CN108752509B - Metallocene catalyst, preparation method and application - Google Patents

Metallocene catalyst, preparation method and application Download PDF

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CN108752509B
CN108752509B CN201810590083.2A CN201810590083A CN108752509B CN 108752509 B CN108752509 B CN 108752509B CN 201810590083 A CN201810590083 A CN 201810590083A CN 108752509 B CN108752509 B CN 108752509B
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perfluoro
polyfluoro
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metallocene catalyst
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CN108752509A (en
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黄启谷
付瑶
时子海
张少蒙
王秋璨
于洪超
杨万泰
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Zhejiang Chain Science And Technology Co ltd
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Beijing University of Chemical Technology
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    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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Abstract

The invention relates to a metallocene catalyst, a preparation method and application thereof. The metallocene catalyst is a compound corresponding to the following general formula;
Figure DDA0001690431710000011
wherein, R is8Or R9Selected from H, F, C1‑C10And X is halogen, etc.; wherein the content of the first and second substances,
Figure DDA0001690431710000012
is C5‑C30Cyclopentadiene or a derivative thereof, etc.; wherein M is selected from Ti, Zr, etc.; wherein A is selected from C, Si, etc. The invention adds catalyst in the process of olefin homopolymerization and binary or above monomer copolymerization to prepare polyolefin, with simple process and low cost, which is suitable for solution polymerization process, gas phase polymerization process, etc. or combined polymerization process.

Description

Metallocene catalyst, preparation method and application
Technical Field
The invention belongs to the field of olefin coordination polymerization catalysts, and particularly relates to a metallocene catalyst, a preparation method and application of polyolefin.
Background
Metallocene polyethylene (mPE) has been used in various fields since its commercial production in 1991. The mPE is mainly used for producing various films (such as heat shrinkable films, high-quality garbage bags, industrial outer packaging bags, agricultural films, composite packaging films, stretching and winding films and the like). With the progress of catalysts and process technology, the application of metallocene High Density Polyethylene (HDPE) and Medium Density Polyethylene (MDPE) in the fields of hollowing, rotational molding, injection molding and pipelines has gradually increased in recent years; metallocene Linear Low Density Polyethylene (LLDPE) is mainly used for high quality films, moldings, pipes and electric wires and cables; metallocene Very Low Density Polyethylene (VLDPE) is used in very thin films, gloves, blow and injection molded parts, flexible sheets, extruded profiles and tubes, medical and heavy goods packaging bags, household interior films, interior liners, health and hygiene products, and the like; POE is mainly used for modifying and toughening PP, PE and PA to manufacture bumpers, mud guards, steering wheels and base plates in the automobile industry, and insulating layers and sheaths with high requirements on heat resistance and environmental resistance in the wire and cable industry. Researchers in our country have made diligent efforts at the beginning of the advent of metallocene catalysts [ Huang Qin Valley, et al, macromolecular Notification, 2010,6,1-33 ]. Through the development of many years, some achievements are made in the research aspect of the basic theory of the metallocene catalyst, and the application aspect of the metallocene catalyst is also tried. However, because of the low capital investment in China, the metallocene catalyst has a tendency of attenuation in the domestic research enthusiasm, and the more important reason is that the difficulty in the aspect of industrial application of the catalyst is not solved, and the metallocene catalyst with intellectual property rights in China is not applied to industrial production in a large scale at present. The metallocene catalyst technology owned by the Beijing chemical research institute of China petrochemical industry only produces film materials and heat-resistant polyethylene pipe materials (PE-RT) in batches on a gas-phase polyethylene industrial device of the Qilu division company. China still has no POE catalyst technology and no POE industrial production report.
German Bayer company adopts 1- (9-fluorenyl) -1,2,3, 6-tetrahydro-1, 3, 3-trimethylcyclopentadienylenezirconiumdichloride/MAO catalytic system to prepare ethylene/propylene/5-ethylidene-2-norbornene copolymer (EPDM), the polymerization temperature is 20-80 ℃, the polymerization pressure is 0.3-3.0 MPa, the ethylene mass fraction of the copolymer is 0.4-0.9, the propylene mass fraction is 0.095-0.59, and the non-conjugated diene mass fraction is 0.005-0.12. EPDM with high molecular weight, narrow molecular weight distribution and low Tg is synthesized by Unilocene catalyst in Uniloc, the polymerization temperature is 30-80 deg.c, the polymerization pressure is 0.07-21 MPa, the ethylene weight fraction of EPDM is 0.35-0.8, and the propylene weight fraction is 0.15-0.6.
With Me2Si(H4Ind)2ZrCl2MAO the copolymerization of ethylene and propylene was studied at 0.1-150MPa,120-220 ℃ and the molar content of propylene in the copolymer was low and the density of the copolymer was high, 0.940-0.946 g/cm3(ii) a With Me2Si(H4Ind)2ZrCl2MAO comparison of the copolymerization of ethylene with propylene, 1-butene, 1-hexene and 1-decene at 0.1-150MPa at 120 ℃ and 220 ℃ found that the higher the carbon number the more difficult the copolymerization of α -olefin with ethylene and the reactivity ratio r of ethylene to 1-butenee/rbWhen the ratio is 53.45/0.02, the ratio of reactivity ratios of ethylene to 1-hexene in copolymerization is re/rh62.70/0.02, the ratio of the reactivity ratios of ethylene to 1-decene in the copolymerization is re/rd80.02/0.01. Using supported metallocene catalyst Et (Ind)2ZrCl2The ethylene and 1-hexene are copolymerized under the pressure of 10MPa, the catalytic activity is as high as 4341.7kg P/mol Zr.h, and the molar content of 1-hexene in the copolymer is about 3%.
Linshanan et al use titanocene Cp Ti (OR)3Synthesis of high randomness and high molecular weight Poly-1-butene elastomers and ethylene/1-butene copolymer elastomers with a/mMAO catalytic System [ Qigu Huang, Shangan Lin, et al.J. of PolymSci, Part A, Polym Chem,2001,39,4068]The ratio of the reactivity ratios of ethylene to 1-butene in the copolymerization is re/rb1.08/0.29, the molar content of 1-butene in the molecular chain of the copolymer is up to 25.4%. One chlorine in the single metallocene titanium trichloride is substituted by phenoxy and then used for ethylene copolymerization, so that a copolymer with higher comonomer insertion amount can be obtained. The results of these studiesIt is shown that when the auxiliary ligand of the metallocene catalyst is a phenol oxyl with strong electron-withdrawing ability, the metallocene catalyst can effectively catalyze the copolymerization of ethylene and olefin containing larger side groups, and the molar insertion amount of the comonomer is high. Comonomers include 1-hexene, 1-octene [ Yuan Kong, Qigu Huang, et al. Polymer,2010,51,3859]Cycloalkenes, styrenes, non-terminal olefins and diolefins, dodecenes, tetradecenes. In tests, the single titanocene (zirconium), titanocene (zirconium) and a plurality of bridged titanocene (zirconium) compounds are easily decomposed at high temperature (more than 80 ℃) to separate out black solid powdery substances, and the substances have no catalytic activity even if activated by MAO at lower temperature (0-30 ℃). Hafnocene compounds are expensive and we have not done similar experiments. We also studied the alcoholic, phenolic, benzidine radicals [ Huangqi Kegu, et al, CN200710121499.1,2007]Silicon hydroxy [ yellow Kentucky, et al, CN201610342348.8,2016]The synthesis and application of the bimetallic metallocene catalyst as the auxiliary ligand improve the thermal stability of the catalyst and have higher catalytic activity at about 100 ℃. Although a group with higher rigidity and larger steric hindrance is connected between the two metallocene compounds, the thermal stability of the catalyst is improved, but the performance of the obtained polyolefin is poorer than that of POE synthesized by a constrained geometry metallocene catalyst (CGC).
The Japan three well petrochemical industry company adopts ethyl bridged metallocene/MAO catalytic system, takes toluene as solvent under normal pressure to 5.0MPa, catalyzes ethylene and α -olefin to copolymerize, synthesize polyolefin elastomer Tafmer, the mole content of α -olefin in polymer molecular chain is up to 9%, the density of the product is low, 0.85-0.92 g/cm3，
The molecular weight distribution is 1.2-4.0. The patent is characterized in that an organosilicon compound is added to a metallocene compound before polymerization. The comonomer in the Tafmer product contains 1-butene and 1-hexene, the performance is not as good as mPE produced by the metallocene catalyst with limited geometric configuration, and the mPE of Mitsui company has relatively high price, so the comonomer cannot become a mainstream product in the market of China. DuPont-Dow Elastomets company develops polyolefin elastomer Engage by using metallocene catalyst/organic boride catalytic system with limited geometric configuration, which comprises 8 new varieties of blow molding, extrusion molding and the like, and belongs to ethylene/1-hexene, ethylene/1-octene copolymers with high melt strength. Experimental research and industrial production experience prove that the metallocene catalyst with limited geometric configuration is the best catalyst for producing POE, has higher catalytic activity in the range of polymerization temperature of 100 ℃ and 180 ℃, and the obtained polyolefin has high molecular weight.
The main ligand structure has a large influence on the activity and catalytic performance of the catalyst. Catalysts containing different substituents on the cyclopentadienyl group, the catalytic activity being in the order of EtMe4CpTi(OMe)3>Cp*Ti(OMe)3>Me3SiMe4CpTi(OMe)3>Me4CpTi(OMe)3>(Me3Si)2CpTi(OMe)3>CpTi(OMe)3，Cp*Is pentamethylcyclopentadienyl, Cp is cyclopentadienyl, -Et, -Me and Me3Si-is an electron-donating group, and the result shows that the existence of the electron-donating substituent group on the cyclopentadienyl ligand can improve the activity of the catalyst. The higher the number of electron-donating substituent groups, the higher the activity of the catalyst.
When the influence of the structure of the ancillary ligand of the metallocene catalyst on the catalytic performance of the metallocene catalyst is researched, the phenolic oxygen group with stronger electron-withdrawing capability [ yellow open valley, etc., CN201510082857.7,2015], benzidine group [ yellow open valley, etc., CN201610342188.7,2016] is introduced into the structure of the metallocene compound, so that the thermal stability of the metallocene catalyst can be improved. The literature [ JingWang, Qigu Huang, et al. catalyst Letters,2016,146(3),609] discloses the law of the influence of ortho-and para-substituents R of the N atom directly attached to the atom Ti (Zr, etc.) of a transition metal on the catalytic performance of a catalyst. The catalyst has the best catalytic performance when R is F compared with R is H, Me: high catalyst activity, high molecular weight of copolymerized olefin and high insertion amount of comonomer. The above results lead to the conclusion that: compared with the catalyst in which R is Me (electron-withdrawing group), F is a strong electron-withdrawing group, and due to the strong electron-withdrawing capability of F, the electron cloud density around the transition metal atom is weakened, and the catalytic activity of the catalyst is increased. The introduction of strong electron-withdrawing groups into the catalyst ligand structure can make the active center of the catalyst more stable and the catalytic activity higher. This result is contrary to the regularity reported in the literature. When R is F, F belongs to Lewis base, and the transition metal atom belongs to Lewis acid, so that F can weaken the Lewis acidity of the transition metal atom, so that the active center of the catalyst is more stable, the beta-H elimination reaction is difficult to occur during the catalytic olefin polymerization, and the polyolefin with high molecular weight can be obtained even at higher polymerization temperature.
The invention discovers that the bridging group of the constrained geometry metallocene catalyst or the introduction of the strong electron-withdrawing group into the cyclopentadiene ring or the non-cyclopentadiene ring has stronger Lewis alkalinity, reduces the Lewis acidity of the transition metal, weakens the beta-H elimination reaction during the olefin polymerization and can obtain the polyolefin with higher molecular weight; as the Lewis acidity of Ti (Zr, Hf, etc.) is weakened, the thermal stability of the catalyst is improved, and the catalyst has high activity in catalyzing olefin polymerization at a high temperature of 80-200 ℃. The preparation method of the polyolefin has the advantages of simple process, low cost, low requirement on equipment, low energy consumption and small environmental pollution.
Disclosure of Invention
The invention aims to provide an olefin coordination polymerization catalyst, a preparation method and application of polyolefin. The catalyst is added in the process of olefin homopolymerization and copolymerization of binary or above monomers to prepare the polyolefin, the process is simple, the cost is low, and the method is suitable for a solution polymerization process, a gas phase polymerization process, a liquid phase bulk polymerization process, a slurry polymerization process, a ring pipe polymerization process or a combined polymerization process.
The metallocene catalyst and the preparation method are characterized in that: the metallocene catalyst corresponds to a compound of a general formula 1;
Figure GDA0002481222680000061
wherein, R is8Or R9Selected from H, F, C1-C10Fatty radical of (C)6-C20Aryl of (C)3-C10Cycloalkyl of, C1-C10Of perfluoro or polyfluoro aliphatic radical, C6-C20Perfluoro or polyfluoro aryl of (C)3-C10Perfluoro or polyfluoro cycloalkyl of (A), C1-C10Alkoxy of C6-C20Aryloxy group of or C3-C10Cycloalkoxy of (a), wherein R8Or R9Attached to the same carbon atom or to different carbon atoms; wherein X is halogen, C1-C10Fatty radical of (C)6-C20Aryl of (C)3-C10Cycloalkyl of, C1-C10Of perfluoro or polyfluoro aliphatic radical, C6-C20Perfluoro or polyfluoro aryl of (C)3-C10Perfluoro or polyfluoro cycloalkyl of (a); wherein the content of the first and second substances,
Figure GDA0002481222680000062
is C5-C30A cyclopentadiene or a derivative group thereof, C9-C30Indene or derivative group thereof or C13-C30A fluorene or its derivative group of (a); wherein M is selected from Ti, Zr, Hf, Y, Sc, V, Fe, Co, Ni, Nd, Sm, Rh, Pd, Ru, Ce, Al, Zn or Mg, etc.; wherein A is selected from C, Si, CH-CH, CF-CF, Se or Sn, etc.; wherein R is10An F-containing aryl group selected from the structures:
Figure GDA0002481222680000063
Figure GDA0002481222680000071
Figure GDA0002481222680000072
etc. of
The metallocene catalyst and the preparation method are characterized in that: wherein the content of the first and second substances,
Figure GDA0002481222680000073
is selected from C9-C30The indene or the derivative thereof of (1), wherein the metallocene catalyst corresponds to a compound of a general formula 2;
Figure GDA0002481222680000074
wherein R is1Selected from H, F, C1-C10Fatty radical of (C)6-C20Aryl of (C)3-C10Cycloalkyl of, C1-C10Of perfluoro or polyfluoro aliphatic radical, C6-C20Perfluoro or polyfluoro aryl of (C)3-C10Perfluoro or polyfluoro cycloalkyl of (a); x is halogen, C1-C10Fatty radical of (C)6-C20Aryl or C of3-C10Cycloalkyl groups of (a); a is selected from C, Si, CH-CH, CF-CF, Se or Sn, etc.; r8Or R9Selected from H, F, C1-C10Fatty radical of (C)6-C20Aryl of (C)3-C10Cycloalkyl of, C1-C10Of perfluoro or polyfluoro aliphatic radical, C6-C20Perfluoro or polyfluoro aryl of (C)3-C10Perfluoro or polyfluoro cycloalkyl of (A), C1-C10Alkoxy of C6-C20Aryloxy group of or C3-C10Cycloalkoxy of (a), wherein R8Or R9Attached to the same carbon atom or to different carbon atoms; m is selected from Ti, Zr, Hf, Y, Sc, V, Fe, Co, Ni, Nd, Sm, Rh, Pd, Ru, Ce, Al, Zn or Mg; wherein R is10An F-containing aryl group selected from the structures:
Figure GDA0002481222680000081
Figure GDA0002481222680000082
etc. of
The metallocene catalyst and the preparation method are characterized in that: wherein the content of the first and second substances,
Figure GDA0002481222680000083
is selected from C5-C30The group of cyclopentadiene or a derivative thereof, said metallocene catalyst corresponding to the compound of formula 3;
Figure GDA0002481222680000084
wherein R is selected from H, F, C1-C10Fatty radical of (C)6-C20Aryl of (C)3-C10Cycloalkyl of, C1-C10Of perfluoro or polyfluoro aliphatic radical, C6-C20Perfluoro or polyfluoro aryl of (C)3-C10Perfluoro or polyfluoro cycloalkyl of (a); x is halogen, C1-C10Fatty radical of (C)6-C20Aryl or C of3-C10Cycloalkyl groups of (a); a is selected from C, Si, CH-CH, CF-CF, Se or Sn, etc.; r8Or R9Selected from H, F, C1-C10Fatty radical of (C)6-C20Aryl of (C)3-C10Cycloalkyl of, C1-C10Of perfluoro or polyfluoro aliphatic radical, C6-C20Perfluoro or polyfluoro aryl of (C)3-C10Perfluoro or polyfluoro cycloalkyl of (A), C1-C10Alkoxy of C6-C20Aryloxy group of or C3-C10Cycloalkoxy of (a), wherein R8Or R9Attached to the same carbon atom or to different carbon atoms; m is selected from Ti, Zr, Hf, Y, Sc, V, Fe, Co, Ni, Nd, Sm, Rh, Pd, Ru, Ce, Al, Zn or Mg; wherein R is10Selected from F-containing aryl groups, preferably F-containing aryl groups of the structure:
Figure GDA0002481222680000091
Figure GDA0002481222680000092
etc. of
The metallocene catalyst and the preparation method are characterized in that: wherein the content of the first and second substances,
Figure GDA0002481222680000093
is selected from C13-C30The tetrahydroindene derivative of (a), the metallocene catalyst corresponding to the compound of formula 4;
Figure GDA0002481222680000101
wherein R is3Selected from H, F, C1-C10Fatty radical of (C)6-C20Aryl of (C)3-C10Cycloalkyl of, C1-C10Of perfluoro or polyfluoro aliphatic radical, C6-C20Perfluoro or polyfluoro aryl of (C)3-C10Perfluoro or polyfluoro cycloalkyl of (a); x is halogen, C1-C10Fatty radical of (C)6-C20Aryl or C of3-C10Cycloalkyl groups of (a); a is selected from C, Si, CH-CH, CF-CF, Se or Sn, etc.; r8Or R9Selected from H, F, C1-C10Fatty radical of (C)6-C20Aryl of (C)3-C10Cycloalkyl of, C1-C10Of perfluoro or polyfluoro aliphatic radical, C6-C20Perfluoro or polyfluoro aryl of (C)3-C10Perfluoro or polyfluoro cycloalkyl of (A), C1-C10Alkoxy of C6-C20Aryloxy group of or C3-C10Cycloalkoxy of (a), wherein R8Or R9Attached to the same carbon atom or to different carbon atoms; m is selected from Ti, Zr, Hf, Y, Sc, V, Fe, Co, Ni, Nd, Sm, Rh, Pd, Ru, Ce, Al, Zn or Mg; wherein R is10Selected from F-containing aryl groups, preferably F-containing aryl groups of the structure:
Figure GDA0002481222680000102
Figure GDA0002481222680000111
etc. of
The metallocene catalyst and the preparation method are characterized in that: wherein the content of the first and second substances,
Figure GDA0002481222680000112
is selected from C13-C30Fluorene or its derivativeSaid metallocene catalyst corresponding to the compound of formula 5;
Figure GDA0002481222680000113
wherein R is4Or R5Selected from H, F, C1-C10Fatty radical of (C)6-C20Aryl or C of3-C10Cycloalkyl groups of (a); x is halogen, C1-C10Fatty radical of (C)6-C20Aryl of (C)3-C10Cycloalkyl of, C1-C10Of perfluoro or polyfluoro aliphatic radical, C6-C20Perfluoro or polyfluoro aryl of (C)3-C10Perfluoro or polyfluoro cycloalkyl of (a); a is selected from C, Si, CH-CH, CF-CF, Se or Sn, etc.; r8Or R9Selected from H, F, C1-C10Fatty radical of (C)6-C20Aryl of (C)3-C10Cycloalkyl of, C1-C10Of perfluoro or polyfluoro aliphatic radical, C6-C20Perfluoro or polyfluoro aryl of (C)3-C10Perfluoro or polyfluoro cycloalkyl of (A), C1-C10Alkoxy of C6-C20Aryloxy group of or C3-C10Cycloalkoxy of (a), wherein R8Or R9Attached to the same carbon atom or to different carbon atoms; m is selected from Ti, Zr, Hf, Y, Sc, V, Fe, Co, Ni, Nd, Sm, Rh, Pd, Ru, Ce, Al, Zn or Mg; wherein R is10Selected from F-containing aryl groups, preferably F-containing aryl groups of the structure:
Figure GDA0002481222680000121
Figure GDA0002481222680000122
etc. of
The metallocene catalyst and the preparation method are characterized in that: the preparation method of the metallocene catalyst comprises the following steps:
(1) in organic solventsAdding C5-C30Cyclopentadiene or a derivative thereof, C9-C30Indene or derivatives thereof, or C13-C30The addition amount of the fluorene or the derivative thereof is calculated by 1 mol of cyclopentadiene or the derivative thereof, indene or the derivative thereof, or the fluorene or the derivative thereof, 1.0 to 1.2 mol of hydrogen-withdrawing compound is added at-60 to 20 ℃, and the reaction is carried out for 3 to 10 hours; adding 0.5 to 1.0 mol of a dihalogen compound or an alkyl compound of the bridging group A, and reacting at-30 to 60 ℃ for 3 to 8 hours to obtain an intermediate which accords with a general formula 6, wherein the yield is higher than 83%; wherein R is8Or R9Selected from H, F, C1-C10Fatty radical of (C)6-C20Aryl of (C)3-C10Cycloalkyl of, C1-C10Of perfluoro or polyfluoro aliphatic radical, C6-C20Perfluoro or polyfluoro aryl of (C)3-C10Perfluoro or polyfluoro cycloalkyl of (A), C1-C10Alkoxy of C6-C20Aryloxy group of or C3-C10Cycloalkoxy of (a), wherein R8Or R9Attached to the same carbon atom or to different carbon atoms; wherein X is Cl, Br or I; wherein the content of the first and second substances,
Figure GDA0002481222680000123
is C5-C30A cyclopentadiene or a derivative group thereof, C9-C30Indene or derivative group thereof, or C13-C30A fluorene or its derivative group of (a); wherein A is selected from C, Si, CH-CH, CF-CF, Se or Sn, etc.;
Figure GDA0002481222680000131
(2) adding 0.5 to 1.0 mol of aryl amine containing F, and reacting at-30 to 60 ℃ for 5 to 12 hours to obtain an intermediate corresponding to the general formula 7;
Figure GDA0002481222680000132
wherein R is8Or R9Selected from H, F, C1-C10Fatty radical of (C)6-C20Aryl of (C)3-C10Cycloalkyl of, C1-C10Of perfluoro or polyfluoro aliphatic radical, C6-C20Perfluoro or polyfluoro aryl of (C)3-C10Perfluoro or polyfluoro cycloalkyl of (A), C1-C10Alkoxy of C6-C20Aryloxy group of or C3-C10Cycloalkoxy of (a), wherein R8Or R9Attached to the same carbon atom or to different carbon atoms; wherein the content of the first and second substances,
Figure GDA0002481222680000133
is C5-C30A cyclopentadiene or a derivative group thereof, C9-C30Indene or derivative group thereof, or C13-C30A fluorene or its derivative group of (a); wherein A is selected from C, Si, CH-CH, CF-CF, Se or Sn, etc.; wherein R is10Selected from F-containing aryl groups, preferably F-containing aryl groups of the structure:
Figure GDA0002481222680000141
Figure GDA0002481222680000142
etc. of
(3) Adding 1.0-1.2 of hydrogen-removing compound at-60-10 ℃ for reaction for 4-10 hours; adding 0.6 to 2.0 mol of transition metal salt at the temperature of between 30 ℃ below zero and 60 ℃ for reaction for 5 to 12 hours; filtering, extracting with organic solvent, concentrating, crystallizing at-30 to 10 deg.C, filtering, and drying to obtain metallocene catalyst corresponding to formula 1;
wherein the organic solvent is selected from benzene, toluene, hexane, heptane or THF, etc.; wherein the hydrogen abstraction compound is selected from NaH, Na, K, n-butyl lithium or Grignard reagent or the mixture thereof and the like.
According to formula 1, it is specifically selected from the following metallocene catalysts (1) to (20), but not limited thereto:
Figure GDA0002481222680000151
Figure GDA0002481222680000161
Figure GDA0002481222680000171
the metallocene catalyst, the preparation method and the application are characterized in that: the metallocene catalyst and the cocatalyst form a catalyst system, and the molar ratio of the metallocene catalyst to the cocatalyst is 1: (0.5-300), wherein the cocatalyst is an aluminum alkyl, an aluminum alkoxide or a blend thereof; typical cocatalysts are as follows: trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-t-butylaluminum, trioctylaluminum, diethylaluminum monochloride, ethylaluminum dichloride, ethylaluminum sesquichloride, MAO or modified MAO, etc., and may be used alone or in combination with several cocatalysts.
The metallocene catalyst is characterized in that the catalyst provided by the invention is used as a catalyst for ethylene polymerization, propylene polymerization or copolymerization of ethylene or propylene and α -olefin, wherein the α -olefin is selected from C3～C20The olefin of (a) is preferably propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 3-methyl-1-butene, cyclopentene, 4-methyl-1-pentene, 1, 3-butadiene, isoprene, styrene, methylstyrene, norbornene and its derivatives, halogenated olefins, hydroxyolefins, carboxyolefins or their blends, etc. The olefin polymerization conditions were: the polymerization temperature is 80-200 ℃, the hydrogen partial pressure is 0.001-0.2 MPa, the ethylene partial pressure is 0.1-50MPa, the propylene partial pressure is 0.5-5MPa, the reaction time is 0.5-4 h, and the molar ratio of the metallocene catalyst to the cocatalyst is 1: (0.1-200); adding an organic solvent when carrying out the olefin polymerization, wherein the organic solvent is selected from C5～C30Saturated hydrocarbon of (C)5～C30Alicyclic hydrocarbon of (2), C6～C30Of aromatic hydrocarbons or C3～C20The saturated heterocyclic hydrocarbon or paraffin oil or a mixed solvent thereof of (2), preferably toluene, xylene, hexane, heptane, octane, decane, cyclohexane, paraffin oil, white oil, dodecane, tetradecane or hexadecane, or a mixed solvent thereof.
The present invention will be further described with reference to the following specific embodiments, but the scope of the present invention is not limited to the following examples.
Detailed Description
Example 1
After a 2-liter stainless steel autoclave was fully replaced with nitrogen, 1L of n-hexane was added to the reactor, 3mg of metallocene catalyst (1) and 3mL of MAO (10% toluene solution) were added, 0.1L of hydrogen was charged, ethylene was charged to a pressure of 0.7MPa, the mixture was stirred, the temperature was raised to 125 ℃ for reaction for 2 hours, and 286 g of a polymerization product was collected.
Example 2
After a 2-liter stainless steel autoclave was sufficiently replaced with nitrogen, 1L of n-heptane was added to the autoclave, 5mg of catalyst (2), 2mL of modified MAO (10% toluene solution), 60mL of 1-hexene were added, 0.05L of hydrogen was charged, ethylene was charged to a pressure of 0.8MPa, stirring was carried out, the temperature was raised to 135 ℃ to react for 2 hours, and 262 g of a polymerization product was collected.
Example 3
After a 2-liter stainless steel autoclave was fully replaced with nitrogen, 1L of n-hexane was added to the reactor, 2mg of metallocene catalyst (3), 2mL of modified MAO (10% toluene solution), 60mL of 1-hexene, 0.1L of hydrogen was charged, 0.5kg of propylene was added, ethylene was charged to a pressure of 0.7MPa, stirring was carried out, the temperature was increased to 110 ℃ for 2 hours, and 275 g of a polymerization product was collected.
Example 4
A2-liter stainless steel autoclave was fully replaced with nitrogen, 1L of toluene was added to the autoclave, 5mg of metallocene catalyst (4), 5mL of MAO (10% toluene solution), 20mL of 1-octene, 0.1L of hydrogen was charged, ethylene was charged to a pressure of 0.7MPa, stirring was carried out, the temperature was raised to 150 ℃ for 2 hours, and 217 g of a polymerization product was collected.
Example 5
A2-liter stainless steel autoclave was fully replaced with nitrogen, 1L of toluene was added to the autoclave, 6mg of metallocene catalyst (5), 5mL of MAO (10% toluene solution), 20mL of 1-octene, 0.2kg of propylene was added, 0.15L of hydrogen was charged, ethylene was charged to a pressure of 0.7MPa, stirring was carried out, the temperature was raised to 165 ℃ for 2 hours, and 221 g of a polymerization product was collected.
Example 6
After a 2 liter stainless steel autoclave was sufficiently replaced with nitrogen, 1L of xylene was added to the autoclave, 10mg of metallocene catalyst (6), 10mL of MAO (10% toluene solution), 30mL of styrene and 0.05L of hydrogen were added, ethylene was charged to a pressure of 0.7MPa, and the mixture was stirred, heated to 180 ℃ to react for 2 hours, and 217 g of a polymerization product was collected.
Example 7
After a 2 liter stainless steel autoclave was sufficiently purged with nitrogen, 1L of heptane, 3mg of metallocene catalyst (7), 6mL of MAO (10% toluene solution), 10mL of 1-hexene, 0.3kg of propylene, and 0.2L of hydrogen were added to the autoclave, and ethylene was charged to a pressure of 0.7MPa, followed by stirring, heating to 90 ℃ for 1 hour, and collecting 278 g of the polymerization product.
Example 8
After a 2 liter stainless steel autoclave was fully replaced with nitrogen, 1L of toluene was added to the autoclave, 2mg of metallocene catalyst (8) was added, 0.3L of hydrogen was added, ethylene was charged to a pressure of 0.8MPa, stirring was carried out, the temperature was raised to 140 ℃ to react for 2 hours, and 306 g of a polymerization product was collected.
Example 9
After a 2-liter stainless steel autoclave was sufficiently purged with nitrogen, 1L of toluene was charged into the autoclave, 5mg of metallocene catalyst (9), 2mL of MAO (10% toluene solution), 1mL of triethylaluminum (1.5M hexane solution), 10mL of 1-hexene, 0.3kg of propylene and 0.1L of hydrogen were charged, ethylene was charged to 0.5MPa, and the temperature was raised to 100 ℃ for 1 hour to obtain 281 g of a polymerization product.
Example 10
After a 2-liter stainless steel autoclave was sufficiently purged with nitrogen, 1L of toluene was added to the autoclave, 5mg of metallocene catalyst (10), 2mL of MAO (10% toluene solution), 0.3kg of propylene, 20 g of MMA, and 0.1L of hydrogen were added, ethylene was charged to a pressure of 0.7MPa, and the temperature was raised to 125 ℃ to react for 2 hours, whereby 189 g of a polymerization product was obtained.
Example 11
After a 2 liter stainless steel autoclave was fully replaced with nitrogen, 1L of toluene was added to the autoclave, 5mg of metallocene catalyst (11), 2mL of MAO (10% toluene solution), 1mL of tri-n-hexylaluminum (1.5M hexane solution), 10mL of 1-hexene was added, 0.05L of hydrogen was added, ethylene was charged to 0.7MPa, and the temperature was raised to 105 ℃ for 2 hours to obtain 289 g of a polymerization product.
Example 12
After a 2-liter stainless steel autoclave was sufficiently replaced with nitrogen, 1L of toluene was added to the autoclave, 10mg of metallocene catalyst (12), 15mL of MAO (10% toluene solution), 0.5kg of propylene was added, 5 g of 1, 7-octadiene was added, 0.05L of hydrogen was added, ethylene was charged to a pressure of 0.8MPa, and the temperature was raised to 160 ℃ to react for 2 hours, thereby obtaining 319 g of a polymerization product.
Example 13
After a 2-liter stainless steel autoclave was sufficiently purged with nitrogen, 1L of toluene was added to the autoclave, 10mg of metallocene catalyst (13), 5mL of MAO (10% toluene solution), 1.5kg of propylene and 0.02L of hydrogen were added, the temperature was raised to 125 ℃ and the reaction was carried out for 2 hours under a polymerization pressure of 2.9MPa, and 309 g of a polymerization product was collected.
Example 14
After a 2-liter stainless steel autoclave was sufficiently replaced with nitrogen, 1L of toluene was added to the autoclave, 10mg of metallocene catalyst (14), 5mL of MAO (10% toluene solution), 1.5kg of propylene and 0.05L of hydrogen were added, ethylene was charged to 0.6MPa, and the temperature was raised to 120 ℃ to react for 2 hours, thereby obtaining 323 g of a polymerization product.
Example 15
After a 2-liter stainless steel autoclave was sufficiently replaced with nitrogen, 1L of water was added to the autoclave, 10mg of metallocene catalyst (16), 15mL of MAO (10% toluene solution), 0.5kg of propylene was added, 5 g of ethylidene norbornene was added, 0.05L of hydrogen was added, ethylene was charged to a pressure of 0.6MPa, and the temperature was raised to 130 ℃ to react for 1 hour, thereby obtaining 165 g of a polymerization product.
Example 16
After a 2-liter stainless steel autoclave was sufficiently purged with nitrogen, 1L of toluene was added to the autoclave, 8mg of metallocene catalyst (16), 10mL of MAO (10% toluene solution), 10 g of 8-bromo-1-octene, 0.05L of hydrogen was added, ethylene was charged to a pressure of 0.8MPa, and the temperature was raised to 165 ℃ to react for 2 hours, thereby obtaining 201 g of a polymerization product.
Example 17
After a 2-liter stainless steel autoclave was sufficiently purged with nitrogen, 1L of toluene was added to the autoclave, 6mg of metallocene catalyst (17), 15mL of MAO (10% toluene solution), 10 g of 8-chloro-1-octene, 0.5kg of propylene was added, 0.05L of hydrogen was added, ethylene was charged to a pressure of 0.6MPa, and the temperature was raised to 110 ℃ to react for 2 hours, thereby obtaining 216 g of a polymerization product.
Example 18
After a 2-liter stainless steel autoclave was sufficiently purged with nitrogen, 1L of cyclohexane was added to the autoclave, 8mg of metallocene catalyst (19), 8mL of MAO (10% toluene solution), 10 g of 8-hydroxy-1-octene was added, 0.05L of hydrogen was added, ethylene was charged to a pressure of 0.7MPa, and the temperature was raised to 170 ℃ to react for 2 hours, thereby obtaining 208 g of a polymerization product.
Example 19
After a 2-liter stainless steel autoclave was sufficiently replaced with nitrogen, 1L of toluene was added to the autoclave, 5mg of metallocene catalyst (19), 5mL of MAO (10% toluene solution), 20 g of hydroxynorbornene, 0.05L of hydrogen was added, ethylene was charged to a pressure of 1.5MPa, and the temperature was raised to 110 ℃ to react for 2 hours, thereby obtaining 211 g of a polymerization product.
Example 20
After a 2-liter stainless steel autoclave was sufficiently replaced with nitrogen, 1L of xylene was added to the autoclave, 5mg of metallocene catalyst (20), 5mL of MAO (10% toluene solution), and 40mL of 1-octene were added, 0.3L of hydrogen was charged, ethylene was charged to a pressure of 0.7MPa, and the temperature was raised to 135 ℃ to react for 2 hours, yielding 286 g of a polymer.
Comparative example 1
A2 liter stainless steel autoclave was fully replaced with nitrogen, 1L of toluene was added to the autoclave, 10mg of trimethylcyclopentadienyl titanium trichloride metallocene catalyst, 15mL of MAO (10% toluene solution) and ethylene were charged to a pressure of 0.7MPa, and the temperature was raised to 100 ℃ for 2 hours to obtain 10 g of a polymer.
Comparative example 2
After a 2-liter stainless steel autoclave was sufficiently replaced with nitrogen, 1L of toluene was added to the autoclave, 10mg of dimethylsilyl-bridged bis-indenyl zirconium dichloride metallocene catalyst and 20mL of MAO (10% toluene solution) were added, ethylene was charged to a pressure of 0.7MPa, and the temperature was raised to 120 ℃ to react for 2 hours without any polymer.
Comparative example 3
A2-liter stainless steel autoclave was fully replaced with nitrogen, 1L of xylene was added to the autoclave, 5mg of dimethylsilyl trimethylcyclopentadienyl tert-butylamidozirconium dichloride metallocene catalyst, 5mL of MAO (10% toluene solution), 40mL of 1-octene were added, 0.3L of hydrogen was charged, ethylene was charged to a pressure of 0.7MPa, and the temperature was raised to 135 ℃ for 2 hours to obtain 55 g of a polymer.
The results are shown in Table 1.
TABLE 1
Figure GDA0002481222680000231
Figure GDA0002481222680000241

Claims (9)

1. A metallocene catalyst characterized by: the metallocene catalyst is a compound corresponding to the general formula 1;
Figure FDA0002511646730000011
wherein, R is8Or R9Selected from H, F, C1-C10Fatty radical of (C)6-C20Aryl of (C)3-C10Cycloalkyl of, C1-C10Of perfluoro or polyfluoro aliphatic radical, C6-C20Perfluoro or polyfluoro aryl of (C)3-C10Perfluoro or polyfluoro cycloalkyl of (A), C1-C10Alkoxy of C6-C20Aryloxy group of or C3-C10Cycloalkoxy of (a), wherein R8Or R9Attached to the same carbon atom or to different carbon atoms; wherein X is halogen, C1-C10Fatty radical of (C)6-C20Aryl of (C)3-C10Cycloalkyl of, C1-C10Of perfluoro or polyfluoro aliphatic radical, C6-C20Perfluoro or polyfluoro aryl of (C)3-C10Perfluoro or polyfluoro cycloalkyl of (a); wherein the content of the first and second substances,
Figure FDA0002511646730000012
is C5-C30A cyclopentadiene or a derivative group thereof, C9-C30Indene or derivative group thereof, or C13-C30A fluorene or its derivative group of (a); wherein M is selected from Ti, Zr, Hf, Y, Sc, V, Fe, Co, Ni, Nd, Sm, Rh, Pd, Ru, Ce, Al, Zn or Mg; wherein A is selected from C, Si, CH-CH, CF-CF, Se or Sn; wherein R is10An F-containing aryl group selected from the structures:
Figure FDA0002511646730000021
2. the metallocene catalyst according to claim 1, characterized in that: wherein the content of the first and second substances,
Figure FDA0002511646730000023
is selected from C9-C30The indene or derivative thereof, said metallocene catalyst corresponding to the compound of formula 2;
Figure FDA0002511646730000022
wherein R is1Selected from H, F, C1-C10Fatty radical of (C)6-C20Aryl of (C)3-C10Cycloalkyl of, C1-C10Of perfluoro or polyfluoro aliphatic radical, C6-C20Perfluoro or polyfluoro aryl of (C)3-C10Perfluoro or polyfluoro cycloalkyl of (a); x is halogen, C1-C10Fatty radical of (C)6-C20Aryl or C of3-C10Cycloalkyl groups of (a); a is selected from C, Si, CH-CH, CF-CF, Se or Sn; r8Or R9Selected from H, F, C1-C10Fatty radical of (C)6-C20Aryl of (C)3-C10Cycloalkyl of, C1-C10Of perfluoro or polyfluoro aliphatic radical, C6-C20Perfluoro or polyfluoro aryl of (C)3-C10Perfluoro or polyfluoro cycloalkyl of (A), C1-C10Alkoxy of C6-C20Aryloxy group of or C3-C10Cycloalkoxy of (a), wherein R8Or R9Attached to the same carbon atom or to different carbon atoms; m is selected from Ti, Zr, Hf, Y, Sc, V, Fe, Co, Ni, Nd, Sm, Rh, Pd, Ru, Ce, Al, Zn or Mg; wherein R is10An F-containing aryl group selected from the structures:
Figure FDA0002511646730000031
3. a metallocene catalyst characterized by: wherein the content of the first and second substances,
Figure FDA0002511646730000033
is selected from C5-C30The group of cyclopentadiene or a derivative thereof, said metallocene catalyst corresponding to the compound of formula 3;
Figure FDA0002511646730000032
wherein R is selected from H, F, C1-C10Fatty radical of (C)6-C20Aryl of (C)3-C10Cycloalkyl of, C1-C10Of perfluoro or polyfluoro aliphatic radical, C6-C20Perfluoro or polyfluoro aryl of (C)3-C10Perfluoro or polyfluoro cycloalkyl of (a); x is halogen, C1-C10Fatty radical of (C)6-C20Aryl or C of3-C10Cycloalkyl groups of (a); a is selected from C, Si, CH-CH, CF-CF, Se or Sn; r8Or R9Selected from H, F, C1-C10Fatty radical of (C)6-C20Aryl of (C)3-C10Cycloalkyl of, C1-C10Of perfluoro or polyfluoro aliphatic radical, C6-C20Perfluoro or polyfluoro aryl of (C)3-C10Perfluoro or polyfluoro cycloalkyl of (A), C1-C10Alkoxy of C6-C20Aryloxy group of or C3-C10Cycloalkoxy of (a), wherein R8Or R9Attached to the same carbon atom or to different carbon atoms; m is selected from Ti, Zr, Hf, Y, Sc, V, Fe, Co, Ni, Nd, Sm, Rh, Pd, Ru, Ce, Al, Zn or Mg; wherein R is10An F-containing aryl group selected from the structures:
Figure FDA0002511646730000041
4. the metallocene catalyst according to claim 1, wherein: wherein the content of the first and second substances,
Figure FDA0002511646730000043
is selected from C13-C30The tetrahydroindene derivative of (a), said metallocene catalyst corresponding to a compound of formula 4;
Figure FDA0002511646730000042
wherein R is3Is selected from C4-C10Fatty radical of (C)6-C20Aryl of (C)4-C10Cycloalkyl of, C4-C10Of perfluoro or polyfluoro aliphatic radical, C6-C20Of perfluoro or polyfluoroAryl radical, C4-C10Perfluoro or polyfluoro cycloalkyl of (a); x is halogen, C1-C10Fatty radical of (C)6-C20Aryl or C of3-C10Cycloalkyl groups of (a); a is selected from C, Si, CH-CH, CF-CF, Se or Sn; r8Or R9Selected from H, F, C1-C10Fatty radical of (C)6-C20Aryl of (C)3-C10Cycloalkyl of, C1-C10Of perfluoro or polyfluoro aliphatic radical, C6-C20Perfluoro or polyfluoro aryl of (C)3-C10Perfluoro or polyfluoro cycloalkyl of (A), C1-C10Alkoxy of C6-C20Aryloxy group of or C3-C10Cycloalkoxy of (a), wherein R8Or R9Attached to the same carbon atom or to different carbon atoms; m is selected from Ti, Zr, Hf, Y, Sc, V, Fe, Co, Ni, Nd, Sm, Rh, Pd, Ru, Ce, Al, Zn or Mg; wherein R is10An F-containing aryl group selected from the structures:
Figure FDA0002511646730000051
5. the metallocene catalyst according to claim 1, wherein: wherein the content of the first and second substances,
Figure FDA0002511646730000053
is selected from C13-C30The fluorene or derivative thereof of (1), said metallocene catalyst corresponding to the compound of formula 5;
Figure FDA0002511646730000052
wherein R is4Or R5Selected from H, F, C1-C10Fatty radical of (C)6-C20Aryl or C of3-C10Cycloalkyl groups of (a); x is halogen, C1-C10Fatty radical of (C)6-C20Aryl of (C)3-C10Cycloalkyl of, C1-C10Of perfluoro or polyfluoro aliphatic radical, C6-C20Perfluoro or polyfluoro aryl of (C)3-C10Perfluoro or polyfluoro cycloalkyl of (a); a is selected from C, Si, CH-CH, CF-CF, Se or Sn; r8Or R9Selected from H, F, C1-C10Fatty radical of (C)6-C20Aryl of (C)3-C10Cycloalkyl of, C1-C10Of perfluoro or polyfluoro aliphatic radical, C6-C20Perfluoro or polyfluoro aryl of (C)3-C10Perfluoro or polyfluoro cycloalkyl of (A), C1-C10Alkoxy of C6-C20Aryloxy group of or C3-C10Cycloalkoxy of (a), wherein R8Or R9Attached to the same carbon atom or to different carbon atoms; m is selected from Ti, Zr, Hf, Y, Sc, V, Fe, Co, Ni, Nd, Sm, Rh, Pd, Ru, Ce, Al, Zn or Mg; wherein R is10An F-containing aryl group selected from the structures:
Figure FDA0002511646730000061
6. a process for preparing a metallocene catalyst according to any of claims 1 to 5, comprising the steps of:
(1) adding C into organic solvent5-C30Cyclopentadiene or a derivative thereof, C8-C30Indene or derivatives thereof, or C13-C30The addition amount of the fluorene or the derivative thereof is calculated by 1 mol of cyclopentadiene or the derivative thereof, indene or the derivative thereof, or the fluorene or the derivative thereof, 1.0 to 1.2 mol of hydrogen-withdrawing compound is added at-60 to 20 ℃, and the reaction is carried out for 3 to 10 hours; adding 0.5 to 1.0 mole of a dihalo or alkyl compound of the bridging group A and reacting at-30 ℃ to 60 ℃ for 3 to 8 hours to obtain an intermediate corresponding to formula 6, wherein R8Or R9Selected from H, F, C1-C10Fatty radical of (C)6-C20Aryl of (C)3-C10Cycloalkyl of, C1-C10Of perfluoro or polyfluoro aliphatic radical, C6-C20Perfluoro or polyfluoro aryl of (C)3-C10Perfluoro or polyfluoro cycloalkyl of (A), C1-C10Alkoxy of C6-C20Aryloxy group of or C3-C10Cycloalkoxy of (a), wherein R8Or R9Attached to the same carbon atom or to different carbon atoms; wherein X is Cl, Br or I; wherein the content of the first and second substances,
Figure FDA0002511646730000073
is C5-C30A cyclopentadiene or a derivative group thereof, C9-C30Indene or derivative group thereof, or C13-C30A fluorene or its derivative group of (a); wherein A is selected from C, Si, CH-CH, CF-CF, Se or Sn;
Figure FDA0002511646730000071
(2) adding 0.5 to 1.0 mol of aryl amine containing F, and reacting at-30 to 60 ℃ for 5 to 12 hours to obtain an intermediate corresponding to the general formula 7;
Figure FDA0002511646730000072
wherein R is8Or R9Selected from H, F, C1-C10Fatty radical of (C)6-C20Aryl of (C)3-C10Cycloalkyl of, C1-C10Of perfluoro or polyfluoro aliphatic radical, C6-C20Perfluoro or polyfluoro aryl of (C)3-C10Perfluoro or polyfluoro cycloalkyl of (A), C1-C10Alkoxy of C6-C20Aryloxy group of or C3-C10Cycloalkoxy of (a), wherein R8Or R9Attached to the same carbon atom or to different carbon atoms; wherein the content of the first and second substances,
Figure FDA0002511646730000074
is C5-C30A cyclopentadiene or a derivative group thereof, C9-C30Indene or derivative group thereof, or C13-C30A fluorene or its derivative group of (a); wherein A is selected from C, Si, CH-CH, CF-CF, Se or Sn; wherein R is10An F-containing aryl group selected from the structures:
Figure FDA0002511646730000081
(3) adding 1.0-1.2 of hydrogen-removing compound at-60-10 ℃ for reaction for 4-10 hours; adding 0.6 to 2.0 mol of transition metal salt at the temperature of between 30 ℃ below zero and 60 ℃ for reaction for 5 to 12 hours; filtering, extracting with organic solvent, concentrating, crystallizing at-30 to 10 deg.C, filtering, drying, and obtaining the metallocene catalyst corresponding to formula 1 with a yield of more than 50%;
wherein the organic solvent is selected from benzene, toluene, hexane, heptane or THF; wherein the hydrogen abstraction compound is selected from NaH, Na, K, n-butyl lithium or Grignard reagent.
7. Use of a metallocene catalyst according to any of claims 1 to 5, characterized in that it is a catalyst for the polymerization of ethylene or propylene or the copolymerization of ethylene or propylene with α -olefins, wherein the α -olefin is selected from the group consisting of C3～C20The olefin of (1).
8. Use of a metallocene catalyst according to claim 7, characterized in that: the olefin polymerization conditions were: the polymerization temperature is 80-200 ℃, the hydrogen partial pressure is 0.001-0.2 MPa, the ethylene partial pressure is 0.1-5MPa, the propylene partial pressure is 0.5-5MPa, the reaction time is 0.5-4 h, and the molar ratio of the metallocene catalyst to the cocatalyst is 1: (0.1-200).
9. Use of a metallocene catalyst according to claim 7, characterized in that: adding an organic solvent when carrying out olefin polymerization, wherein the organic solvent is selected from C5～C30Saturated hydrocarbon of (C)5～C30Alicyclic hydrocarbon of (2), C6～C30Of aromatic hydrocarbons or C3～C20Or a paraffin oil or a mixed solvent thereof.
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