CN100523016C - Preparation of metallocene catalyst containing substituting imine for olefin polymerization/copolymerization - Google Patents
Preparation of metallocene catalyst containing substituting imine for olefin polymerization/copolymerization Download PDFInfo
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- CN100523016C CN100523016C CNB2006100310554A CN200610031055A CN100523016C CN 100523016 C CN100523016 C CN 100523016C CN B2006100310554 A CNB2006100310554 A CN B2006100310554A CN 200610031055 A CN200610031055 A CN 200610031055A CN 100523016 C CN100523016 C CN 100523016C
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- imine
- copolymerization
- organic solvent
- olefin polymerization
- metallocene catalyst
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Abstract
The present invention discloses preparation process of metallocene catalyst containing substituting imine for polymerization and copolymerization of olefin. The catalyst is prepared through the first reaction of cyclopentadiene containing substituting imine and NaH or BuLi and the subsequent reaction with metal oxide. The catalyst has adjusted structure of imine substituent on the cyclopentadienyl ring and the central metal for the homopolymerization and copolymerization of different types of olefins. The catalyst has the advantages of both metallocene catalyst and post-transition metal catalyst combined and is one kind of multifunctional polymer.
Description
Technical field
The invention belongs to orgnometallic catalyst preparation and high molecular polymerization field, relate to the metallocene catalyst containing substituting imine that a kind of olefin polymerization/copolymerization is used, provide this Preparation of catalysts method simultaneously and the alkene homopolymerization finished with this class catalyzer or the method for copolyreaction.
Background technology
Since nineteen fifty-three Ziegler-Natta catalyzer comes out, the development of polyolefin industry is advanced by leaps and bounds, and up to the present, the polyolefinic throughput in the whole world has reached 8,000 ten thousand tons every year, principal item is polyethylene and polypropylene, and both output sums account for more than 80%.Poly output accounts for more than 50%, comprises LDPE, LLDPE and HDPE three big kinds, and the production and marketing of LDPE and HDPE occupies first place in the plastics and the 3rd.The development of core technology-olefin polymerization catalysis has wherein obtained huge development.Ziegler-Natta catalyst system (Angew.Chem., 1955,67:541-546 appearred in short 50 years; Angew.Chem., 1956,68:393-396), metallocene catalysis system (Catalysis Today, 2000,62:23-34) and Nonmetallocene catalyst system (Chem.Rev., 2000,100:1169-1203; Chem.Rev., 2003,103 (1): 283-316) three important milestones.Because olefin polymerization catalysis not only can improve polymerizing condition, improve throughput, and the novel material that obtains has the new capability of the excellence that former material did not have, and all demonstrated premium properties as the poly-third type alkene of high density polyethylene(HDPE), isotactic, syndiotactic polystyrene and the hyperbranched polyethylene that obtains with organometallic catalytic.Therefore, develop and develop the olefin polymerization catalysis with specific function is the focus of field of polymer technology research always.
In the evolution of olefin polymerization catalysis, nitrogenous compound occupies very most of in whole olefin polymerization catalysis as the title complex of part.From the CGC structure, the part that contains the secondary amine structure occurs in catalyzer.Along with the catalyst center metal develops to rear transition metal, except the tertiary amine structure, a series of title complexs that contain imine structure have appearred also.In olefin polymerization catalysis, common imine structure has: FI catalyzer (Adv.Synth.Catal.2002,344 (5): 477-493; J.Am.Chem.Soc.2003,125:4293-4305); Brookhart diimine Ni, Pd catalyzer (J.Am.Chem.Soc., 1995,117:6414-6415; Organometallics, 2003,22:250-256); Pyridine diimine Fe, Co catalyzer (J.Am.Chem.Soc.1998,120:4049-4050; Chem.Comm., 1998:849-850); Imines acid amides Ni catalyzer (J.Am.Chem.Soc.2001,123:5352-5353 that Bazen proposes; Organometallics 2002,21:3082-3084); (Organometallics 1998,17:3149-3151 for Grubbs salicylic alidehyde imine Ni catalyzer; Science, 2000,21:460-462); And Jolly Cp quinoline Cr series catalysts (Organometallics 2000,19:388-402).Make a general survey of these catalyzer, we are not difficult to find that in ligand structure, the title complex that contains imine ligand is easier to obtain advantages of high catalytic activity, and central metal mostly is rear transition metal.In containing fragrant phosphine neutral compound, except direct complexible imines N, generally can provide the group of reactive hydrogen in addition, as SH, NH, OH etc. form chelate structure with central metal, to guarantee the stability of title complex.
Yet preparation and this applied research of class catalyzer in alkene homopolymerization or copolymerization of relevant metallocene catalyst containing substituting imine are very few.The contriver to metallocene catalyst and non-metallocene catalyst, especially contains the research of the late transition metal catalyst of imine ligand based on for many years, the synthetic metallocene catalyst that contains the imines replacement of design.In this catalyst structure, central metal and Cp can form η on the one hand
5Coordination; On the other hand, the N of imines and central metal coordination, thus preparation is in conjunction with a metallocene catalyst and late transition metal catalyst class polyfunctional catalyst of advantage separately, to satisfy the further demand of polyolefin industry development.
Summary of the invention
The invention provides a kind of olefin polymerization/copolymerization preparation method with metallocene catalyst containing substituting imine, promptly contain imines substituted-cyclopentadienyl and NaH or BuLi reaction after, metallizing thing reaction generation metallocene catalyst containing substituting imine again.By regulating the substituent structure of imines on the luxuriant ring, reach homopolymerization or the copolymerization of central metal realization to dissimilar alkene, this class catalyzer is the multi-functional catalyzer of a class in conjunction with metallocene catalyst and late transition metal catalyst advantage separately.
This olefin polymerization/copolymerization metallocene catalyst containing substituting imine provided by the invention, its structure has following general formula
Among formula (I), (II), R1 is aryl, the C1～C12 haloalkyl of C1～C12 alkyl, C6～C12, the fluoro-alkyl of the alkyl of preferred C1～C4, phenyl, C1～C4; R2, R3 can be identical or different, is respectively hydrogen, C1～C12 alkyl, C1～C12 alkoxyl group, nitro, the alkyl of preferred hydrogen, C1～C4, C1～C4 alkoxyl group, nitro etc.; X is halogen, aryl, is preferably chlorine, phenyl; Y is halogen, triaryl phosphine, trialkyl phosphine, is preferably chlorine, triphenylphosphine; Central metal M is the transition metal in the periodic table of elements, preferred chromium (Cr), titanium (Ti), iron (Fe), nickel (Ni).
The olefin polymerization/copolymerization preparation of metallocene catalyst containing substituting imine comprises that step is as follows:
Under protection of inert gas; the cyclopentadiene that will contain the imines replacement is dissolved in aromatic hydrocarbons or the ether organic solvent; add NaH or BuLi; containing the cyclopentadiene of imines replacement and the mol ratio of NaH or BuLi is 1:1-6; preferably containing the cyclopentadiene of imines replacement and the mol ratio of NaH is 1:2-4; or contain cyclopentadiene that imines replaces and the mol ratio of BuLi is 1:1-1.2; reacted 0.5-6 hour down at low temperature-78-5 ℃; preferably-78 ℃, shift clear liquid to metallic compound MX to-40 ℃ of reactions 3-4 hour down
3Or trans-Ni (PPh
3)
2(Ph) in the aromatic hydrocarbons of Cl or the ether organic solvent solution, the cyclopentadiene metallizing thing mol ratio that contains the imines replacement is 1～3:1, preferred 1～2:1, in temperature-20 ℃-5 ℃ of following reactions 10-48 hour, preferably-20 ℃ to-10 ℃ of reactions 20-30 hour down, drain aromatic hydrocarbons or ether organic solvent after the reaction, residuum organic solvent recrystallization obtains the lenticular catalyzer.Described recrystallization is formed by two class organic solvent compatibilities with organic solvent, one class is one of toluene, benzene, tetrahydrofuran (THF) (THF), trichloromethane, methylene dichloride, another kind of is a kind of of normal hexane, sherwood oil, two class organic solvent volume ratios of compatibility are controlled to be 1-9:1, preferred 4-6:1, the combination of preferred toluene of the used organic solvent of recrystallization and sherwood oil.
Used aromatic hydrocarbons or the ether organic solvent of reaction can be toluene, benzene, tetrahydrofuran (THF) etc. among the present invention, wherein is best with the tetrahydrofuran (THF).
With the metallocene catalyst containing substituting imine is Primary Catalysts, can realize the polymerization or the copolymerization of alkene, it is to implement like this: olefinic polymerization or copolymerization, it is characterized in that with the metallocene catalyst containing substituting imine being Primary Catalysts, with the alkylaluminoxane is promotor, and the preferable methyl aikyiaiurnirsoxan beta makes alkene 30～80 ℃ of following polymerizations, wherein the aluminium in the promotor is 100～4000:1 with metal molar ratio in the Primary Catalysts, preferred 200～1500:1.
Olefine polymerizing process of the present invention, alkene are selected from ethene, propylene, vinylbenzene, methyl methacrylate etc., can be homopolymerization, also can be copolymerization.Polymerization methods can adopt mass polymerization, slurry polymerization, or vapour phase polymerization.
The present invention compared with prior art has following obvious advantage:
Olefin polymerization/copolymerization provided by the invention combines metallocene catalyst and late transition metal catalyst advantage separately with metallocene catalyst containing substituting imine, is the multi-functional catalyzer of a class.By regulating the substituent structure of imines on the luxuriant ring, and central metal can realize the homopolymerization to dissimilar alkene, and their copolymerization.This class catalyst activity height, purposes is wide, and is synthetic flexible.Further specify the present invention below by embodiment, but the invention is not restricted to this.
Embodiment 1 [η
5-C
5H
4C (CF
3)=N (2,6-
iPr
2C
6H
3)] TiCl
2Synthetic
Under protection of inert gas, in the Schlenk of 100mL bottle, add C
5H
5C (CF
3)=N-(2,6-
iPr
2C
6H
3) (0.14g 4.66mmol), adds THF 30mL down at-78 ℃, and temperature is gone up naturally, behind the stirring reaction 4h, leaves standstill 0.5h for 0.75g (2.33mmol) and NaH.Under-20 ℃, supernatant liquid is filtered to TiCl
33THF (0.72g, in THF 2.00mmol) (30mL) solution, go up naturally, reacted 10 hours by temperature.Drain solvent, excess is the organic solvent recrystallization of 1:1 assembly with the volume ratio with toluene and normal hexane, obtains solid 0.45g, productive rate 51.25%.
Embodiment 2 [η
5-C
5H
4C (Me)=N (2,6-Et
2C
6H
3)] CrCl
2Synthetic
Under protection of inert gas, in the Schlenk of 100mL bottle with C
5H
5C (Me)=N-(2,6-Et
2C
6H
3) 0.83g (3.48mmol) is dissolved among the 30mL THF ,-60 ℃ slowly drip down BuLi (2.2mL, 3.52mmol), stirring reaction 0.5h.Then, under-10 ℃, reaction solution is slowly dropped to CrCl33THF, and (0.725g is in 30mL THF solution 2.00mmol).Temperature is gone up naturally to room temperature, stirs 20h, drains solvent, and excess is the organic solvent recrystallization of 9:1 assembly with the volume ratio with toluene and sherwood oil, obtains solid 0.43g, productive rate 59.56%.
Embodiment 3 [η
5-C
5H
4C (Ph)=N (4-NO
2C
6H
4)] FeCl
2Synthetic
Under protection of inert gas, in the Schlenk of 100mL bottle with C
5H
5C (Ph)=N-(4-NO
2C
6H
4) 0.96g (3.3mmol) is dissolved among the 30mL THF ,-40 ℃ slowly drip down BuLi (2.5mL, 3.96mmol), stirring reaction 2h.Then, under 0 ℃, reaction solution is slowly dripped FeCl3, and (0.536g is in 30mL THF solution 3.30mmol).Temperature is gone up naturally to room temperature, stirs 24h, drains solvent, and the organic solvent recrystallization of excess THF, sherwood oil assembly, the wherein volume of THF: the volume of sherwood oil is 4:1, obtains solid 0.42g, productive rate 50.48%.
Embodiment 4 [η
5-C
5H
4C (Ph)=N (4-MeOC
6H
4)] TiCl
2Synthetic
Under protection of inert gas, in the Schlenk of 100mL bottle with C
5H
5C (Ph)=N-(4-MeOC
6H
4) 0.94g (3.4mmol) is dissolved among the 30mL THF, 5 ℃ slowly drip down NaH (0.49g, 20.4mmol), stirring reaction 3h.Then, under 5 ℃, reaction solution is slowly dripped TiCl
3(0.41g is in 30mL THF solution 1.14mmol) for 3THF.Temperature is gone up naturally to room temperature, stirs 30h, drains solvent, and excess is the organic solvent recrystallization of 6:1 assembly with the volume ratio with methylene dichloride and sherwood oil, obtains solid 0.37g, productive rate 47.7%.
Embodiment 5 η
5-C
5H
3[C (CF
3)=N (C
6H
5)]
2Ni (Ph) (PPh
3) synthetic
Under protection of inert gas, in the Schlenk of 100mL bottle with C
5H
4[C (CF
3)=N-C
6H
5)]
21.31g (3.21mmol) be dissolved among the 30mL THF, (0.39g, 12.84mmol), stirring reaction 6h leaves standstill 0.5h to-20 ℃ of adding NaH (80%).Under-10 ℃, supernatant liquid is filtered to trans-Ni (PPh
3)
2(Ph) Cl (1.80g, in THF 2.59mmol) (30mL) solution, go up naturally, reacted 48 hours by temperature.Drain solvent, excess obtains red crystals 1.06g, productive rate 50.73% with toluene/normal hexane recrystallization.
MS，m/e(％)(EI)：542(M
+—PPh
3，10.73％)，465(M
+—PPh
3-Ph，1.58％)，407(Ligand，1.63％)，292([Ni+Cp(CF
3)C＝NPh]
+，1.10％)，262(PPh
3，100.00％)，216([Ni+Cp(CF
3)C＝N]
+，1.54％)，183
MS，m/e(％)(ESI)：827.1([M
++Na]
+，76.44％)，805.1(M
+，13.79％)。
EA：Anal.Calcd.For?C
45H
33F
6N
2NiP：C，67.11；H，4.13，N，3.48；Found：C，66.83；H，4.12；N，3.36。
IR(KBr，cm
-1)：3350m，3021m，1645s，1623s，1584s，1573m，1467m，1435m，1222s，1188s，1136s，1097m，1018m，986m，918s，778m，759m，734m，694s，535s，509m。
Embodiment 6
The ethylene catalyst polymerization, the metallocene catalyst containing substituting imine that obtains with embodiment 1 is a Primary Catalysts, with the methylaluminoxane is promotor, wherein aluminium in the promotor and the central metal mol ratio in the Primary Catalysts are 4000:1, the condition of polyreaction is 30 ℃, 0.1Mpa the catalytic activity of reaction is 3.8 * 10
5GPE/molCat.h.
Embodiment 7
The propylene catalyzed polymerization, the metallocene catalyst containing substituting imine that obtains with embodiment 2 is a Primary Catalysts, with modified methylaluminoxane (MMAO) is promotor, wherein aluminium in the promotor and the central metal mol ratio in the Primary Catalysts are 2000:1, the condition of polyreaction is 50 ℃, 0.1Mpa the catalytic activity of reaction is 2.0 * 10
5GPE/molCat.h.
Embodiment 8
The vinylbenzene catalyzed polymerization, the metallocene catalyst containing substituting imine that obtains with embodiment 3 is a Primary Catalysts, with the methylaluminoxane is promotor, wherein aluminium in the promotor and the central metal mol ratio in the Primary Catalysts are 500:1, the condition of polyreaction is 80 ℃, and the catalytic activity of reaction is 5.9 * 10
6GPS/molCat.h.
Embodiment 9
The methyl methacrylate catalyzed polymerization, the metallocene catalyst containing substituting imine that obtains with embodiment 4 is a Primary Catalysts, with modified methylaluminoxane (MMAO) is promotor, wherein aluminium in the promotor and the central metal mol ratio in the Primary Catalysts are 500:1, the condition of polyreaction is 60 ℃, and the catalytic activity of reaction is 6.8 * 10
6GPMMA/molCat.h.
Embodiment 10
Ethene and methyl methacrylate catalyzed copolymerization are closed, the metallocene catalyst containing substituting imine that obtains with embodiment 5 is a Primary Catalysts, with the methylaluminoxane is promotor, wherein aluminium in the promotor and the central metal mol ratio in the Primary Catalysts are 100:1, the condition of polyreaction is 40 ℃, ethene 0.1Mpa, the catalytic activity of reaction is 2.1 * 10
6GPolymer/molCat.h.
Claims (11)
1. olefin polymerization/copolymerization metallocene catalyst containing substituting imine is characterized in that structure has following general formula:
Among formula (I), (II), R1 is aryl, the C1～C12 haloalkyl of C1～C12 alkyl, C6～C12; R2, R3 can be identical or different, is respectively hydrogen, C1～C12 alkyl, C1～C12 alkoxyl group, nitro; X is halogen, aryl; Y is halogen, triaryl phosphine, trialkyl phosphine; Central metal M is the transition metal in the periodic table of elements.
2. olefin polymerization/copolymerization metallocene catalyst containing substituting imine according to claim 1 is characterized in that among formula (I), (II), and R1 is alkyl, the phenyl of C1～C4, the fluoro-alkyl of C1～C4; R2, R3 are alkyl, C1～C4 alkoxyl group, the nitro of hydrogen, C1～C4; X is chlorine, phenyl; Y is chlorine, triphenylphosphine; Central metal M is chromium, titanium, iron, nickel.
3. olefin polymerization/copolymerization is characterized in that comprising that step is as follows with the preparation method of metallocene catalyst containing substituting imine:
Under protection of inert gas; the cyclopentadiene that will contain the imines replacement is dissolved in aromatic hydrocarbons or the ether organic solvent; add NaH or BuLi; containing the cyclopentadiene of imines replacement and the mol ratio of NaH or BuLi is 1:1-6; low temperature-78～5 ℃ following reaction 0.5～6 hour, shift clear liquid to metallic compound MX
3Or trans-Ni (PPh
3)
2(Ph) in the aromatic hydrocarbons of Cl or the ether organic solvent solution, the cyclopentadiene metallizing thing mol ratio that contains the imines replacement is 1～3:1, in temperature-20 ℃～5 ℃ reaction 10～48 hours down, drain aromatic hydrocarbons or ether organic solvent after the reaction, residuum organic solvent recrystallization, obtain the lenticular catalyzer, described recrystallization is formed by two class organic solvent compatibilities with organic solvent, one class is a toluene, benzene, tetrahydrofuran (THF), trichloromethane, one of methylene dichloride, another kind of is normal hexane, sherwood oil a kind of, two class organic solvent volume ratios of compatibility are controlled to be 1-9:1; MX
3Middle X is halogen, aryl, and M is the transition metal in the periodic table of elements; Trans-Ni (PPh
3)
2(Ph) Ph among the Cl is a phenyl; The structural formula that contains the cyclopentadiene of imines replacement is:
Among formula (III), (IV), R1 is aryl, the C1～C12 haloalkyl of C1～C12 alkyl, C6～C12; R2, R3 can be identical or different, is respectively hydrogen, C1～C12 alkyl, C1～C12 alkoxyl group, nitro.
4. the olefin polymerization/copolymerization according to claim 3 preparation method of metallocene catalyst containing substituting imine, it is characterized in that containing cyclopentadiene that imines replaces and the mol ratio of NaH is 1:2-4, or to contain the cyclopentadiene that imines replaces be 1:1-1.2 with the mol ratio of BuLi, reacted 3-4 hour at-78 ℃ to-40 ℃ times.
5. olefin polymerization/copolymerization according to claim 3 is characterized in that with the preparation method of metallocene catalyst containing substituting imine clear liquid is transferred to metallic compound MX
3Or trans-Ni (PPh
3)
2(Ph) in the organic solvent solution of Cl, reacted 20-30 hour down in-20 ℃ to-10 ℃, the cyclopentadiene metallizing thing mol ratio that contains the imines replacement is 1-2:1.
6. olefin polymerization/copolymerization according to claim 3 is with the preparation method of metallocene catalyst containing substituting imine, and it is characterized in that reacting with aromatic hydrocarbons or ether organic solvent is a kind of of toluene, benzene, tetrahydrofuran (THF).
7. olefin polymerization/copolymerization according to claim 3 is characterized in that with the preparation method of metallocene catalyst containing substituting imine recrystallization is controlled to be 4-6:1 with two class organic solvent volume ratios of organic solvent compatibility.
8. olefin polymerization/copolymerization according to claim 3 is characterized in that with the preparation method of metallocene catalyst containing substituting imine recrystallization is formed by toluene and sherwood oil compatibility with organic solvent.
9. replace the olefin polymerization/copolymerization reaction that metallocene is a catalyzer to contain imines, it is characterized in that with the described metallocene catalyst containing substituting imine of claim 1 be Primary Catalysts, with the alkylaluminoxane is promotor, make alkene 30～80 ℃ of following polymerization/copolymerizations, wherein aluminium in the promotor and the central metal mol ratio in the Primary Catalysts are 100～4000:1.
10. olefin polymerization/copolymerization reaction according to claim 9 is characterized in that promotor is a methylaluminoxane.
11. olefin polymerization/copolymerization reaction according to claim 9 is characterized in that aluminium and the central metal mol ratio in the Primary Catalysts in the promotor is 200～1500:1.
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| WO2014169017A1 (en) * | 2013-04-11 | 2014-10-16 | Exxonmobil Chemical Patents Inc. | Process of producing polyolefins using metallocene polymerization catalysts and copolymers therefrom |
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Assignee: Jiangsu Tian-zhu Chemical Technology Co., Ltd. Assignor: East China University of Science and Technology Contract record no.: 2010320000756 Denomination of invention: Prepn of metallocene catalyst containing substituting imine for olefin polymerization/copolymerization Granted publication date: 20090805 License type: Exclusive License Open date: 20070321 Record date: 20100621 |
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