system, the catalyst characteristics structural formula is as follows:
Figure C021108440004C1
Wherein:
: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage;
A, B, E, G, q, m, M, n, X, 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, phosphorus-containing groups, wherein N, O, S, Se, P are ligating atom;
Catalyst system, nitrogen-containing group, oxy radical, sulfur-containing group, contain the definition of seleno group, phosphorus-containing groups with identical described in the claim 1.
3, a kind of olefinic polymerization as claimed in claim 2 and copolymerization catalyst or catalyst system, the catalyst characteristics structural formula is as follows:
Wherein:
: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage;
R 4, R 10, R 11, R 12: hydrogen, C 1-C 30Alkyl, halogen atom, C 1-C 30Substituted hydrocarbon radical or safing function group, above-mentioned group can be the same or different to each other, wherein adjacent group can be each other in key Cheng Huan;
A, E, F, G, q, m, M, n, X, R 1, R 2, R 3With identical described in the aforementioned claim 2;
Catalyst system, substituted hydrocarbon radical, safing function group, nitrogen-containing group, oxy radical, sulfur-containing group, contain the definition of seleno group, phosphorus-containing groups with identical described in the claim 1.
4, a kind of olefinic polymerization as claimed in claim 3 and copolymerization catalyst or catalyst system, the catalyst characteristics structural formula is as follows:
Figure C021108440006C1
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;
A, E, F, G, q, m, M, n, X, R 3, R 4, R 10, R 11, R 12With identical described in the aforementioned claim 3;
R 3, R 4, R 6, R 7, R 8, R 9, R 10, R 11, R 12Can be the same or different, adjacent group can be each other in key Cheng Huan;
Catalyst system, substituted hydrocarbon radical and safing function group its definition with claim 1 in identical.
5, a kind of olefinic polymerization as claimed in claim 4 and copolymerization catalyst or catalyst system, the catalyst characteristics structural formula is as follows:
Figure C021108440007C1
Wherein:
: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage;
R 10, R 11, R 13, R 14, R 15, R 16, R 17, R 18, R 19, R 20, R 21: hydrogen, C 1-C 30Alkyl, halogen atom, C 1-C 30Substituted hydrocarbon radical or safing function group, above-mentioned group can be the same or different to each other, wherein adjacent group can be each other in key Cheng Huan;
R 26Refer to lone-pair electron, hydrogen, C on the nitrogen 1-C 30Alkyl, C 1-C 30Alkyl, the oxy radical of replacement comprise hydroxyl, alkoxyl group-OR 31, the alkyl that has ehter bond comprises-T-OR 31, sulfur-containing group comprises-SR 30,-T-SR 30, nitrogen-containing group comprises-NR 23R 24,-T-NR 23R 24, phosphorus-containing groups comprises-PR 24R 25,-T-PR 24R 25,-T-P (O) R 24R 25Work as R 26During for oxy radical, sulfur-containing group, nitrogen-containing group, contain seleno group, phosphorus-containing groups, N, O, S, P can participate in the coordination with metal;
Y, Z: nitrogen-containing group, sulfur-containing group, oxy radical, phosphorus-containing groups, contain seleno group;
T, M, X, n, catalyst system, substituted hydrocarbon radical, safing function group, nitrogen-containing group, sulfur-containing group, oxy radical, phosphorus-containing groups, contain the definition of seleno group with identical described in the aforementioned claim 1.
6, alkene homopolymerization as claimed in claim 1 and copolymerization catalyst synthetic method, it is characterized in that in organic solvent and at-78 ℃, arriving under the temperature that refluxes, reacted 0.5～40 hour with mol ratio 1: 0.1～6 by the part of following structural formula or the negative ion metallizing thing of part
Described ligand structure formula is as follows:
Figure C021108440008C1
Wherein: A, B, D, E, G, → ,-, R 1, R 2, R 3With identical described in the aforementioned claim 1.
7, the purposes of a kind of olefinic polymerization as claimed in claim 1 and copolymerization catalyst or catalyst system, it is characterized in that directly or under the promotor effect as homogeneous phase or nonhomogeneous system catalysis in olefine polymerization, this catalyst system is used for the homopolymerization that comprises oligomerisation and the copolymerization of catalyzed alkene, alkene refers to ethene, alpha-olefin, vinylbenzene, various olefin(e) acids and derivative thereof, enol and derivative thereof, diolefine, cycloolefin or other contain the alkene of functional groups at interior alkene, described alpha-olefin is meant propylene, 1-butylene, the 1-amylene, the 1-hexene, the 1-octene, 4-methyl-1-pentene and its mixture are at interior C 3～C 16Alkene; Cycloolefin finger ring amylene, tetrahydrobenzene, norbornylene and derivative thereof.
8, the purposes of a kind of olefinic polymerization as claimed in claim 7 and copolymerization catalyst, it is characterized in that described copolymerization is copolymerization, the ethene of ethene and alpha-olefin and contains copolymerization, the alpha-olefin of the alkene of functional groups and contain the copolymerization and the alpha-olefin copolymerization to each other of the alkene of functional groups that the definition of described alkene, the alkene that contains functional groups or alpha-olefin is with identical described in the aforementioned claim 7.
9, the purposes of a kind of olefinic polymerization as claimed in claim 7 and copolymerization catalyst is characterized in that described catalyzer is to use separately or use with carrier loadedization back.
CN 02110844 2001-07-23 2002-02-09 New olefine polymerization catalyst Expired - Fee Related CN1218970C (en)

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