CN101062960A - Transition metal polymerization catalyst containing CO bidentate ligand - Google Patents
Transition metal polymerization catalyst containing CO bidentate ligand Download PDFInfo
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Abstract
The invention discloses a transient metal polymerization catalyst with [CO] double teeth ligand and synthesis and appliance, which is characterized by the following: including polyolefin polymerization of N-heterocyclic carbene ligand with ortho-hydroxyl group aryl replacement, method for synthesizing and application research. This activator relates to the third tufts to the eleven tufts transient metal complex with a new type double teeth ligand.
Description
Technical field
The present invention relates to N-heterocycle carbine metallic compound that a kind of neighbour-hydroxyaryl replaces, synthetic method and as the applied research of homogeneous phase (not load is directly used) or heterogeneous (using) catalysis cyclic olefin polymerization with carrier loaded back such as silicon oxide, aluminum oxide, magnesium chloride.This compounds relates to three races's to the 11 group transition metal compounds of the novel bitooth ligand of a class.
Background technology
The N-heterocycle carbine is a kind of bielectron donor, has the ability that π-electronics is fed back in very strong σ-electron donation and weak acceptance.These characteristics provide the character that is different from other traditional neutral parts for its metallic compound.There has been the N-heterocycle carbine title complex of report display part metal to have higher reaction and catalytic activity (Scholl, M. than its traditional title complex; Ding, S.; Lee, C.W.; Grubbs, R.H.Org.Lett.1999,1,953; Morgan, J.P.; Grubbs, R.H.Org.Lett.2000,2,3153; Viciu, M.H.; Kissling, R.M.; Stevens, E.D.; Nolan, S.P.Org.Lett.2002,4,2229; Viciu, M.S.; Germaneau, R.F.; Nolan, S.P.Org.Lett.2002,4,4053; Herrmann, W.A.Angew.Chem., Int.Ed.2002,41,1290; McGuinness, D.S.; Cavell, K.J.Organometallics 1999,18, and 1596; McGuinness, D.S.; Cavell, K.J.Organometallics 2000,19, and 741 etc.).Because its structural characteristic, the substituting group on the change N atom can change the steric effect and the electronic effect of N-heterocycle carbine easily, and this also provides convenience for reaction and the catalytic performance of controlling its metallic compound.Therefore, study various different replace, the N-heterocyclic carbene ligand of chelating just becomes the popular domain in the current chemical research.
In recent years, salicylic alidehyde imine class part is in organic synthesis and catalysis, and particularly the application of catalysis in olefine polymerization aspect has obtained research (Matsui, S. in depth; Mitani, M.; Saito, J.; Tohi, Y.; Makio, H.; Matsukawa, N.; Takagi, Y.; Kazutaka, T.; Nitabaru, M.; Nakano, T.; Tankaka, H.; Kashiwa, N.; Fujita, T.J.Am.Chem.Soc.2001,123,6847; Wang, C.; Friedrich, A.; Younkin, T.R.; Li, R.T.; Grubbs, R.H.; Bansleben, A.; Day, M.W.Organometallics 1998,17, and 3149; Younkin, T.R.; Connor, E.F.; Henderson, J.I.; Friedrich, S.K.; Grubbs, R.H.; Bansleben, D.A.Science 2000,287, and 460; Tian, J.; Hustad, P.D.; Coates, G.W.J.Am.Chem.Soc.2001,123,5134; Connor, E.F.; Younkin, T.R.; Henderson, J.I.; Waltman, A.W.; Grubbs, R.H.Chem.Commun.2003,2272 etc.).What be different from the N-heterocycle carbine is that imine ligand is that σ well-to body, the while also is good π-acceptor.The difference of this character may be brought beyond thought reactivity with the similar N-heterocyclic carbene ligand of salicylic alidehyde imine class part.The metallic compound of the N-heterocyclic carbene ligand that this neighbour-hydroxyaryl that contains similar schiff base of salicylaldehyde replaces may show excellent reaction and catalytic performance.
King one hundred congruent people has reported synthetic (Ren, the H. of a kind of neighbour-hydroxyaryl N-heterocycle carbine precursor and palladium allylic cpd thereof; Yao, P.; Xu, S.; Song, H.; Wang, B.J.Organomet.Chem.2007,692,2092.), but their results aspect catalysis in olefine polymerization do not reported.Therefore, we disclose a kind of prepare a series of neighbours-N-heterocycle carbine metallic compound of hydroxyaryl replacement and the application on catalysis in olefine polymerization thereof here.
Summary of the invention
The object of the present invention is to provide a class to contain the transition metal cyclic olefin polymerization and the copolymerization catalyst (catalyst system) of the N-heterocyclic carbene ligand of neighbour-hydroxyaryl replacement, 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 bitooth ligand of cyclic olefin polymerization, and the synthetic method of above-mentioned catalyzer.
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, is used for the homopolymerization that comprises oligomerisation and the copolymerization of catalysis cycloolefin.
Cyclic olefin polymerization provided by the invention and copolymerization catalyst are the described title complex of following structural formula (I):
In said structure:
tBu: the tertiary butyl;
M:1,2 or 3;
M: transition metal atoms, the especially titanium of ten gangs of three races to the, zirconium, hafnium, vanadium, chromium, iron, ruthenium, cobalt, nickel, palladium or copper;
N:0,1,2,3 or 4;
X: be halogen atom, hydrogen atom, C
1-C
20Alkyl, substituted hydrocarbon radical, 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;
The halogen atom here is meant fluorine, chlorine, bromine or iodine;
R
1: be meant C
1-C
20The aliphatics substituting group or aromatic substituents in a kind of, these substituting groups comprise the group that contains and do not contain aerobic, nitrogen heteroatom;
R
2, R
3Be meant hydrogen, halogen atom, C
1-C
20Aliphatics substituting group, aromatic substituents in a kind of, these substituting groups comprise the group that contains and do not contain aerobic, nitrogen heteroatom;
In the structural formula absolute value of all part negative charge sums should with metal M in the structural formula positively charged absolute value identical;
Alkyl refers to contain C
1-C
20Alkyl, C
1-C
20Cyclic hydrocarbon group, C
2-C
20Group, the C of carbon-carbon double bonds
2-C
20Carbon containing carbon triple-linked group, C
6-C
20Aryl radical, C
8-C
20Condensed ring alkyl or C
4-C
20Heterogeneous ring compound;
The alkyl that replaces refers to contain on the above-mentioned alkyl substituted radical of one or more safing function group, promptly contain in the process of compound of substituted hydrocarbon radical in use, these substituting groups are inert, related process are not had substantial interference, be these substituting groups generally not with metal-complexing, these substituting groups refer generally to contain the group of 1～20 carbon atom, and substituting group also comprises C
6-C
20Aryl radical, C
8-C
20Condensed ring alkyl or C
4-C
20Heterogeneous ring compound.
Safing function type group is meant other carbon containing functional groups that are different from 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 group, and the indication functional groups comprises halogen (fluorine here, chlorine, bromine, iodine), ether, 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 or contain tin group, when functional groups when the atoms metal, the coordination ability of itself and metal is not better than Cabbeen and phenol oxygen base, promptly these functional groups should not replace desirable coordinating 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 catalyst system 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, a kind of neutral Lewis acid (Lewis acid), this 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 of alkoxy aluminum compound especially methylaluminoxane 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 alkoxy aluminum compound 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, alkoxy aluminum compound or borine B (C
6F
5)
3Form weakly coordinating anion;
Weakly coordinating anion is to be selected from R
3AlX
-, R
2AlX
2 -, RAlX
3 -, SbF
5 -, PF
6 -, BF
4 -, (C
6F
5)
4B
-, CF
3SO
3 -Deng coordinate negatively charged ion not relatively.
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 precursor of following structural formula or this precursor 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, tetracol phenixin, ether, 2,4-dioxane or 1,2-ethylene dichloride etc.Described front body structure formula is as follows:
Wherein:
tBu: the tertiary butyl;
R
1: be meant C
1-C
20The aliphatics substituting group or aromatic substituents in a kind of, these substituting groups comprise the group that contains and do not contain aerobic, nitrogen heteroatom;
R
2, R
3Be meant hydrogen, halogen atom, C
1-C
20Aliphatics substituting group, aromatic substituents in a kind of, these substituting groups comprise the group that contains and do not contain aerobic, nitrogen heteroatom;
Y: various weak coordinate negatively charged ion such as halogen atom or various organic and inorganic acid ions.
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 cyclic olefin polymerization, described cyclic olefin polymerization is equal polymerization or the copolymerization that comprises oligomerisation, can use or use separately with promotor usually.
The present invention relates to following cyclic 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. cycloolefin.
Above-mentioned catalyst system of the present invention can be used for the catalysis cyclic olefin polymerization, and cycloolefin is meant cyclopentenes, tetrahydrobenzene, norbornylene etc. and derivative thereof; Polymerization comprises the above-mentioned monomeric equal polymerization polymerization together that comprises oligomerisation.
The polymerization technique of slurry polymerization, endless tube polymerization, vapour phase polymerization or other form is 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 separation of polymeric product, inert solvent can use the hydro carbons less than 12 carbon, is exemplified below but not only for therewith 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), borine such as B (C
6F
5)
3Deng.
Catalyzer and promotor W can carry out polymerization by any addition sequence.The variable-scale of employed catalyzer of polymerization and promotor W.Usually the mol ratio of catalyzer and promotor is 1: 1～5000, generally can be 1: 10～3000 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 to more clearly understand 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 four kinds of catalyst system 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.
Promotor W is meant that a kind of neutral can take out X from metal M
-Form (WX)
-Lewis acid (Lewis acid); 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 alkoxy aluminum compound 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 alkoxy aluminum compound 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, alkoxy aluminum compound or borine B (C
6F
5)
3Form weakly coordinating anion;
Weakly coordinating anion is meant relatively not coordinate negatively charged ion, its coordination situation can referring to document (Beck, W.et al.Chem.Rev.1988,88,1405-1421, and Stares, S.H.Chem.Rev.1993,93,927-942.), R for example
3AlX
-, R
2AlX
2 -, RAlX
3 -, SbF
5 -, PF
6 -, BF
4 -, (C
6F
5)
4B
-, CF
3SO
3 -
Alkyl refers to contain C
1-C
20Alkyl, C
1-C
20Cyclic hydrocarbon group, C
2-C
20Group, the C of carbon-carbon double bonds
2-C
20Carbon containing carbon triple-linked group, C
6-C
20Aryl radical, C
8-C
20Condensed ring alkyl or C
4-C
20Heterogeneous ring compound;
The alkyl that replaces refers to contain on the above-mentioned alkyl substituted radical of one or more safing function group, promptly contain in the process of compound of substituted hydrocarbon radical in use, these substituting groups are inert, related process are not had substantial interference, be these substituting groups generally not with metal-complexing, these substituting groups refer generally to contain the group of 1～20 carbon atom, and substituting group also comprises C
6-C
20Aryl radical, C
8-C
20Condensed ring alkyl or C
4-C
20Heterogeneous ring compound.
Safing function type group is meant other carbon containing functional groups that are different from 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 group, and the indication functional groups comprises halogen (fluorine here, chlorine, bromine, iodine), ether, 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 or contain tin group, when functional groups when the atoms metal, the coordination ability of itself and metal is not better than Cabbeen and phenol oxygen base, promptly these functional groups should not replace desirable coordinating group
In sum, the invention provides a kind of cyclic olefin 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 precursor metallizing thing to obtain.This catalyzer provided by the invention can be separately or is being used for the catalysis cycloolefin, is containing the equal polymerization polymerization together that comprises oligomerisation of the cycloolefin etc. of functionalization group as homogeneous phase (not load is directly used) or heterogeneous (publish the body load with silicon oxide, aluminum oxide, magnesium chloride then use) system under the effect of promotor.
Embodiment
Following examples have shown not ipsilateral of the present invention.Given embodiment comprises the synthetic of metal complexes, 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.
Embodiment 1～embodiment 10 declaratives transition metal carbene complexes synthetic, embodiment 11～embodiment 20 declaratives catalyst system catalysis norbornene polymerization results.
Ligand precursor L1-L3 and Compound C 7-C9 reference (Ren, H.; Yao, P.; Xu, S.; Song, H.; Wang, B..J.Organomet.Chem.2007,692,2092.) reported method is synthetic.
Embodiment 1 title complex C1's is synthetic
In the reaction flask of 100mL, in the THF (30mL) of 0.41g (1.0mmol) ligand L 1 suspension liquid, dropwise dripping 1.2mL (1.7N under 0 ℃, 2.0mmol) hexane solution of n-BuLi, stirred 0.5 hour down at 0 ℃, slowly rise to room temperature, then to the NiCl that wherein adds 0.33g (0.5mmol)
2(PPh
3)
2, stirred overnight at room temperature.Drain solvent, separate with alumina column chromatography, with 1: 1 CH
2Cl
2The drip washing of/sherwood oil, the component that obtains are drained solvent and are obtained 0.33g title complex C1, productive rate 92%.
Ultimate analysis: actual measurement (calculating) 70.35 (70.68); H, 8.57 (8.76); N, 7.46 (7.85);
1H?NMR(400MHz，CDCl
3)：δ7.19(d，1H，im-H，J＝1.69Hz)，7.12(s，1H，Ar-H)，7.05(s，1H，Ar-H)，7.02(d，im-CH，J＝2.04Hz)，1.66(s，9H，C(CH)
3)，1.54(s，9H，C(CH)
3)，1.37(s，9H，C(CH)
3)；
Embodiment 2 title complex C2's is synthetic
In the reaction flask of 100mL, in the THF (30mL) of 0.44g (1.0mmol) ligand L 2 suspension liquid, dropwise dripping 1.2mL (1.7N under 0 ℃, 2.0mmol) hexane solution of n-BuLi, stirred 0.5 hour down at 0 ℃, slowly rise to room temperature, then to the NiCl that wherein adds 0.33g (0.5mmol)
2(PPh
3)
2, stirred overnight at room temperature.Drain solvent, separate with alumina column chromatography, with 1: 1 CH
2Cl
2The drip washing of/sherwood oil, the component that obtains are drained solvent and are obtained 0.37g title complex C2, productive rate 95%.
Ultimate analysis: actual measurement (calculating) 72.07 (72.15); H, 8.95 (8.69); N, 7.52 (7.32);
1H?NMR(300MHz，CDCl
3)：δ7.22(d，1H，im-CH，J＝1.94Hz)，7.19(d，1H，Ar-H，J＝2.40Hz)，7.04(d，1H，Ar-H，J＝2.40Hz)，6.93(d，1H，im-CH，J＝1.96Hz)，3.52(m，1H，N(CH)(CH2)5)，1.55(s，9H，C(CH)
3)，1.34(s，9H，C(CH)
3)，1.75~1.26(m，10H，(CH
2)
5)；
Embodiment 3 title complex C3's is synthetic
In the reaction flask of 100mL, in the THF (30mL) of 0.47g (1.0mmol) ligand L 3 suspension liquid, dropwise dripping 1.2mL (1.7N under 0 ℃, 2.0mmol) hexane solution of n-BuLi, stirred 0.5 hour down at 0 ℃, slowly rise to room temperature, then to the NiCl that wherein adds 0.33g (0.5mmol)
2(PPh
3)
2, stirred overnight at room temperature.Drain solvent, separate with alumina column chromatography, with 1: 1 CH
2Cl
2The drip washing of/sherwood oil, the component that obtains are drained solvent and are obtained 0.41g title complex C3, productive rate 97%.
Ultimate analysis: actual measurement (calculating) 74.08 (74.55); H, 8.21 (7.94); N, 6.53 (6.69);
1H?NMR(300MHz，CDCl
3)：δ?7.26(s，1H，Ar-H)，6.91(s，1H，im-CH)，6.90(s，1H，im-CH)，6.72(s，1H，Ar-H)，6.64(s，2H，Ar-H)，3.53(s，3H，Ar-CH
3)，2.26(s，3H，Ar-CH
3)，1.80(s，3H，Ar-CH
3)，1.56(s，9H，C(CH)
3)，1.45(s，9H，C(CH)
3)；
Embodiment 4 title complex C4's is synthetic
In the 100mL two-mouth bottle that reflux condensing tube is housed, add 0.41g (1.0mmol) ligand L 1,0.12g (0.5mmol) Pd (OAc)
2With 0.45g K
2CO
3(excessive) adds the dioxane of 20mL then, and reflux is spent the night.Solvent removed in vacuo, remaining solid Al
2O
3Column chromatography chromatogram separates, and uses CH
2Cl
2The drip washing of/sherwood oil obtains 0.35g yellow solid C4, productive rate 92%.
Ultimate analysis: actual measurement (calculating) 66.84 (66.25); H, 8.95 (8.21); N, 7.52 (7.36);
1H?NMR(300MHz，CDCl
3)：δ7.47(s，1H，Ar-H)，7.40(s，1H，Ar-H)，7.09(s，1H，im-CH)，6.88(s，1H，im-CH)，1.50(s，9H，C(CH)
3)，1.46(s，9H，C(CH)
3)，1.34(s，9H，C(CH)
3)；
Embodiment 5 title complex C5's is synthetic
In the 100mL two-mouth bottle that reflux condensing tube is housed, add 0.44g (1.0mmol) ligand L 2,0.12g (0.5mmol) Pd (OAc)
2With 0.45g K
2CO
3(excessive) adds the dioxane of 20mL then, and reflux is spent the night.Solvent removed in vacuo, remaining solid Al
2O
3Column chromatography chromatogram separates, and uses CH
2Cl
2The drip washing of/sherwood oil obtains 0.37g yellow solid C5, productive rate 92%.
Ultimate analysis: actual measurement (calculating) 67.54 (67.92); H, 8.67 (8.18); N, 6.73 (6.89);
1H?NMR(300MHz，CDCl
3)：δ7.23(s，2H，Ar-H)，7.14(s，2H，Ar-H)，7.04(d，2H，im-CH，J＝1.81Hz)，6.98(d，2H，im-CH，J＝1.68Hz)，5.20(m，2H，N(CH)(CH
2)
5)，1.27(s，18H，C(CH)
3)，1.26(s，18H，C(CH)
3)，1.06~2.26(m，20H，(CH
2)
5)；
Embodiment 6 title complex C6's is synthetic
In the 100mL two-mouth bottle that reflux condensing tube is housed, add 0.47g (1.0mmol) ligand L 3,0.12g (0.5mmol) Pd (OAc)
2With 0.45g K
2CO
3(excessive) adds the dioxane of 20mL then, and reflux is spent the night.Solvent removed in vacuo, remaining solid Al
2O
3Column chromatography chromatogram separates, and uses CH
2Cl
2The drip washing of/sherwood oil obtains 0.39g yellow solid C6, productive rate 92%.
Ultimate analysis: actual measurement (calculating) 70.01 (70.53); H, 7.68 (7.51); N, 6.43 (6.33);
1H?NMR(300MHz，CDCl
3)：δ7.25(s，2H，Ar-H)，7.02(s，2H，Ar-H)，6.79(s，4H，Ar-H)，6.67(s，1H，im-CH)，6.58(s，2H，im-CH)，2.56(s，6H，Ar-CH
3)，2.24(s，6H，Ar-CH
3)，1.79(s，6H，Ar-CH
3)，1.61(s，18H，C(CH)
3)，1.42(s，18H，C(CH)
3)；
Embodiment 7 title complex C10's is synthetic
CH to 0.47g (1.0mmol) title complex C7
2Cl
2The dioxane solution that adds the HCl of 0.5mL 2N in the solution stirs behind the 20min to wherein adding 0.26g (1.0mmol) PPh
3Stirred overnight at room temperature.Use Al after being spin-dried for solvent
2O
3Column chromatography chromatogram separates, and uses CH
2Cl
2The drip washing of/sherwood oil obtains 0.27g light yellow solid C10, productive rate 35%.
Ultimate analysis: actual measurement (calculating) 60.85 (60.98); H, 6.44 (6.17); N, 3.42 (3.65);
1H?NMR(400?MHz，CDCl
3)：δ8.16(s，1H，Ar-OH)，7.55(s，1H，Ar-H)，7.32(s，1H，Ar-H)，7.08~7.87(m，15H，PPh
3-H)，6.93(s，1H，im-CH)，6.40(s，1H，im-CH)，2.00(s，9H，C(CH)
3)，1.53(s，9H，C(CH)
3)，1.02(s，9H，C(CH)
3)。
31P?NMR(CDCl
3)：26.8；
Embodiment 8 title complex C11's is synthetic
CH to 0.50g (1.0mmol) title complex C8
2Cl
2The dioxane solution that adds the HCl of 0.5mL 2N in the solution stirs behind the 20min to wherein adding 0.26g (1.0mmol) PPh
3Stirred overnight at room temperature.Use Al after being spin-dried for solvent
2O
3Column chromatography chromatogram separates, and uses CH
2Cl
2The drip washing of/sherwood oil obtains 0.41g light yellow solid C11, productive rate 47%.
Ultimate analysis: actual measurement (calculating) 64.57 (64.99); H, 6.44 (6.39); N, 3.70 (3.38);
1H?NMR(400MHz，CDCl
3)：δ7.62(m，6H，Ar-H)，7.42(m，3H，Ar-H)，7.32(m，6H，Ar-H)，7.25(s，2H，im-CH)，7.15(s，1H，Ar-H)，6.78(s，1H，Ar-H)，3.77(m，1H，N(CH)(CH2)5)，1.56(s，9H，C(CH)
3)，1.36(s，9H，)，0.95~2.66(m，10H，(CH2)5)。
31P?NMR(CDCl
3)：30.2；
Single crystal structure:
Embodiment 9 title complex C12's is synthetic
CH to 0.53g (1.0mmol) title complex C9
2Cl
2The dioxane solution that adds the HCl of 0.5mL 2N in the solution stirs behind the 20min to wherein adding 0.26g (1.0mmol) PPh
3Stirred overnight at room temperature.Use Al after being spin-dried for solvent
2O
3Column chromatography chromatogram separates, and uses CH
2Cl
2The drip washing of/sherwood oil obtains 0.42g light yellow solid C12, productive rate 47%.
Ultimate analysis: actual measurement (calculating) 66.07 (66.58); H, 6.49 (6.10); N, 3.17 (3.53);
1H?NMR(400MHz，CDCl
3)：δ7.43(d，1H，im-CH，J＝1.96Hz)，7.15～7.36(m，17H，Ar-H)，6.88(s，1H，Ar-H)，6.81(d，1H，im-CH，J＝1.96Hz)，6.56(s，1H，Ar-H)，2.66(s，3H，Ar-CH
3)，2.28(s，3H，Ar-CH
3)，1.60(s，9H，C(CH)
3)，1.42(s，9H，C(CH)
3)，0.98(s，3H，Ar-CH
3)。
31P?NMR(CDCl
3)：28.3；
Embodiment 10 title complex C13's is synthetic
In the 100mL two-mouth bottle that reflux condensing tube is housed, add 0.41g (1.0mmol) ligand L 1,0.18g (1.0mmol) Cu (OAc)
2With 0.45g K
2CO
3(excessive) adds the dioxane of 20mL then, and reflux is spent the night.Solvent removed in vacuo, remaining solid Al
2O
3Column chromatography chromatogram separates, and uses CH
2Cl
2The drip washing of/sherwood oil obtains 0.35g yellow solid C13, productive rate 92%.
Ultimate analysis: actual measurement (calculating) 70.07 (70.21); H, 8.84 (8.70); N, 7.65 (7.80);
Mass spectrum: m/z=781;
Single crystal structure:
Embodiment 11
To the 100mL exsiccant toluene solution (containing the 1.0g norbornylene) that adds the 4.5mL norbornylene in the two-mouth bottle of magneton and the toluene solution (1.4N) of 0.38mLMAO are housed, under agitation place 80 ℃ oil bath preheating 2 minutes then, then to wherein injecting the toluene solution (0.2mol/L) that 1.0mL newly prepares C1.Behind the reaction 10min, to wherein adding 50mL acidifying ethanol (ethanol/HCl
Conc=9: 1) solution cancellation reaction.The polymkeric substance that filters gained in 80 ℃ vacuum drying oven, weigh after the dried overnight polynorbornene 0.038g, monomer conversion is 3.8%.
Embodiment 12
To the 100mL exsiccant toluene solution (containing the 1.0g norbornylene) that adds the 4.5mL norbornylene in the two-mouth bottle of magneton and the toluene solution (1.4N) of 0.38mLMAO are housed, under agitation place 80 ℃ oil bath preheating 2 minutes then, then to wherein injecting the toluene solution (0.2mol/L) that 1.0mL newly prepares C3.Behind the reaction 10min, to wherein adding 50mL acidifying ethanol (ethanol/HCl
Conc=9: 1) solution cancellation reaction.The polymkeric substance that filters gained in 80 ℃ vacuum drying oven, weigh after the dried overnight polynorbornene 0.23g, monomer conversion is 23%.
Embodiment 13
To the 100mL exsiccant toluene solution (containing the 1.0g norbornylene) that adds the 4.5mL norbornylene in the two-mouth bottle of magneton and the toluene solution (1.4N) of 0.38mLMAO are housed, under agitation place 80 ℃ oil bath preheating 2 minutes then, then to wherein injecting the toluene solution (0.2mol/L) that 1.0mL newly prepares C5.Behind the reaction 10min, to wherein adding 50mL acidifying ethanol (ethanol/HCl
Conc=9: 1) solution cancellation reaction.The polymkeric substance that filters gained in 80 ℃ vacuum drying oven, weigh after the dried overnight polynorbornene 0.49g, monomer conversion is 49%.
Embodiment 14
To the 100mL exsiccant toluene solution (containing the 1.0g norbornylene) that adds the 4.5mL norbornylene in the two-mouth bottle of magneton and the toluene solution (1.4N) of 0.38mLMAO are housed, under agitation place 80 ℃ oil bath preheating 2 minutes then, then to wherein injecting the toluene solution (0.2mol/L) that 1.0mL newly prepares C6.Behind the reaction 10min, to wherein adding 50mL acidifying ethanol (ethanol/HCl
Conc=9: 1) solution cancellation reaction.The polymkeric substance that filters gained in 80 ℃ vacuum drying oven, weigh after the dried overnight polynorbornene 0.65g, monomer conversion is 65%.
Embodiment 15
To the 100mL exsiccant toluene solution (containing the 1.0g norbornylene) that adds the 4.5mL norbornylene in the two-mouth bottle of magneton and the toluene solution (1.4N) of 0.38mLMAO are housed, under agitation place 80 ℃ oil bath preheating 2 minutes then, then to wherein injecting the toluene solution (0.2mol/L) that 1.0mL newly prepares C7.Behind the reaction 10min, to wherein adding 50mL acidifying ethanol (ethanol/HCl
Conc=9: 1) solution cancellation reaction.The polymkeric substance that filters gained in 80 ℃ vacuum drying oven, weigh after the dried overnight polynorbornene 0.77g, monomer conversion is 77%.
Embodiment 16
To the 100mL exsiccant toluene solution (containing the 1.0g norbornylene) that adds the 4.5mL norbornylene in the two-mouth bottle of magneton and the toluene solution (1.4N) of 0.38mLMAO are housed, under agitation place 80 ℃ oil bath preheating 2 minutes then, then to wherein injecting the toluene solution (0.2mol/L) that 1.0mL newly prepares C8.Behind the reaction 10min, to wherein adding 50mL acidifying ethanol (ethanol/HCl
Conc=9: 1) solution cancellation reaction.The polymkeric substance that filters gained in 80 ℃ vacuum drying oven, weigh after the dried overnight polynorbornene 0.96g, monomer conversion is 96%.
Embodiment 17
To the 100mL exsiccant toluene solution (containing the 1.0g norbornylene) that adds the 4.5mL norbornylene in the two-mouth bottle of magneton and the toluene solution (1.4N) of 0.38mLMAO are housed, under agitation place 80 ℃ oil bath preheating 2 minutes then, then to wherein injecting the toluene solution (0.2mol/L) that 1.0mL newly prepares C9.Behind the reaction 10min, to wherein adding 50mL acidifying ethanol (ethanol/HCl
Conc=9: 1) solution cancellation reaction.The polymkeric substance that filters gained in 80 ℃ vacuum drying oven, weigh after the dried overnight polynorbornene 0.88g, monomer conversion is 88%.
Embodiment 18
To the 100mL exsiccant toluene solution (containing the 1.0g norbornylene) that adds the 4.5mL norbornylene in the two-mouth bottle of magneton and the toluene solution (1.4N) of 0.38mLMAO are housed, under agitation place 80 ℃ oil bath preheating 2 minutes then, then to wherein injecting the toluene solution (0.2mol/L) that 1.0mL newly prepares C10.Behind the reaction 10min, to wherein adding 50mL acidifying ethanol (ethanol/HCl
Conc=9: 1) solution cancellation reaction.The polymkeric substance that filters gained in 80 ℃ vacuum drying oven, weigh after the dried overnight polynorbornene 0.83g, monomer conversion is 83%.
Embodiment 19
To the 100mL exsiccant toluene solution (containing the 1.0g norbornylene) that adds the 4.5mL norbornylene in the two-mouth bottle of magneton and the toluene solution (1.4N) of 0.38mLMAO are housed, under agitation place 80 ℃ oil bath preheating 2 minutes then, then to wherein injecting the toluene solution (0.2mol/L) that 1.0mL newly prepares C11.Behind the reaction 6min, to wherein adding 50mL acidifying ethanol (ethanol/HCl
Conc=9: 1) solution cancellation reaction.The polymkeric substance that filters gained in 80 ℃ vacuum drying oven, weigh after the dried overnight polynorbornene 0.76g, monomer conversion is 76%.
Embodiment 20
To the 100mL exsiccant toluene solution (containing the 1.0g norbornylene) that adds the 4.5mL norbornylene in the two-mouth bottle of magneton and the toluene solution (1.4N) of 0.38mLMAO are housed, under agitation place 80 ℃ oil bath preheating 2 minutes then, then to wherein injecting the toluene solution (0.2mol/L) that 1.0mL newly prepares C12.Behind the reaction 10min, to wherein adding 50mL acidifying ethanol (ethanol/HCl
Conc=9: 1) solution cancellation reaction.The polymkeric substance that filters gained in 80 ℃ vacuum drying oven, weigh after the dried overnight polynorbornene 0.86g, monomer conversion is 86%.
Claims (8)
1, a kind of cyclic olefin polymerization and copolymerization catalyst that contains the transition metal of the N-heterocyclic carbene ligand that neighbour-hydroxyaryl replaces is characterized in that the structural formula of described catalyzer is as follows:
Wherein:
tBu: be the tertiary butyl;
M: be 1,2 or 3;
M: the transition metal atoms that is ten gangs of three races to the;
N: be 0,1,2,3 or 4;
X: be halogen atom, hydrogen atom, C
1-C
20Alkyl, substituted hydrocarbon radical, 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;
R
1: be meant C
1-C
20The aliphatics substituting group or aromatic substituents in a kind of, these substituting groups comprise the group that contains and do not contain aerobic, nitrogen heteroatom;
R
2, R
3Be meant hydrogen, halogen atom, C
1-C
20Aliphatics substituting group, aromatic substituents in a kind of, these substituting groups comprise the group that contains and do not contain aerobic, nitrogen heteroatom;
In the structural formula absolute value of all part negative charge sums should with metal M in the structural formula positively charged absolute value identical.
2, catalyzer according to claim 1 is characterized in that:
Transition metal atoms is meant titanium, zirconium, hafnium, chromium, iron, ruthenium, cobalt, nickel, palladium or copper;
Halogen atom is meant fluorine, chlorine, bromine or iodine;
Alkyl refers to contain C
1-C
20Alkyl, C
1-C
20Cyclic hydrocarbon group, C
2-C
20Group, the C of carbon-carbon double bonds
2-C
20Carbon containing carbon triple-linked group, C
6-C
20Aryl radical, C
8-C
20Condensed ring alkyl or C
4-C
20Heterogeneous ring compound;
The alkyl that replaces refers to contain on the above-mentioned alkyl substituted radical of one or more safing function group, contain in the process of compound of substituted hydrocarbon radical in use, these substituting groups are inert, related process are not had substantial interference, be these substituting groups generally not with metal-complexing, these substituting groups refer generally to contain the group of 1～20 carbon atom, and substituting group also comprises C
6-C
20Aryl radical, C
8-C
20Condensed ring alkyl or C
4-C
20Heterogeneous ring compound;
Safing function type group is meant other carbon containing functional groups that are different from 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 group, and the indication functional groups comprises halogen atom here, ether, 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 or contain tin group, when functional groups when the atoms metal, the coordination ability of itself and metal is not better than Cabbeen and phenol oxygen base, promptly these functional groups should not replace desirable coordinating group.
3, the synthetic method of the described catalyzer of a kind of claim 1, it is characterized in that in organic solvent and at-78 ℃, arriving under the temperature that refluxes, be respectively reaction in 1: 0.1～6 o'clock by the negative ion of the precursor of following structural formula or this precursor and transistion metal compound with mol ratio and obtained in 0.5～40 hour, described front body structure formula is as follows:
Wherein:
tBu, R
1, R
2, R
3With identical described in the claim 1; Y is meant weak coordinate negatively charged ion such as halogen atom, mineral acid or organic acid acid ion; The absolute value of all negative charge sums should be identical with the absolute value of positive charge in the structural formula in the structural formula;
Described organic solvent is tetrahydrofuran (THF), sherwood oil, toluene, methylene dichloride, tetracol phenixin, ether, 2,4-dioxane or 1,2-ethylene dichloride.
4, the described Application of Catalyst of a kind of claim 1, it is characterized in that described catalyzer directly or under promotor W effect as homogeneous phase or nonhomogeneous system catalysis cyclic olefin polymerization, this catalyst system is used for the homopolymerization that comprises oligomerisation and the copolymerization of catalysis cycloolefin; Cycloolefin is meant cyclopentenes, tetrahydrobenzene, norbornylene and derivative thereof;
Be aggregated in the inert solvent and carry out; Polymerization temperature maintains-50～150 ℃; Polymerization pressure changes in 0.1～10Mpa.
5, Application of Catalyst according to claim 4 is characterized in that inert solvent is hydro carbons, cyclic hydrocar-bons or aromatic hydrocarbons; Maintain 0～120 ℃ for reaching good catalytic activity and throughput polymerization temperature; Polymerization pressure is in 0.1～3Mpa.
6, Application of Catalyst according to claim 5 is characterized in that inert solvent uses the hydro carbons less than 12 carbon in order to help reactor operation and separation of polymeric product.
7, Application of Catalyst according to claim 6 is characterized in that inert solvent is propane, Trimethylmethane, Skellysolve A, 2-methylbutane, hexane, toluene, chlorobenzene and composition thereof.
8, according to each described Application of Catalyst in the claim 4 to 7, it is characterized in that described catalyzer or catalyzer and promotor W one reinstate carrier loaded back and use, described carrier is meant silicon oxide, aluminum oxide, magnesium chloride, titanium oxide or their mixture; Promotor W is meant methylaluminoxane MAO, the methylaluminoxane MMAO of modification, ethyl aikyiaiurnirsoxan beta EAO, butyl aikyiaiurnirsoxan beta BAO, LiR (R=C
1-C
10Alkyl), AlR
3(R=C
1-C
10Alkyl), borine such as B (C
6F
5)
3The mol ratio of catalyzer and promotor is 1: 1～5000;
Promotor W is a kind of neutral, can take out X from metal M
-Form (WX)
-Lewis acid (Lewis acid);
As (WX)
-When being weak coordinate negatively charged ion, W can be with alkyl or hydrogen transference on metal M, as the methylaluminoxane of alkoxy aluminum compound especially methylaluminoxane or modification; Two kinds of compounds of use perhaps also capable of being combined, wherein a kind of can be on metal M, as alkoxy aluminum compound especially AlEt with alkyl or hydrogen transference
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, alkoxy aluminum compound or borine B (C
6F
5)
3Form weakly coordinating anion;
Weakly coordinating anion is to be selected from R
3AlX
-, R
2AlX
2 -, RAlX
3 -, SbF
5 -, PF
6 -, BF
4 -, (C
6F
5)
4B
-, CF
3SO
3 -Deng coordinate negatively charged ion not relatively.
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| CN109529936A (en) * | 2018-12-12 | 2019-03-29 | 怀化学院 | MOPs loads application of the bidentate chelating type metallic catalyst in suzuki reaction |
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| CN115819644A (en) * | 2021-09-18 | 2023-03-21 | 中国科学技术大学 | Supported catalyst and preparation method and application thereof |
| CN115819644B (en) * | 2021-09-18 | 2024-01-09 | 中国科学技术大学 | Supported catalyst and preparation method and application thereof |
| CN114057649A (en) * | 2021-11-16 | 2022-02-18 | 大赛璐（中国）投资有限公司 | Polymerizable ligand compound, polymer ligand and metal complex thereof |
| CN114395056A (en) * | 2022-02-16 | 2022-04-26 | 青岛科技大学 | Preparation of NNO-coordinated chromium metal catalyst and application of NNO-coordinated chromium metal catalyst in olefin polymerization |
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