Metallocene catalyst, preparation method and application
1. A metallocene catalyst characterized by: the metallocene catalyst is a compound corresponding to the general formula 1;
general formula 1
Wherein, R and R are1Or R2Selected from H, halogen, C1-C20Fatty radical of (C)6-C30Aryl of (C)3-C30Cycloalkyl of, C1-C20Of perfluoro or polyfluoro aliphatic radical, C6-C30Perfluoro or polyfluoro aryl of (C)3-C30Perfluoro or polyfluoro cycloalkyl of (A), C1-C20Alkoxy of C6-C30Aryloxy group of or C3-C30Cycloalkoxy of (a), wherein R1And R2Attached 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,is C5-C30Cyclopentadiene and derivatives thereof, C9-C30Indene and derivatives thereof, C9-C30Tetrahydroindenyl group and derivative thereof, C13-C30Fluorene and its derivatives of (A), C13-C30Hydrogenated fluorenyl group or derivative thereof or C11-C30The sulfur-bridged benzocyclopentadienyl group of (a) or a derivative thereof; 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, P is phosphorus element, and P and M are linked through coordination bond or chemical bond; wherein said metallocene is catalyzedThe catalyst and the cocatalyst form a catalyst system, and the molar ratio of the metallocene catalyst to the cocatalyst is 1: (5-2000), wherein said cocatalyst is an aluminum alkyl, an aluminum alkoxide, or a blend thereof.
2. The metallocene catalyst according to claim 1, characterized in that: wherein the content of the first and second substances,is selected from C9-C30The indenyl or derivative thereof group of (a), said metallocene catalyst corresponding to the compound of formula 2;
general formula 2
Wherein R is1，R2Or R3Selected from H, halogen, C1-C20Fatty radical of (C)6-C30Aryl of (C)3-C30Cycloalkyl of, C1-C20Of perfluoro or polyfluoro aliphatic radical, C6-C30Perfluoro or polyfluoro aryl of (C)3-C30Perfluoro or polyfluoro cycloalkyl of (A), C1-C20Alkoxy of C6-C30Aryloxy group of or C3-C30Cycloalkoxy of (a), wherein R1And R2Attached 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 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, P is selected from phosphorus element, and P and M are linked through coordination bond or chemical bond.
3. The metallocene catalyst according to claim 1, characterized in that: wherein the content of the first and second substances,is selected from C5-C30The cyclopentadienyl group or derivative thereof of (1), said metallocene catalyst corresponding to the compound of formula 3;
general formula 3
Wherein R, R1Or R2Selected from H, halogen, C1-C20Fatty radical of (C)6-C30Aryl of (C)3-C30Cycloalkyl of, C1-C20Of perfluoro or polyfluoro aliphatic radical, C6-C30Perfluoro or polyfluoro aryl of (C)3-C30Perfluoro or polyfluoro cycloalkyl of (A), C1-C20Alkoxy of C6-C30Aryloxy group of or C3-C30Cycloalkoxy of (a), wherein R1And R2Attached 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 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, P is selected from phosphorus element, and P and M are linked through coordination bond or chemical bond.
4. The metallocene catalyst according to claim 1, characterized in that: wherein the content of the first and second substances,is selected from C9-C30The tetrahydroindenyl group or derivative thereof of (a), said metallocene catalyst corresponding to the compound of formula 4;
general formula 4
Wherein R is1，R2Or R5Selected from H, halogen, C1-C20Fatty radical of (C)6-C30Aryl of (C)3-C30Cycloalkyl of, C1-C20Of perfluoro or polyfluoro aliphatic radical, C6-C30Perfluoro or polyfluoro aryl of (C)3-C30Perfluoro or polyfluoro cycloalkyl of (A), C1-C20Alkoxy of C6-C30Aryloxy group of or C3-C30Cycloalkoxy of (a), wherein R1And R2Attached 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 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, P is selected from phosphorus element, and P and M are linked through coordination bond or chemical bond.
5. The metallocene catalyst according to claim 1, characterized in that: wherein the content of the first and second substances,is selected from C13-C30The fluorenyl group or derivative thereof of (1), the metallocene catalyst corresponding to the compound of formula 5;
general formula 5
Wherein R is1，R2，R6Or R7Selected from H, halogen, C1-C20Fatty radical of (C)6-C30Aryl of (C)3-C30Cycloalkyl of, C1-C20Of perfluoro or polyfluoro aliphatic radical, C6-C30Perfluoro or polyfluoro aryl of (C)3-C30Perfluoro or polyfluoro cycloalkyl of (A), C1-C20Alkoxy of C6-C30Aryloxy group of or C3-C30Cycloalkoxy of (a), wherein R1And R2Attached 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 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, P is selected from phosphorus element, and P and M are linked through coordination bond or chemical bond.
6. The metallocene catalyst according to claim 1, characterized in that: wherein the content of the first and second substances,is selected from C13-C30The hydrogenated fluorenyl group or derivative thereof, the metallocene catalyst corresponding to the compound of formula 6;
general formula 6
Wherein R is1，R2，R8Or R9Selected from H, halogen, C1-C20Fatty radical of (C)6-C30Aryl of (C)3-C30Cycloalkyl of, C1-C20Of perfluoro or polyfluoro aliphatic radical, C6-C30Perfluoro or polyfluoro aryl of (C)3-C30Perfluoro or polyfluoro cycloalkyl of (A), C1-C20Alkoxy of C6-C30Aryloxy group of or C3-C30Cycloalkoxy of (a), wherein R1And R2Attached 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 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, P is selected from phosphorus element, and P and M are linked through coordination bond or chemical bond.
7. The metallocene catalyst according to claim 1, characterized in that: wherein the content of the first and second substances,is selected from C11-C30Said metallocene catalyst corresponds to a compound of formula 7;
general formula 7
Wherein R is1，R2，R10，R11，R12，R13，R14Or R15Selected from H, Me, halogen, C2-C20Fatty radical of (C)6-C30Aryl of (C)3-C30Cycloalkyl of, C1-C20Of perfluoro or polyfluoro aliphatic radical, C6-C30Perfluoro or polyfluoro aryl of (C)3-C30Perfluoro or polyfluoro cycloalkyl of (A), C1-C20Alkoxy of C6-C30Aryloxy group of or C3-C30Cycloalkoxy of (a), wherein R1And R2Attached 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 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, P is selected from phosphorus element, and P and M are linked through coordination bond or chemical bond.
8. A process for preparing a metallocene catalyst according to any of claims 1 to 7, comprising the steps of:
(1) adding C into organic solvent5-C30Cyclopentadiene or a derivative thereof, C9-C30Indene or derivatives thereof, C13-C30Fluorene or a derivative thereof, C13-C30A hydrogenated fluorenyl group or a derivative group thereof, or C11-C30The addition amount of the sulfur-bridged benzocyclopentadienyl or the derivative group thereof is calculated by 1 mol of cyclopentadiene or the derivative thereof, indene or the derivative thereof, fluorene or the derivative thereof, or hydrogenated fluorenyl or the derivative group thereof, or the sulfur-bridged benzocyclopentadienyl or the derivative group thereof, 1.0 to 1.2 mol of hydrogen-withdrawing compound is added at-60 to 20 ℃ for reaction for 1 to 15 hours; adding 1 mol of P (III) organic compound, reacting at-60-20 deg.C for 3-8 hr to obtain intermediate corresponding to formula 8, wherein P (III) organic compound is monohalogen organophosphorus compound, wherein R1Or R2Selected 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 R1And R2Attached 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,is cyclopentadienyl or a derivative thereof, indenyl or a derivative thereof or fluorenyl or a derivative thereof;
general formula 8
(2) Adding 1.0 to 1.2 mol of hydrogen-withdrawing compound at the temperature of between 60 ℃ below zero and 10 ℃ for reaction for 4 to 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.
9. Use of a metallocene catalyst according to claim 1, characterized in that: is a catalyst for ethylene polymerization, propylene polymerization, copolymerization of ethylene and alpha-olefin, or copolymerization of propylene and alpha-olefin, wherein the alpha-olefin is selected from C3～C20Or a blend thereof.
10. A metallocene catalyst characterized by: the olefin polymerization conditions were: after the polymerization temperature is 0 ℃ to 200 DEG CHydrogen partial pressure is 0-0.2MPa, ethylene partial pressure is 0.1-10MPa, propylene partial pressure is 0.5-10MPa, reaction time is 0.1-4 h, and the molar ratio of the metallocene catalyst to the cocatalyst is 1: (1-2000); 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～C20Or a paraffin oil or a mixed solvent thereof.
Background
In recent years, the yield of plastic products in China is increased year by year, and the capacity is also increased continuously. The polyolefin product has the characteristics of rich raw materials, low price, easy processing and forming, long service life, excellent comprehensive performance and the like, and is popular with people. At present, polyolefin products are widely applied to various fields such as agriculture, building industry, packaging industry, automobile industry, medical industry, daily life and the like. However, common polyolefin products are not easily compatible with other materials, which greatly limits the application range, and the use requirements of the materials are higher and higher due to the improvement of the living standard of people. Therefore, the development of high value-added, high performance polyolefin products is imminent.
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 packages, self-supporting bags, agricultural films, composite packaging films, stretching and winding films and the like). The mPE products which are circulated in the market of China rapidly with the increasing demand of mPE high-end polyethylene products are products produced by ExxonMobil company and Dow chemical company. The Korean Dalin company introduces the technology of Dow chemical company, and the produced mPE products are put into the market and have the lowest price, thus becoming the main source of mPE in China. The mPE produced by mitsui chemical company of japan occupies a relatively small share of the market due to its high price. 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 obtained in the research aspect of the basic theory of the metallocene catalyst [ Huangqi Guaigu, etc.. the metallocene catalyst, the preparation method and the application thereof, CN108752509A.2018], and the application aspect thereof 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. The more important reason is that the difficulties encountered in the industrial application of the catalyst have not been solved until the metallocene catalysts have not been used in the industrial production in our country. 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. The Daqing petrochemical company of China introduced metallocene catalyst patent technology of Univariation company in America, and only 3000 tons of film-grade mPE was produced since 2007. China still has no POE catalyst technology and no POE industrial production report.
DuPont-Dow Elastometers (DuPont Dow. polyofin elastomer Engage [ J ]. Polymer, 1996,33(8):76 ]) developed an ethylene-octene thermoplastic elastomer Engage with good transparency and high strength using a constrained geometry metallocene catalyst. 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 120 ℃ and 180 ℃, and the obtained polyolefin has high molecular weight.
JP, EP 0495099A 1]The ethylene and alpha-olefin are catalyzed to be copolymerized under the condition of normal pressure to 5.0MPa by adopting an ethyl bridged metallocene/MAO catalytic system and using toluene as a solvent to synthesize the polyolefin elastomer Tafmer, the mole content of the alpha-olefin in a polymer molecular chain is high (up to 9 percent), the density of a product is low, and the product is 0.85-0.92g/cm3The molecular weight distribution is 1.2-4.0. The characteristics of the patentCharacterized in that an organosilicon compound is added to the metallocene compound before the 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.
Soares[Colin Li Pi Shan,et al.Macromol.Chem.Phys.2000,201(16),2195–2202]Using supported metallocene catalyst Et (Ind)2ZrCl2The ethylene and 1-hexene are catalyzed and copolymerized under the pressure of 10MPa, the catalytic activity is up to 4341.7kg PE/mol Zr.h, and the molar content of 1-hexene in the copolymer is about 3 percent. The results of the above studies indicate that the copolymerization capacity of alpha-olefins (above C4) with ethylene is low despite the use of metallocene catalysts (except for constrained geometry) and high alpha-olefin feed ratios.
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 electron-donating group, and the result shows that the existence of electron-donating substituent group on cyclopentadienyl ligand can make the active center more stable and can raise the activity of 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 activity and 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. We [ JingWang, Qigu Huang, et al. catalyst Letters,2016,146(3),609] investigated the law of the influence of ortho-and para-substituents R of the N atom directly attached to the atom of the early transition metal Ti (Zr, etc.) on the catalytic performance of the catalyst. When R is F, the catalyst has the best catalytic performance, high catalytic activity, high molecular weight of the copolymerized olefin, and high insertion amount of the comonomer, as compared with when R is H, Me. Compared with Me (electron-withdrawing group), F is a strong electron-withdrawing group, and when R is F, the electron cloud density around the transition metal atom is weakened due to the strong electron-withdrawing capability of F, so that the catalytic activity of the catalyst is improved. 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 high molecular weight polyolefin can be obtained even at the higher polymerization temperature of 160 ℃.
The present invention has unexpectedly found a novel phosphine-containing metallocene catalyst, the main ring of which is composed of a phosphine-containing compound, Cp or a derivative thereof and a transition metal atom. By introducing a strong electron-withdrawing group into the ligand, the Lewis alkalinity of the strong electron-withdrawing group is stronger, the Lewis acidity of the transition metal is reduced, and the beta-H elimination reaction of olefin polymerization is weakened; and the thermal stability of the catalyst is improved because the Lewis acidity of the transition metal is weakened. In the presence of a cocatalyst of aluminum alkoxide or aluminum alkyl, the catalyst can efficiently catalyze multiple copolymerization such as ethylene homopolymerization, propylene homopolymerization, ethylene and alpha-olefin copolymerization, propylene and alpha-olefin copolymerization, ethylene and polar olefin monomer copolymerization or propylene and polar olefin monomer copolymerization and the like at the high temperature of 10-200 ℃ to obtain the polyolefin with higher molecular weight. The preparation method of the polyolefin has the advantages of simple process, high catalytic activity, low cost, low requirement on equipment, low energy consumption and low environmental pollution.
Disclosure of Invention
The invention aims to provide a novel olefin coordination polymerization catalyst, and a preparation method and application of polyolefin. In particular to a metallocene catalyst for catalyzing olefin homopolymerization or copolymerization. In the process of olefin homopolymerization, or copolymerization of binary or above monomers, 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 polymerization process or a combined polymerization process.
The metallocene catalyst and the preparation method are characterized in that: the metallocene catalyst is a compound corresponding to the general formula 1;
wherein, R and R are1Or R2Selected from H, halogen, C1-C20Fatty radical of (C)6-C30Aryl of (C)3-C30Cycloalkyl of, C1-C20Of perfluoro or polyfluoro aliphatic radical, C6-C30Perfluoro or polyfluoro aryl of (C)3-C30Perfluoro or polyfluoro cycloalkyl of (A), C1-C20Alkoxy of C6-C30Aryloxy group of or C3-C30Cycloalkoxy of (a), wherein R1And R2Attached 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,is C5-C30Cyclopentadiene and derivatives thereof, C9-C30Indene and derivatives thereof, C9-C30Tetrahydroindenyl group and derivative thereof, C13-C30Fluorene and its derivatives of (A), C13-C30Hydrogenated fluorenyl group or derivative thereof or C11-C30The sulfur-bridged benzocyclopentadienyl group of (a) or a derivative thereof; 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, P is selected from phosphorus element, P and M are linked through coordination bond or chemical bond; wherein said metallocene catalyst is a metallocene withThe cocatalyst constitutes a catalyst system, and the molar ratio of the metallocene catalyst to the cocatalyst is 1: (5-2000), wherein said cocatalyst is an aluminum alkyl, an aluminum alkoxide, or a blend thereof.
A metallocene catalyst characterized by: wherein the content of the first and second substances,is selected from C9-C30The indenyl or derivative thereof group of (a), said metallocene catalyst corresponding to the compound of formula 2;
wherein R is1，R2Or R3Selected from H, halogen, C1-C20Fatty radical of (C)6-C30Aryl of (C)3-C30Cycloalkyl of, C1-C20Of perfluoro or polyfluoro aliphatic radical, C6-C30Perfluoro or polyfluoro aryl of (C)3-C30Perfluoro or polyfluoro cycloalkyl of (A), C1-C20Alkoxy of C6-C30Aryloxy group of or C3-C30Cycloalkoxy of (a), wherein R1And R2Attached 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 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, P is selected from phosphorus element, P and M are linked through coordination bond or chemical bond;
a metallocene catalyst characterized by: wherein the content of the first and second substances,is selected from C5-C30The cyclopentadienyl group or derivative thereof of (1), said metallocene catalyst corresponding to the compound of formula 3;
wherein R, R1Or R2Selected from H, halogen, C1-C20Fatty radical of (C)6-C30Aryl of (C)3-C30Cycloalkyl of, C1-C20Of perfluoro or polyfluoro aliphatic radical, C6-C30Perfluoro or polyfluoro aryl of (C)3-C30Perfluoro or polyfluoro cycloalkyl of (A), C1-C20Alkoxy of C6-C30Aryloxy group of or C3-C30Cycloalkoxy of (a), wherein R1And R2Attached 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 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, P is selected from phosphorus element, P and M are linked through coordination bond or chemical bond;
a metallocene catalyst characterized by: wherein the content of the first and second substances,is selected from C9-C30The tetrahydroindenyl group or derivative thereof of (a), said metallocene catalyst corresponding to the compound of formula 4;
wherein R is1，R2Or R5Selected from H, halogen, C1-C20Fatty radical of (C)6-C30Aryl of (C)3-C30Cycloalkyl of, C1-C20Of perfluoro or polyfluoro aliphatic radical, C6-C30Perfluoro or polyfluoro aryl of (C)3-C30Perfluoro or polyfluoro cycloalkyl of (A), C1-C20Alkoxy of C6-C30Aryloxy group of or C3-C30Cycloalkoxy of (a), wherein R1And R2Attached 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 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, P is phosphorus element, and P and M are linked through coordination bond or chemical bond;
a metallocene catalyst characterized by: wherein the content of the first and second substances,is selected from C13-C30The fluorenyl group or derivative thereof of (1), the metallocene catalyst corresponding to the compound of formula 5;
wherein R is1，R2，R6Or R7Selected from H, halogen, C1-C20Fatty radical of (C)6-C30Aryl of (C)3-C30Cycloalkyl of, C1-C20Of perfluoro or polyfluoro aliphatic radical, C6-C30Perfluoro or polyfluoro aryl of (C)3-C30Perfluoro or polyfluoro cycloalkyl of (A), C1-C20Alkoxy of C6-C30Aryloxy group of or C3-C30Cycloalkoxy of (a), wherein R1And R2Attached 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 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, P is selected from phosphorus element, P and M are linked through coordination bond or chemical bond;
a metallocene catalyst characterized by: wherein the content of the first and second substances,is selected from C13-C30The hydrogenated fluorenyl group or derivative thereof, the metallocene catalyst corresponding to the compound of formula 6;
wherein R is1，R2，R8Or R9Selected from H, halogen, C1-C20Fatty radical of (C)6-C30Aryl of (C)3-C30Cycloalkyl of, C1-C20Of perfluoro or polyfluoro aliphatic radical, C6-C30Perfluoro or polyfluoro aryl of (C)3-C30Perfluoro or polyfluoro cycloalkyl of (A), C1-C20Alkoxy of C6-C30Aryloxy group of or C3-C30Cycloalkoxy of (a), wherein R1And R2Attached 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 a perfluorinated or polyfluorinated aliphatic group of (a),C6-C20perfluoro or polyfluoro aryl of (C)3-C10Perfluoro or polyfluoro cycloalkyl 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, P is selected from phosphorus element, P and M are linked through coordination bond or chemical bond;
a metallocene catalyst characterized by: wherein the content of the first and second substances,is selected from C11-C30Said metallocene catalyst corresponds to a compound of formula 7;
wherein R is1，R2，R10，R11，R12，R13，R14Or R15Selected from H, Me, halogen, C2-C20Fatty radical of (C)6-C30Aryl of (C)3-C30Cycloalkyl of, C1-C20Of perfluoro or polyfluoro aliphatic radical, C6-C30Perfluoro or polyfluoro aryl of (C)3-C30Perfluoro or polyfluoro cycloalkyl of (A), C1-C20Alkoxy of C6-C30Aryloxy group of or C3-C30Cycloalkoxy of (a), wherein R1And R2Attached 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 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, P is selected from phosphorus element, P and M are linked through coordination bond or chemical bond;
the preparation method of the metallocene catalyst is characterized by comprising the following steps:
(1) adding C into organic solvent5-C30Cyclopentadiene or a derivative thereof, C9-C30Indene or derivatives thereof, C13-C30Fluorene or a derivative thereof, C13-C30A hydrogenated fluorenyl group or a derivative group thereof, or C11-C30The addition amount of the sulfur-bridged benzocyclopentadienyl or the derivative group thereof is calculated by 1 mol of cyclopentadiene or the derivative thereof, indene or the derivative thereof, fluorene or the derivative thereof, or hydrogenated fluorenyl or the derivative group thereof, or the sulfur-bridged benzocyclopentadienyl or the derivative group thereof, 1.0 to 1.2 mol of hydrogen-withdrawing compound is added at-60 to 20 ℃ for reaction for 1 to 15 hours; adding 1 mol of P compound, reacting at-60-20 deg.C for 3-8 hr to obtain intermediate corresponding to formula 6, 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 R1And R2Attached 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,is cyclopentadienyl or a derivative thereof, indenyl or a derivative thereof or fluorenyl or a derivative thereof;
(2) 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.
According to formula 1, it is specifically selected from the following metallocene catalysts (1) to (19), but not limited thereto:
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: (5-2000), wherein said cocatalyst is an aluminum alkyl, an aluminum alkoxide, or a mixture thereof; compared to 5, more classical cocatalysts such as: 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 and the application thereof are characterized in that: the application of the catalyst provided by the invention is as follows: is a catalyst for ethylene polymerization, propylene polymerization or copolymerization of ethylene (or propylene) and alpha-olefin, wherein the alpha-olefin is selected from C3～C20The olefin of (2) is preferably propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 3-decene-methyl-1-butene, cyclopentene, 4-methyl-1-pentene, 1, 3-butadiene, isoprene, styrene, methylstyrene, 1, 7-octadiene, 1, 8-nonadiene, 1, 9-decadiene, norbornene, ethylidene norbornene or derivatives thereof, halogenated olefins, hydroxy olefins, carboxy olefins, ester olefins, or blends thereof. The olefin polymerization conditions were: after the polymerization temperature is 0-200 ℃, the hydrogen partial pressure is 0-0.2MPa, the ethylene partial pressure is 0.1-10MPa, the propylene partial pressure is 0.5-10MPa, the reaction time is 0.1-4 h, and the molar ratio of the metallocene catalyst to the cocatalyst is 1: (5-2000). 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 their mixed solvent is selected from toluene, xylene, hexane, heptane, octane, decane, cyclohexane, petroleum ether, paraffin oil, white oil, dodecane, tetradecane or hexadecane, or their mixed solvent.
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
(1) Synthesis of ligand compound L1 [ L1 structure: r in the general formula (6) is H, R1、R2To obtain phenyl]
Taking 40ml tetrahydrofuran and 10ml cyclopentadiene in a 300ml schlenk bottle, adding 0.69g metallic sodium at-10 ℃, stirring, reacting for 8 hours, adding diphenyl phosphine chloride with the molar equivalent to the metallic sodium, reacting for 6 hours at-30 ℃, removing the solvent in vacuum, adding 100ml normal hexane into the residual solid, dissolving and filtering, and recrystallizing the filtrate to obtain 4.87g cyclopentadienyl diphenylphosphine solid with the yield: and (4) 64.9%.1H NMR(400MHz,CDCl3:7.26ppm):δ＝7.42(m,4H,Ph)；7.33(m,6H,Ph)；6.99(d,2H,Cp)；6.65(m,2H,Cp)；3.48(t,1H,Cp)；Anal.Calcd.(％)for C17H15P(250):C,81.58；H,6.04；found:C,81.56；H,6.07；ESI-MS m/z calculated for[M+H]+.C17H15P:250.09,found,251.09。
(2) Preparation of the procatalyst
20ml of toluene and 1g of ligand L1 are taken in a 300ml schlenk bottle, n-butyllithium which is equimolar with the ligand is added at-30 ℃, the mixture is stirred and reacted for 4 hours, and TiCl which is equimolar with the ligand is added4The reaction was carried out at-30 ℃ for 5 hours, the solvent was removed in vacuo, washed 3 times with 300ml of n-hexane and dried in vacuo to obtain catalyst (1) in 83.6% yield.1H NMR(400MHz,CDCl3:7.26ppm):δ＝7.21(m,10H,Ph)；4.56(d,2H,Cp)；3.58(d,2H,Cp)；Anal.Calcd.(％)for C17H14Cl3PTi(403):C,50.61；H,3.50；found:C,50.63；H,3.49。
(3) Ethylene polymerization:
A2L stainless steel autoclave was fully replaced with nitrogen under anhydrous and anaerobic conditions, 1L toluene was added to the autoclave, 5mg catalyst (1) and 3mL (10 wt%) MAO solution were added, 0.1L hydrogen was added, ethylene was added to a pressure of 0.7MPa, the mixture was stirred, the temperature was increased to 120 ℃ for 2 hours, and 267 g polymerization product was collected.
(4) Ethylene copolymerization:
A2L stainless steel autoclave was fully replaced with nitrogen under anhydrous and oxygen-free conditions, 1L toluene was added to the autoclave, 5mg catalyst (1), 3mL (10 wt%) MAO solution, 90mL 1-hexene, 0.05L hydrogen was charged, ethylene was charged to 0.8MPa, stirring was carried out, the temperature was increased to 120 ℃ for 2 hours, and 218 g polymerization product was collected.
Example 2
(1) Synthesis of ligand compound L2 [ L2 structure: in the general formula (6)Taking tetramethyl cyclopentadiene, R1、R2Taking isopropyl]
Taking 40ml tetrahydrofuran and 3.66g tetramethyl cyclopentadiene in a 300ml schlenk bottle, adding 0.69g metal sodium at-10 ℃, stirring, reacting for 8 hours, adding diisopropyl phosphine chloride with the same mole of the metal sodium, reacting for 6 hours at-30 ℃, removing the solvent in vacuum, and adding the restAdding 100ml of n-hexane into the remaining solid, dissolving and filtering, and recrystallizing the filtrate to obtain 4.97g of tetramethylcyclopentadienyl diisopropyl phosphine solid with the yield: 69.5 percent.1H NMR(400MHz,CDCl3:7.26ppm):δ＝3.56(m,1H,Cp)；1.98(s,6H,Cp-CH3)；1.92(m,2H,-CH)；1.85(d,6H,Cp-CH3)；1.05(d,12H,P-CH3)；Anal.Calcd.(％)for C15H27P(238):C,75.59；H,11.42；found:C,75.61；H,11.41；ESI-MS m/z calculated for[M+H]+.C15H27P:238.19,found,239.19。
(2) Preparation of the procatalyst
20ml of toluene and 1g of ligand L2 were put into a 300ml schlenk flask, n-butyllithium equimolar to the ligand was added at-30 ℃ and stirred to react for 4 hours, and NdCl equimolar to the ligand was added3The reaction was carried out at-30 ℃ for 5 hours, the solvent was removed in vacuo, washed 3 times with 300ml of n-hexane and dried in vacuo to obtain catalyst (2) in 75.6% yield.1H NMR(400MHz,CDCl3:7.26ppm):δ＝1.89(m,2H,-CH)；0.95(d,12H,P-CH3)；0.91(s,6H,Cp-CH3)；0.81(s,6H,Cp-CH3)；Anal.Calcd.(％)for C15H26Cl2PNd(452):C,39.82；H,5.79；found:C,39.86；H,5.82。
(3) Ethylene polymerization:
A2L stainless steel autoclave is fully replaced by nitrogen under anhydrous and oxygen-free conditions, 1L toluene is added into the autoclave, 5mg catalyst (2) and 5mL (10 wt%) MAO solution are added, 0.1L hydrogen is filled, ethylene is filled to the pressure of 0.7MPa, the mixture is stirred, the temperature is raised to 130 ℃ for reaction for 2 hours, and 253 g polymerization product is collected.
(4) Ethylene copolymerization:
A2L stainless steel autoclave is fully replaced by nitrogen under anhydrous and anaerobic conditions, 1L toluene is added into the autoclave, 5mg catalyst (2), 3mL (10 wt%) MAO solution and 110mL 1-hexene are added, 0.05L hydrogen is filled, ethylene is filled to the pressure of 0.8MPa, the mixture is stirred, the temperature is raised to 130 ℃ for reaction for 2 hours, and 236 g polymerization product is collected.
Example 3
(1) Ligand combinationSynthesis of compound L3 [ L3 structure: r in the general formula (6) is H, R1、R2To get methyl]
Taking 40ml tetrahydrofuran and 10ml cyclopentadiene in a 300ml schlenk bottle, adding 0.69g metallic sodium at-10 ℃, stirring, reacting for 8 hours, adding dimethyl phosphine chloride with the same mole as the metallic sodium, reacting for 6 hours at-30 ℃, removing the solvent in vacuum, adding 100ml normal hexane into the residual solid, dissolving and filtering, and recrystallizing the filtrate to obtain 2.89g cyclopentadienyl dimethyl phosphine solid with the yield: 76.4 percent.1H NMR(400MHz,CDCl3:7.26ppm):δ＝6.65(d,2H,Cp)；6.22(m,2H,Cp)；3.68(m,1H,Cp)；0.98(d,6H,P-CH3)；Anal.Calcd.(％)for C7H11P(126):C,66.65；H,8.79；found:C,66.63；H,8.80；ESI-MS m/z calculated for[M+H]+.C7H11P:126.06,found,127.05。
(2) Preparation of the procatalyst
20ml of toluene and 1g of ligand L3 were put in a 300ml schlenk flask, n-butyllithium equimolar to the ligand was added at-30 ℃ and stirred to react for 4 hours, and ZrCl equimolar to the ligand was added4The reaction was carried out at-30 ℃ for 5 hours, the solvent was removed in vacuo, washed 3 times with 300ml of n-hexane and dried in vacuo to obtain catalyst (3) in 67.9% yield.1H NMR(400MHz,CDCl3:7.26ppm):δ＝3.78(d,2H,Cp)；3.66(d,2H,Cp)；0.96(s,6H,P-CH3)；Anal.Calcd.(％)for C7H10Cl3PZr(322):C,26.05；H,3.12；found:C,26.03；H,3.11。
(3) Ethylene polymerization:
A2L stainless steel autoclave is fully replaced by nitrogen under anhydrous and anaerobic conditions, 1L toluene is added into the autoclave, 2mg catalyst (3) and 2mL (10 wt%) MAO solution are added, 0.1L hydrogen is filled, ethylene is filled to the pressure of 0.7MPa, the mixture is stirred, the temperature is increased to 110 ℃ for reaction for 2 hours, and 262 g polymerization product is collected.
(4) Ethylene copolymerization:
a2 liter stainless steel autoclave was fully replaced with nitrogen under anhydrous and oxygen-free conditions, 1L of toluene was added to the autoclave, 3mg of catalyst (3), 5mL (10 wt%) of MAO solution, 65mL of 1-octene was added, 0.05L of hydrogen was charged, ethylene was charged to a pressure of 0.8MPa, the mixture was stirred, the temperature was increased to 110 ℃ for 2 hours, and 173 g of a polymerization product was collected.
Example 4
(1) Synthesis of ligand compound L4 [ L4 structure: in the general formula (6)Taking indenyl, R1、R2To obtain phenyl]
40ml of tetrahydrofuran and 3.6ml of indene are taken in a 300ml schlenk bottle, equimolar n-butyllithium is added at-10 ℃, stirred and reacted for 8 hours, then equimolar diphenyl phosphine chloride is added and reacted for 6 hours at-30 ℃, the solvent is removed in vacuum, 100ml of n-hexane is added to the residual solid, dissolved and filtered, and the filtrate is recrystallized to obtain 4.95g of indenyl diphenylphosphine solid, the yield: 54.9 percent.1H NMR(400MHz,CDCl3:7.26ppm):δ＝7.33(m,4H,Ph)；7.30-7.27(m,2H,In)；7.24-7.22(m,8H,In,Ph)；7.02(d,1H,In)；6.73(t,1H,In)；3.62(d,1H,In)；Anal.Calcd.(％)for C21H17P(300):C,83.98；H,5.71；found:C,83.96；H,5.70；ESI-MS m/z calculated for[M+H]+.C21H17P:300.11,found,301.11。
(2) Preparation of the procatalyst
20ml of toluene and 1g of ligand L4 were taken in a 300ml schlenk flask, n-butyllithium equimolar to the ligand was added at-30 ℃, stirred, reacted for 4 hours, and VCl equimolar to the ligand was added4The reaction was carried out at-30 ℃ for 5 hours, the solvent was removed in vacuo, washed 3 times with 300ml of n-hexane and dried in vacuo to obtain catalyst (4) in 52.1% yield.1H NMR(400MHz,CDCl3:7.26ppm):δ＝7.32(m,4H,Ph)；7.28(m,6H,Ph)；6.68(m,1H,In)；6.52(m,1H,In)；6.46(m,1H,In)；6.26(m,1H,In)；4.03(d,1H,In)；3.52(d,1H,In)；Anal.Calcd.(％)for C21H16Cl3PV(456):C,55.24；H,3.53；found:C,55.22；H,3.50。
(3) Ethylene polymerization:
A2L stainless steel autoclave is fully replaced by nitrogen under anhydrous and anaerobic conditions, 1L xylene is added into the autoclave, 6mg catalyst (4) and 5mL (10 wt%) MAO solution are added, 0.15L hydrogen is filled, ethylene is filled to the pressure of 0.7MPa, the mixture is stirred, the temperature is raised to 140 ℃ for reaction for 2 hours, and 212 g polymerization product is collected.
(4) Ethylene copolymerization:
A2L stainless steel autoclave is fully replaced by nitrogen under anhydrous and anaerobic conditions, 1L xylene is added into the autoclave, 6mg catalyst (4), 5mL (10 wt%) MAO solution and 75mL 1-octene are added, 0.15L hydrogen is filled, ethylene is filled to the pressure of 0.8MPa, the mixture is stirred, the temperature is raised to 140 ℃ for reaction for 2 hours, and 201 g polymerization product is collected.
Example 5
(1) Synthesis of ligand compound L5 [ L5 structure: in the general formula (6)Taking fluorenyl radical, R1、R2Taking 4-fluorophenyl]
Taking 40ml tetrahydrofuran and 4.98g fluorene in a 300ml schlenk bottle, adding n-butyllithium with equal mole at-10 ℃, stirring, reacting for 8 hours, adding bis (4-fluorophenyl) phosphonium chloride with equal mole, reacting for 6 hours at-30 ℃, removing the solvent in vacuum, adding 100ml n-hexane into the residual solid, dissolving and filtering, and recrystallizing the filtrate to obtain 4.90g fluorenyl bis (4-fluorophenyl) phosphine solid with the yield: 42.3 percent.1H NMR(400MHz,CDCl3:7.26ppm):δ＝7.72(m,2H,Fl)；7.32(m,4H,Ph)；7.23(m,6H,Fl)；7.02(m,4H,Ph)；4.16(s,1H,Fl)；Anal.Calcd.(％)for C25H17PF2(386):C,77.71；H,4.43；found:C,77.69；H,4.42；ESI-MS m/z calculated for[M-H]-.C25H17PF2:386.10,found,385.10。
(2) Preparation of the procatalyst
20ml of toluene and 1g of ligand L5 were put into a 300ml schlenk bottle, n-butyllithium equimolar to the ligand was added at-30 ℃ and stirred to react for 4 hours, and SmCl equimolar to the ligand was added3Reacting with-30 deg.C for 5 hr, removing solvent under vacuum, washing with 300ml n-hexane for 3 times, and vacuum drying to obtainCatalyst (5) in 62.7% yield.1H NMR(400MHz,CDCl3:7.26ppm):δ＝7.46(m,4H,Ph)；7.15(m,4H,Ph)；6.70(m,2H,Fl)；6.58(m,6H,Fl)；Anal.Calcd.(％)for C25H16Cl2F2PSm(606):C,49.50；H,2.66；found:C,49.46；H,2.67。
(3) Ethylene polymerization:
A2L stainless steel autoclave is fully replaced by nitrogen under anhydrous and anaerobic conditions, 1L heptane is added into the autoclave, 3mg catalyst (5) and 6mL (10 wt%) MAO solution are added, 0.2L hydrogen is charged, ethylene is charged to the pressure of 0.7MPa, the mixture is stirred, the temperature is raised to 90 ℃ for reaction for 1 hour, and 273 g polymerization product is collected.
(4) Ethylene copolymerization:
A2L stainless steel autoclave is fully replaced by nitrogen under anhydrous and anaerobic conditions, 1L heptane is added into the autoclave, 3mg catalyst (5), 6mL (10 wt%) MAO solution and 80mL 1-hexene are added, 0.2L hydrogen is charged, ethylene is charged to 0.5MPa, the mixture is stirred, the temperature is raised to 100 ℃ for reaction for 1 hour, and 236 g polymerization product is collected.
Example 6
(1) Synthesis of ligand compound L6 [ L6 structure: in the general formula (6)Taking tetrahydroindenyl, R1、R2To obtain phenyl]
Taking 40ml tetrahydrofuran and 3.61g 4,5,6, 7-tetrahydroindene, adding equimolar n-butyl lithium at-10 ℃ in a 300ml schlenk bottle, stirring, reacting for 8 hours, adding equimolar diphenyl phosphine chloride, reacting for 6 hours at-30 ℃, removing the solvent in vacuum, adding 100ml n-hexane to the residual solid, dissolving and filtering, and recrystallizing the filtrate to obtain 6.02g tetrahydroindenyl diphenylphosphine solid, wherein the yield is as follows: 65.9 percent.1H NMR(400MHz,CDCl3:7.26ppm):δ＝7.38(m,4H,Ph)；7.28(m,6H,Ph)；7.02(d,1H,In)；6.66(m,1H,In)；4.35(d,1H,In)；2.55(m,2H,In)；2.01(t,2H,In)；1.71(m,2H,In)；1.59(m,2H,In)；Anal.Calcd.(％)for C21H21P(304):C,82.87；H,6.95；found:C,82.88；H,6.93；ESI-MS m/z calculated for[M+H]+.C21H21P:304.14,found,305.14。
(2) Preparation of the procatalyst
20ml of toluene and 1g of ligand L6 are taken in a 300ml schlenk bottle, n-butyllithium which is equimolar with the ligand is added at-30 ℃, the mixture is stirred and reacted for 4 hours, and TiCl which is equimolar with the ligand is added4The reaction was carried out at-30 ℃ for 5 hours, the solvent was removed in vacuo, washed 3 times with 300ml of n-hexane and dried in vacuo to obtain catalyst (6) in 51.8% yield.1H NMR(400MHz,CDCl3:7.26ppm):δ＝7.35(m,4H,Ph)；7.29(m,6H,Ph)；3.66(d,1H,In)；3.03(d,1H,In)；1.73(m,2H,In)；1.53(m,6H,In)；Anal.Calcd.(％)for C21H20Cl3PTi(457):C,55.12；H,4.41；found:C,55.12；H,4.40。
(3) Ethylene polymerization:
A2L stainless steel autoclave was fully replaced with nitrogen under anhydrous and oxygen-free conditions, 1L toluene was added to the autoclave, 5mg catalyst (6), 2mL (10 wt%) MAO solution, 1mL triethylaluminum (1.5M hexane solution), 0.1L hydrogen was charged, ethylene was charged to a pressure of 0.7MPa, stirring was carried out, the temperature was raised to 125 ℃ for 2 hours, and 283 g polymerization product was collected.
(4) Ethylene copolymerization:
A2L stainless steel autoclave was fully replaced with nitrogen under anhydrous and oxygen-free conditions, 1L toluene was added to the autoclave, 5mg catalyst (6), 2mL (10 wt%) MAO solution, 1mL triethylaluminum (1.5M in hexane), 80mL 1-hexene, 0.2L hydrogen was charged, ethylene was charged to a pressure of 0.6MPa, stirring was carried out, the temperature was raised to 125 ℃ for 2 hours, and 246 g polymerization product was collected.
Example 7
(1) Synthesis of ligand compound L7 [ L7 structure: in the general formula (6)Taking hydrogenated fluorenyl radical, R1、R2Taking 2,4, 6-trimethylphenyl]
40ml of tetrahydrofuran and 5.23g of octahydrofluorene were taken in a 300ml schlenk flask and equimolar amounts of tetrahydrofuran and octahydrofluorene were added at-10 ℃N-butyllithium, stirred, reacted for 8 hours, added with bis (2,4, 6-trimethylphenyl) phosphonium chloride equimolar thereto, reacted for 6 hours at-30 ℃, the solvent was removed in vacuo, 100ml of n-hexane was added to the remaining solid, dissolved, filtered, and the filtrate was recrystallized to obtain 9.63g of hydrogenated fluorenyl bis (2,4, 6-trimethylphenyl) phosphine solid, yield: 72.5 percent.1H NMR(400MHz,CDCl3:7.26ppm):δ＝6.76(s,4H,Ph)；4.66(s,1H,Fl)；2.32(s,6H,-CH3)；2.26(m,4H,Fl)；2.18(s,12H,-CH3)；2.08(t,4H,Fl)；1.68(m,8H,Fl)；Anal.Calcd.(％)for C31H39P(442):C,84.12；H,8.88；found:C,84.10；H,8.88；ESI-MS m/z calculated for[M+H]+.C31H39P:442.28,found,443.28。
(2) Preparation of the procatalyst
20ml of toluene and 1g of ligand L7 were put in a 300ml schlenk flask, n-butyllithium equimolar to the ligand was added at-30 ℃ and stirred to react for 4 hours, and CeCl equimolar to the ligand was added3The reaction was carried out at-30 ℃ for 5 hours, the solvent was removed in vacuo, washed 3 times with 300ml of n-hexane and dried in vacuo to obtain catalyst (7) in 52.5% yield.1H NMR(400MHz,CDCl3:7.26ppm):δ＝6.78(s,4H,Ph)；2.18(s,6H,-CH3)；2.06(s,12H,-CH3)；1.55(m,16H,Fl)；Anal.Calcd.(％)for C31H38Cl2PCe(652):C,57.05；H,5.87；found:C,57.03；H,5.88。
(3) Ethylene polymerization:
A2L stainless steel autoclave is fully replaced by nitrogen under anhydrous and anaerobic conditions, 1L toluene is added into the autoclave, 5mg catalyst (7), 2mL (10 wt%) MAO solution and 1mL tri-n-hexylaluminum (1.5M hexane solution) are added, 0.05L hydrogen is charged, ethylene is charged to 0.7MPa pressure, stirring is carried out, the temperature is increased to 115 ℃ for reaction for 2 hours, and 288 g polymerization product is collected.
(4) Ethylene copolymerization:
A2L stainless steel autoclave is fully replaced by nitrogen under anhydrous and anaerobic conditions, 1L toluene is added into the autoclave, 5mg catalyst (7), 2mL (10 wt%) MAO solution, 1mL tri-n-hexylaluminum (1.5M hexane solution), 68mL 4-methyl-1-pentene, 0.05L hydrogen is filled, ethylene is filled to the pressure of 0.7MPa, stirring is carried out, the temperature is increased to 115 ℃ for reaction for 2 hours, and 258 g polymerization product is collected.
Example 8
(1) Synthesis of ligand compound L8 [ L8 structure: in the general formula (6)Taking indenyl, R1、R2Taking cyclohexyl]
40ml of tetrahydrofuran and 3.6ml of indene were taken in a 300ml schlenk flask, equimolar n-butyllithium was added at-10 ℃, stirred and reacted for 8 hours, and equimolar dicyclohexylphosphine chloride was added and reacted for 6 hours at-30 ℃, the solvent was removed in vacuo, 100ml of n-hexane was added to the remaining solid, dissolved and filtered, and the filtrate was recrystallized to obtain 7.65g of indenyl dicyclohexylphosphine solid, yield: 81.6 percent.1H NMR(400MHz,CDCl3:7.26ppm):δ＝7.28(m,4H,In)；7.06(d,1H,In)；6.36(m,1H,In)；4.66(d,1H,In)；2.02(m,2H,Cy)；1.53-1.12(m,20H,Cy)；Anal.Calcd.(％)for C21H29P(312):C,80.73；H,9.36；found:C,80.70；H,9.35；ESI-MS m/z calculated for[M+H]+.C21H29P:312.20,found,313.20。
(2) Preparation of the procatalyst
20ml of toluene and 1g of ligand L8 were put in a 300ml schlenk flask, n-butyllithium equimolar to the ligand was added at-30 ℃ and stirred to react for 4 hours, and RhCl equimolar to the ligand was added3The reaction was carried out at-30 ℃ for 5 hours, the solvent was removed in vacuo, washed 3 times with 300ml of n-hexane and dried in vacuo to obtain catalyst (8) in 55.8% yield.1H NMR(400MHz,CDCl3:7.26ppm):δ＝6.69(m,1H,In)；6.56(m,2H,In)；6.39(m,1H,In)；4.08(d,1H,In)；3.45(d,1H,In)；2.06(m,2H,Cy)；1.33-1.02(m,20H,Cy)；Anal.Calcd.(％)for C21H28Cl2PRh(485):C,51.98；H,5.82；found:C,51.96；H,5.83。
(3) Ethylene polymerization:
under the anhydrous and anaerobic condition, a 2L stainless steel autoclave is fully replaced by nitrogen, 1L cyclohexane is added into the autoclave, 8mg catalyst (8) and 5mL (10 wt%) MAO solution are added, 0.05L hydrogen is filled, ethylene is filled to the pressure of 0.7MPa, the mixture is stirred, the temperature is increased to 160 ℃ for reaction for 2 hours, and 349 g polymerization product is collected.
(4) Ethylene copolymerization:
under anhydrous and anaerobic conditions, a 2L stainless steel autoclave is fully replaced by nitrogen, 1L cyclohexane is added into the autoclave, 8mg catalyst (8), 5mL (10 wt%) MAO solution, 1mL tri-n-hexylaluminum (1.5M hexane solution), 120mL 1-octene are added, 0.05L hydrogen is filled, ethylene is filled to the pressure of 0.7MPa, the mixture is stirred, the temperature is increased to 160 ℃ for reaction for 2 hours, and 317 g of polymerization product is collected.
Example 9
(1) Synthesis of ligand compound L9 [ L9 structure: in the general formula (6)Taking 5-methylindenyl, R1、R2Butyl of tert]
40ml of tetrahydrofuran and 3.91g of 5-methylindene were taken in a 300ml schlenk flask, equimolar n-butyllithium was added at-10 ℃ and stirred to react for 8 hours, equimolar di-tert-butylphosphine chloride was added to react with-30 ℃ for 6 hours, the solvent was removed in vacuo, 100ml of n-hexane was added to the remaining solid, dissolved and filtered, and the filtrate was recrystallized to give 6.22g of 5-methylindenyl di-tert-butylphosphine as a solid, yield: 75.6 percent.1H NMR(400MHz,CDCl3:7.26ppm):δ＝7.12(d,1H,In)；7.08(m,1H,In)；6.98(d,1H,In)；6.88(d,1H,In)；6.38(t,1H,In)；4.36(d,1H,In)；2.08(s,3H,In-CH3)；0.82(s,18H,tBu)；Anal.Calcd.(％)for C18H27P(274):C,78.79；H,9.92；found:C,78.78；H,9.90；ESI-MS m/z calculated for[M+H]+.C18H27P:274.19,found,275.19。
(2) Preparation of the procatalyst
20ml of toluene and 1g of ligand L9 were taken in a 300ml schlenk flask, n-butyllithium equimolar to the ligand was added at-30 ℃, stirred, reacted for 4 hours, and VCl equimolar to the ligand was added4And-30After 5 hours of reaction, the solvent was removed in vacuo, washed 3 times with 300ml of n-hexane and dried in vacuo to obtain catalyst (9) in 67.3% yield.1H NMR(400MHz,CDCl3:7.26ppm):δ＝6.68(m,1H,In)；6.51(dd,1H,In)；6.26(m,1H,In)；3.86(d,1H,In)；3.39(d,1H,In)；1.86(m,3H,In-CH3)；0.82(s,18H,tBu)；Anal.Calcd.(％)for C18H26Cl3PV(430):C,50.20；H,6.09；found:C,50.18；H,6.06。
(3) Ethylene polymerization:
A2L stainless steel autoclave is fully replaced by nitrogen under anhydrous and anaerobic conditions, 1L xylene is added into the autoclave, 6mg catalyst (9) and 8mL (10 wt%) MAO solution are added, 0.05L hydrogen is filled, ethylene is filled to the pressure of 0.8MPa, the mixture is stirred, the temperature is raised to 130 ℃ for reaction for 1 hour, and 236 g polymerization product is collected.
(4) Ethylene copolymerization:
A2L stainless steel autoclave was fully replaced with nitrogen under anhydrous and oxygen-free conditions, 1L xylene was added to the autoclave, 6mg catalyst (9) was added, 8mL (10 wt%) MAO solution, 42g ethylidene norbornene was charged, 0.05L hydrogen was charged, ethylene was charged to 0.8MPa pressure, stirred, heated to 130 deg.C for 2 hours, and 202 g polymerization product was collected.
Example 10
(1) Synthesis of ligand compound L10 [ L10 structure: in the general formula (6)Taking a sulfur-bridged benzo cyclopentadienyl, R1、R2Taking 3, 5-difluorophenyl]
40ml of tetrahydrofuran, 5.16g of benzo [ b ]]Cyclopentylthiophene in a 300ml schlenk flask, equimolar n-butyllithium was added at-10 ℃ and stirred to react for 8 hours, and then equimolar bis (3, 5-difluorophenyl) phosphine chloride was added to react with-30 ℃ for 6 hours, the solvent was removed in vacuo, 100ml of n-hexane was added to the remaining solid, dissolved and filtered, and the filtrate was recrystallized to give 6.75g of a thiobenzocyclopentadienylbis (3, 5-difluorophenyl) phosphine solid, yield: 52.5 percent.1H NMR(400MHz,CDCl3:7.26ppm):δ＝7.85(m,1H,-Cp)；7.73(m,1H,-Cp)；7.42(m,1H,-Cp)；7.34(m,1H,-Cp)；7.18(d,4H,Ph)；6.99(d,1H,-Cp)；6.88(t,2H,Ph)；6.56(m,1H,-Cp)；4.39(d,1H,-Cp)；Anal.Calcd.(％)for C23H13PSF4(428):C,64.49；H,3.06；found:C,64.48；H,3.06；ESI-MS m/z calculated for[M-H]-.C23H13PSF4:428.04,found,427.04。
(2) Preparation of the procatalyst
20ml of toluene and 1g of ligand L10 were put into a 300ml schlenk bottle, n-butyllithium equimolar to the ligand was added at-30 ℃, stirred, reacted for 4 hours, and YCl equimolar to the ligand was added3The reaction was carried out at-30 ℃ for 5 hours, the solvent was removed in vacuo, washed 3 times with 300ml of n-hexane and dried in vacuo to obtain the catalyst (10) in 53.9% yield.1H NMR(400MHz,CDCl3:7.26ppm):δ＝7.33(m,1H,-Cp)；7.28(m,1H,-Cp)；7.16(d,4H,Ph)；7.10(dd,1H,-Cp)；6.99(dd,1H,-Cp)；6.85(t,2H,Ph)；3.88(d,1H,-Cp)；3.45(d,1H,-Cp)；Anal.Calcd.(％)for C23H12Cl2PSF4Y(587):C,47.05；H,2.06；found:C,47.06；H,2.05。
(3) Ethylene polymerization:
A2L stainless steel autoclave is fully replaced by nitrogen under anhydrous and anaerobic conditions, 1L toluene is added into the autoclave, 3mg catalyst (10) and 8mL (10 wt%) MAO solution are added, 0.02L hydrogen is filled, ethylene is filled to the pressure of 0.8MPa, the mixture is stirred, the temperature is raised to 135 ℃ for reaction for 1 hour, and 304 g polymerization product is collected.
(4) Ethylene copolymerization:
A2L stainless steel autoclave was fully replaced with nitrogen under anhydrous and oxygen-free conditions, 1L toluene was added to the autoclave, 10mg catalyst (10) and 8mL (10 wt%) MAO solution were added, 30g 1, 7-octadiene was added, 0.5kg propylene was added, 0.05L hydrogen was charged, ethylene was charged to a pressure of 0.8MPa, stirring was carried out, the temperature was increased to 160 ℃ and the reaction was carried out for 1 hour, and 259 g polymerization product was collected.
Example 11
(1) Synthesis of ligand compound L11 [ L11 structure: in the general formula (6)Taking 5-methylindenyl, R1、R2Taking methoxyphenyl]
40ml of tetrahydrofuran and 3.91g of 5-methylindene were taken in a 300ml schlenk flask, equimolar n-butyllithium was added at-10 ℃ and stirred to react for 8 hours, equimolar dimethoxyphenylphosphine chloride was added thereto and reacted at-30 ℃ for 6 hours, the solvent was removed in vacuo, 100ml of n-hexane was added to the remaining solid, dissolved and filtered, and the filtrate was recrystallized to give 7.74g of 5-methylindenyldimethoxyphenyl solid in a yield: 68.9 percent.1H NMR(400MHz,CDCl3:7.26ppm):δ＝7.47(dd,2H,Ph)；7.25(m,3H,In/Ph)；7.21(m,2H,In)；7.08(m,1H,In)；7.02(d,1H,In)；6.98(d,1H,In)；6.92(t,1H,In)；6.76(dd,2H,In)；4.63(d,1H,In)；3.26(s,6H,-CH3)；2.02(s,3H,-CH3)；Anal.Calcd.(％)for C24H23O2P(374):C,76.99；H,6.19；found:C,76.98；H,6.18；ESI-MS m/z calculated for[M+H]+.C24H23O2P:374.14,found,375.14。
(2) Preparation of the procatalyst
20ml of toluene and 1g of ligand L11 were taken in a 300ml schlenk flask, n-butyllithium equimolar to the ligand was added at-30 ℃, stirred, reacted for 4 hours, and VCl equimolar to the ligand was added4The reaction was carried out at-30 ℃ for 5 hours, the solvent was removed in vacuo, washed 3 times with 300ml of n-hexane and dried in vacuo to obtain catalyst (11) in 66.9% yield.1H NMR(400MHz,CDCl3:7.26ppm):δ＝7.38(dd,2H,Ph)；7.16(m,2H,Ph)；7.08(m,2H,Ph)；6.83(dd,2H,Ph)；6.61(m,1H,In)；6.45(dd,1H,In)；6.06(m,1H,In)；3.89(d,1H,In)；3.27(s,6H,-CH3)；3.18(d,1H,In)；1.68(t,3H,-CH3)；Anal.Calcd.(％)for C24H22Cl3O2PV(530):C,54.32；H,4.18；found:C,54.30；H,4.16。
(3) Ethylene polymerization:
A2L stainless steel autoclave is fully replaced by nitrogen under anhydrous and anaerobic conditions, 1L toluene is added into the autoclave, 10mg catalyst (11) and 5mL (10 wt%) MAO solution are added, 0.05L hydrogen is filled, ethylene is filled to the pressure of 0.6MPa, the mixture is stirred, the temperature is increased to 120 ℃ for reaction for 2 hours, and 318 g polymerization product is collected.
(4) Ethylene copolymerization:
A2L stainless steel autoclave was fully replaced with nitrogen under anhydrous and oxygen-free conditions, 1L toluene was added to the autoclave, 10mg catalyst (11), 5mL (10 wt%) MAO solution, 18g 8-bromo-1-octene was charged with 0.05L hydrogen, ethylene was charged to a pressure of 0.8MPa, stirring was carried out, the temperature was increased to 120 ℃ for 2 hours, and 215 g polymer was collected.
Example 12
(1) Synthesis of ligand compound L12 [ L12 structure: r in the general formula (6) is H, R1、R2Taking cyclopentyl]
Taking 40ml tetrahydrofuran and 10ml cyclopentadiene in a 300ml schlenk bottle, adding 0.69g metallic sodium at-10 ℃, stirring, reacting for 8 hours, adding dicyclohexyl phosphine chloride with the molar equivalent to the metallic sodium, reacting for 6 hours at-30 ℃, removing the solvent in vacuum, adding 100ml normal hexane into the residual solid, dissolving and filtering, and recrystallizing the filtrate to obtain 4.70g cyclopentadienyl dicyclohexyl phosphine solid with the yield: 66.8 percent.1H NMR(400MHz,CDCl3:7.26ppm):δ＝6.85(d,2H)；6.26(m,2H)；3.68(t,1H)；2.36(m,2H)；1.68-1.52(m,8H)；1.23(m,8H)；Anal.Calcd.(％)for C15H23P(234):C,76.89；H,9.89；found:C,76.88；H,9.88；ESI-MS m/z calculated for[M+H]+.C15H23P:234.15,found,235.15。
(2) Preparation of the procatalyst
20ml of toluene and 1g of ligand L12 are taken in a 300ml schlenk bottle, n-butyllithium which is equimolar with the ligand is added at-30 ℃, the mixture is stirred and reacted for 4 hours, and TiCl which is equimolar with the ligand is added4The reaction was carried out at-30 ℃ for 5 hours, the solvent was removed in vacuo, washed 3 times with 300ml of n-hexane and dried in vacuo to obtain catalyst (12) in 76.9% yield.1H NMR(400MHz,CDCl3:7.26ppm):δ＝4.08(d,2H)；3.38(d,2H)；2.36(m,2H)；1.54(m,8H)；1.33(m,8H)；Anal.Calcd.(％)for C15H22Cl3PTi(387):C,46.49；H,5.72；found:C,46.46；H,5.70。
(3) Ethylene polymerization:
A2L stainless steel autoclave is fully replaced by nitrogen under anhydrous and anaerobic conditions, 1L toluene is added into the autoclave, 5mg catalyst (12) and 12mL (10 wt%) MAO solution are added, 0.05L hydrogen is filled, ethylene is filled to the pressure of 0.6MPa, the mixture is stirred, the temperature is increased to 110 ℃ for reaction for 2 hours, and 293 g polymerization product is collected.
(4) Ethylene copolymerization:
a2 liter stainless steel autoclave was fully replaced with nitrogen under anhydrous and oxygen-free conditions, 1L of toluene was added to the autoclave, 6mg of catalyst (12), 12mL (10 wt%) of MAO solution, 120mL of 1-octene was 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 110 ℃ for 2 hours, and 269 g of the polymerization product was collected.
Example 13
(1) Synthesis of ligand compound L13 [ L13 structure: in the general formula (6)Taking fluorenyl radical, R1、R2Taking isopropyl]
Taking 40ml tetrahydrofuran and 4.98g fluorene in a 300ml schlenk bottle, adding equimolar n-butyllithium at-10 ℃, stirring, reacting for 8 hours, adding equimolar diisopropyl phosphine chloride, reacting for 6 hours at-30 ℃, removing the solvent in vacuum, adding 100ml n-hexane into the residual solid, dissolving and filtering, and recrystallizing the filtrate to obtain 4.96g fluorenyl diisopropyl phosphine solid with the yield: 58.6 percent.1H NMR(400MHz,CDCl3:7.26ppm):δ＝7.62(d,2H,Fl)；7.29(m,6H,Fl)；4.76(s,1H,Fl)；1.96(m,2H,iPr)；0.86(d,12H,-CH3)；Anal.Calcd.(％)for C19H23P(282):C,80.82；H,8.21；found:C,80.80；H,8.20；ESI-MS m/z calculated for[M+H]+.C19H23P:282.15,found,283.15。
(2) Preparation of the procatalyst
20ml of toluene and 1g of ligand L13 were taken in a 300ml schlenk flask and added equimolar to the ligand at-30 DEGStirring and reacting for 4 hours with n-butyllithium, adding SmCl which is equimolar with ligand3The reaction was carried out at-30 ℃ for 5 hours, the solvent was removed in vacuo, washed 3 times with 300ml of n-hexane and dried in vacuo to obtain catalyst (13) in 59.8% yield.1H NMR(400MHz,CDCl3:7.26ppm):δ＝6.71-6.53(m,8H,Fl)；1.98(m,2H,iPr)；0.83(d,12H,-CH3)；Anal.Calcd.(％)for C19H22Cl2PSm(503):C,45.40；H,4.41；found:C,45.36；H,4.43。
(3) Ethylene polymerization:
A2L stainless steel autoclave was fully replaced with nitrogen under anhydrous and oxygen-free conditions, 1L cyclohexane was added to the autoclave, 8mg catalyst (13) and 8mL (10 wt%) MAO solution were added, 0.05L hydrogen was added, ethylene was added to a pressure of 0.8MPa, the mixture was stirred, the temperature was raised to 170 ℃ and the reaction was carried out for 2 hours, and 238 g of the polymerization product was collected.
(4) Ethylene copolymerization:
A2L stainless steel autoclave was fully replaced with nitrogen under anhydrous and oxygen-free conditions, 1L cyclohexane was added to the autoclave, 8mg catalyst (13), 8mL (10 wt%) MAO solution, 20mL 8-hydroxy-1-octene was charged with 0.05L hydrogen, ethylene was charged to a pressure of 0.7MPa, stirring was carried out, the temperature was raised to 170 ℃ for 2 hours, and 219 g polymer was collected.
Example 14
(1) Synthesis of ligand compound L14 [ L14 structure: in the general formula (6)Taking 5, 7-difluoro-1H-indenyl, R1、R2Taking trifluoromethyl]
40ml of tetrahydrofuran and 4.56g of 5, 7-difluoro-1H-indene were taken in a 300ml schlenk flask, equimolar n-butyllithium was added at-10 ℃ and stirred and reacted for 8 hours, then equimolar bis (trifluoromethyl) phosphine chloride was added and reacted for 6 hours at-30 ℃, the solvent was removed in vacuo, 100ml of n-hexane was added to the remaining solid, dissolved and filtered, and the filtrate was recrystallized to give 6.99g of 5, 7-difluoro-1H-indenyl bis (trifluoromethyl) phosphine as a solid in yield: 72.8 percent.1H NMR(400MHz,CDCl3:7.26ppm):δ＝7.10(d,1H,In)；7.08(d,1H,In)；6.78(d,1H,In)；6.60(m,1H,In)；4.62(d,1H,In)；Anal.Calcd.(％)for C11H5F8P(320):C,41.27；H,1.57；found:C,41.28；H,1.56；ESI-MS m/z calculated for[M-H]-.C11H5F8P:320.00,found,319.01。
(2) Preparation of the procatalyst
20ml of toluene and 1g of ligand L14 are taken in a 300ml schlenk bottle, n-butyllithium which is equimolar with the ligand is added at-30 ℃, the mixture is stirred and reacted for 4 hours, and TiCl which is equimolar with the ligand is added4The reaction was carried out at-30 ℃ for 5 hours, the solvent was removed in vacuo, washed 3 times with 300ml of n-hexane and dried in vacuo to obtain catalyst (14) in 59.6% yield.1H NMR(400MHz,CDCl3:7.26ppm):δ＝6.45(d,1H,In)；6.26(d,1H,In)；3.86(d,1H,In)；3.65(d,1H,In)；Anal.Calcd.(％)for C11H4Cl3PF8Ti(473):C,27.91；H,0.85；found:C,27.89；H,0.86。
(3) Ethylene polymerization:
A2L stainless steel autoclave was fully replaced with nitrogen under anhydrous and oxygen-free conditions, 1L toluene was added to the autoclave, 6mg catalyst (14) and 15mL (10 wt%) MAO solution were added, 0.05L hydrogen was added, ethylene was added to a pressure of 0.7MPa, the mixture was stirred, the temperature was increased to 110 ℃ for 2 hours, and 266 g polymerization product was collected.
(4) Ethylene copolymerization:
A2L stainless steel autoclave was fully replaced with nitrogen under anhydrous and oxygen-free conditions, 1L toluene was added to the autoclave, 6mg catalyst (14), 15mL (10 wt%) MAO solution, 20g 8-chloro-1-octene was charged with 0.05L hydrogen, ethylene was charged to a pressure of 0.7MPa, stirring was carried out, the temperature was increased to 110 ℃ for 2 hours, and 239 g polymer product was collected.
Example 15
(1) Synthesis of ligand compound L15 [ L15 structure: in the general formula (6)Taking tetrahydroindenyl, R1Methoxy radical, R2Taking chlorine]
40ml of tetrahydrofuran and 3.61g of 4,5,6, 7-tetrahydro-1H-indene are taken in a 300ml schlenk flask, equimolar n-butyllithium is added at-10 ℃, stirred, reacted for 8 hours, equimolar methoxyphosphine dichloride is added, reacted for 6 hours at-30 ℃, the solvent is removed in vacuo, 100ml of n-hexane is added to the remaining solid, dissolved and filtered, and the filtrate is recrystallized to obtain 4.73g of tetrahydroindenyl methoxyphosphine chloride solid, the yield: 72.8 percent.1H NMR(400MHz,CDCl3:7.26ppm):δ＝6.98(d,1H,In)；6.60(m,1H,In)；3.81(d,1H,In)；3.26(s,3H,-CH3)；2.58(t,2H,In)；2.02(t,2H,In)；1.66-1.49(m,4H,In)；Anal.Calcd.(％)for C10H14PClO(216):C,55.44；H,6.51；found:C,55.43；H,6.53；ESI-MS m/z calculated for[M-H]-.C10H14PClO:216.05,found,215.05。
(2) Preparation of the procatalyst
20ml of toluene and 1g of ligand L15 were taken in a 300ml schlenk flask, n-butyllithium equimolar to the ligand was added at-30 ℃, stirred, reacted for 4 hours, and VCl equimolar to the ligand was added4The reaction was carried out at-30 ℃ for 5 hours, the solvent was removed in vacuo, washed 3 times with 300ml of n-hexane and dried in vacuo to obtain catalyst (15) in 61.9% yield.1H NMR(400MHz,CDCl3:7.26ppm):δ＝3.87(d,1H,In)；3.82(d,1H,In)；3.36(s,3H,-CH3)；1.63-1.51(m,8H,In)；Anal.Calcd.(％)for C10H13Cl4POV(372):C,32.21；H,3.51；found:C,32.20；H,3.49。
(3) Ethylene polymerization:
A2L stainless steel autoclave is fully replaced by nitrogen under anhydrous and anaerobic conditions, 1L toluene is added into the autoclave, 10mg catalyst (15) and 5mL (10 wt%) MAO solution are added, 0.02L hydrogen is filled, ethylene is filled to the pressure of 0.8MPa, the mixture is stirred, the temperature is raised to 125 ℃ for reaction for 2 hours, and 336 g polymerization product is collected.
(4) And (2) propylene copolymerization:
a2 liter stainless steel autoclave was fully replaced with nitrogen under anhydrous and oxygen-free conditions, 1L of toluene was added to the autoclave, 10mg of catalyst (15), 5mL (10 wt%) of MAO solution, 110mL of 1-hexene, 1.1kg of propylene was charged, 0.02L of hydrogen was charged, the mixture was stirred, the temperature was raised to 125 ℃ for 2 hours, and 297 g of a polymerization product was collected.
Example 16
(1) Synthesis of ligand compound L16 [ L16 structure: r in the general formula (6) is H, R1、R2Taking 2-isopropoxyphenyl]
Taking 40ml tetrahydrofuran and 10ml cyclopentadiene in a 300ml schlenk bottle, adding 0.69g metallic sodium at-10 ℃, stirring, reacting for 8 hours, adding bis (2-isopropoxyphenyl) phosphine chloride which is equimolar with the metallic sodium, reacting for 6 hours at-30 ℃, removing the solvent in vacuum, adding 100ml n-hexane into the residual solid, dissolving and filtering, and recrystallizing the filtrate to obtain 7.50g cyclopentadienyl bis (2-isopropoxyphenyl) phosphine solid with the yield: 68.2 percent.1H NMR(400MHz,CDCl3:7.26ppm):δ＝7.60(dd,2H,Ph)；7.23(m,4H,Ph)；6.98(d,2H,Cp)；6.62(m,2H,Ph)；6.45(m,2H,Cp)；4.88(t,1H,Cp)；4.59(m,2H,-CH)；1.32(d,12H,-CH3)；Anal.Calcd.(％)for C23H27PO2(366):C,75.39；H,7.43；found:C,75.36；H,7.43；ESI-MS m/z calculated for[M+H]+.C23H27PO2:366.17,found,367.17。
(2) Preparation of the procatalyst
20ml of toluene and 1g of ligand L16 were put into a 300ml schlenk flask, n-butyllithium equimolar to the ligand was added at-30 ℃ and stirred to react for 4 hours, and NdCl equimolar to the ligand was added3The reaction was carried out at-30 ℃ for 5 hours, the solvent was removed in vacuo, washed 3 times with 300ml of n-hexane and dried in vacuo to obtain catalyst (16) in 69.9% yield.1H NMR(400MHz,CDCl3:7.26ppm):δ＝7.52(m,2H,Ph)；7.16(m,4H,Ph)；6.80(m,2H,Ph)；4.59(m,2H,-CH)；3.36(d,2H,Cp)；2.54(d,2H,Cp)；1.10(d,12H,-CH3)；Anal.Calcd.(％)for C23H26Cl2PNdO2(580):C,47.58；H,4.51；found:C,47.56；H,4.53。
(3) Ethylene polymerization:
A2L stainless steel autoclave is fully replaced by nitrogen under anhydrous and anaerobic conditions, 1L toluene is added into the autoclave, 10mg catalyst (16) and 15mL (10 wt%) MAO solution are added, 0.05L hydrogen is filled, ethylene is filled to the pressure of 0.6MPa, the mixture is stirred, the temperature is increased to 180 ℃ for reaction for 2 hours, and 319 g polymerization product is collected.
(4) Ethylene copolymerization:
A2L stainless steel autoclave was fully replaced with nitrogen under anhydrous and oxygen-free conditions, 1L toluene was added to the autoclave, 10mg catalyst (16), 15mL (10 wt%) MAO solution, 65mL styrene, 0.05L hydrogen was charged, ethylene was charged to a pressure of 0.6MPa, stirred, heated to 180 ℃ for 2 hours, and 238 g polymerization product was collected.
Example 17
(1) Synthesis of ligand compound L17 [ L17 structure: in the general formula (6)Taking 1,2, 4-trimethyl cyclopentadiene, R1、R2Taking pentafluorophenyl]
Taking 40ml tetrahydrofuran, 3.25g1,2, 4-trimethyl cyclopentadiene in a 300ml schlenk bottle, adding 0.69g metallic sodium at-10 ℃, stirring, reacting for 8 hours, adding bis (pentafluorophenyl) phosphonium chloride which is equimolar with the metallic sodium, reacting for 6 hours at-30 ℃, removing the solvent in vacuum, adding 100ml n-hexane to the residual solid, dissolving and filtering, and recrystallizing the filtrate to obtain 9.66g1,2, 4-trimethyl cyclopentadienyl bis (pentafluorophenyl) phosphonium solid with the yield: 68.2 percent.1H NMR(400MHz,CDCl3:7.26ppm):δ＝6.66(m,1H,Cp)；5.23(m,1H,Cp)；2.08(d,3H,-CH3)；1.92(d,3H,-CH3)；1.81(t,3H,-CH3)；Anal.Calcd.(％)for C20H11PF10(472):C,50.87；H,2.35；found:C,50.86；H,2.33；ESI-MS m/z calculated for[M-H]-.C20H11PF10:472.04,found,471.04。
(2) Preparation of the procatalyst
20ml of toluene and 1g of ligand L17 were put in a 300ml schlenk flask, n-butyllithium equimolar to the ligand was added at-30 ℃ and stirred to react for 4 hours, and then, n-butyllithium equimolar to the ligand was addedHfCl4The reaction was carried out at-30 ℃ for 5 hours, the solvent was removed in vacuo, washed 3 times with 300ml of n-hexane and dried in vacuo to obtain catalyst (17) in 56.6% yield.1H NMR(400MHz,CDCl3:7.26ppm):δ＝3.47(s,1H,Cp)；0.96(s,3H,-CH3)；0.78(d,6H,-CH3)；Anal.Calcd.(％)for C20H10Cl3F10HfP(756):C,31.77；H,1.33；found:C,31.76；H,1.33。
(3) Ethylene polymerization:
A2L stainless steel autoclave was fully replaced with nitrogen under anhydrous and anaerobic conditions, 1L toluene was added to the autoclave, 5mg catalyst (17) and 5mL (10 wt%) MAO solution were added, 0.05L hydrogen was added, ethylene was added to a pressure of 1.2MPa, the mixture was stirred, the temperature was increased to 110 ℃ for 2 hours, and 279 g polymerization product was collected.
(4) Ethylene copolymerization:
A2L stainless steel autoclave was fully replaced with nitrogen under anhydrous and oxygen-free conditions, 1L toluene was added to the autoclave, 5mg catalyst (17) and 5mL (10 wt%) MAO solution were added, 25g hydroxynorbornene was added, 0.8kg propylene was added, 0.05L hydrogen was added, ethylene was added to a pressure of 1.2MPa, stirring was carried out, the temperature was increased to 110 ℃ for 2 hours, and 258 g polymer was collected.
Example 18
(1) Synthesis of ligand compound L18 [ L18 structure: in the general formula (6)Taking 5-fluoro 1H indenyl, R1、R2Taking 3, 5-difluorophenyl]
40ml of tetrahydrofuran and 4.02g of 5-fluoro-1H indene are taken in a 300ml schlenk flask, equimolar n-butyllithium is added at-10 ℃ and stirred to react for 8 hours, then equimolar bis (3, 5-difluorophenyl) phosphine chloride is added to react with the solution at-30 ℃ for 6 hours, the solvent is removed in vacuo, 100ml of n-hexane is added to the remaining solid, the solution is dissolved and filtered, and the filtrate is recrystallized to obtain 7.76g of 5-fluoro-1H indenyl bis (3, 5-difluorophenyl) phosphine as a solid with the yield: 66.3 percent.1H NMR(400MHz,CDCl3:7.26ppm):δ＝7.39(d,1H,In)；7.24(d,1H,In)；7.18(d,4H,Ph)；7.06(m,1H,In)；6.90(t,2H,Ph)；6.88(d,1H,In)；6.58(t,1H,In)；5.69(d,1H,In)；Anal.Calcd.(％)for C21H12F5P(390):C,64.63；H,3.10；found:C,64.66；H,3.12；ESI-MS m/z calculated for[M-H]-.C21H12F5P:390.06,found,389.06。
(2) Preparation of the procatalyst
20ml of toluene and 1g of ligand L18 were put into a 300ml schlenk bottle, n-butyllithium equimolar to the ligand was added at-30 ℃, stirred, reacted for 4 hours, and YCl equimolar to the ligand was added3The reaction was carried out at-30 ℃ for 5 hours, the solvent was removed in vacuo, washed 3 times with 300ml of n-hexane and dried in vacuo to obtain catalyst (18) in 59.6% yield.1H NMR(400MHz,CDCl3:7.26ppm):δ＝7.10(d,4H,Ph)；6.88(t,2H,Ph)；6.76(dd,1H,In)；6.55(dd,1H,In)；6.32(m,1H,In)；3.94(d,1H,In)；3.82(d,1H,In)；Anal.Calcd.(％)for C21H11Cl2F5PY(549):C,45.94；H,2.02；found:C,45.95；H,2.02。
(3) Ethylene polymerization:
A2L stainless steel autoclave is fully replaced by nitrogen under anhydrous and anaerobic conditions, 1L xylene is added into the autoclave, 5mg catalyst (18) and 5mL (10 wt%) MAO solution are added, 0.3L hydrogen is filled, ethylene is filled to the pressure of 0.8MPa, the mixture is stirred, the temperature is raised to 155 ℃ for reaction for 2 hours, and 232 g polymerization product is collected.
(4) Ethylene copolymerization:
A2L stainless steel autoclave was fully replaced with nitrogen under anhydrous and oxygen-free conditions, 1L xylene was added to the autoclave, 5mg catalyst (18), 5mL (10 wt%) MAO solution, 115mL 1-octene was charged with 0.3L hydrogen, ethylene was charged to a pressure of 0.8MPa, stirred, heated to 155 ℃ for 2 hours, and 197 g of polymerization product was collected.
Example 19
(1) Synthesis of ligand compound L19 [ L19 structure: in the general formula (6)Taking hydrogenated fluorenyl radicals，R1、R2Taking 4-trifluoromethylphenyl]
40ml of tetrahydrofuran and 5.23g of octahydro-1H-fluorene are taken in a 300ml schlenk flask, equimolar n-butyllithium is added at-10 ℃, stirred and reacted for 8 hours, then equimolar bis (4-trifluoromethylphenyl) phosphine chloride is added and reacted for 6 hours at-30 ℃, the solvent is removed in vacuum, 100ml of n-hexane is added to the residual solid, dissolved and filtered, and the filtrate is recrystallized to obtain 9.81g of hydrogenated fluorenyl bis (2,4, 6-trimethylphenyl) phosphine solid, the yield is: 66.1 percent.1H NMR(400MHz,CDCl3:7.26ppm):δ＝7.66(m,8H,Ph)；4.68(s,1H,Fl)；2.28(m,4H,Fl)；2.16(t,4H,Fl)；1.73(m,4H,Fl)；1.58(m,4H,Fl)；Anal.Calcd.(％)for C27H25F6P(494):C,65.59；H,5.10；found:C,65.55；H,5.13；ESI-MS m/z calculated for[M-H]-.C27H25F6P:494.16,found,493.16。
(2) Preparation of the procatalyst
20ml of toluene and 1g of ligand L19 were put in a 300ml schlenk flask, n-butyllithium equimolar to the ligand was added at-30 ℃ and stirred to react for 4 hours, and CeCl equimolar to the ligand was added3The reaction was carried out at-30 ℃ for 5 hours, the solvent was removed in vacuo, washed 3 times with 300ml of n-hexane and dried in vacuo to obtain catalyst (19) in 63.9% yield.1H NMR(400MHz,CDCl3:7.26ppm):δ＝7.68(m,4H,Ph)；7.56(m,4H,Ph)；1.63(m,16H,Fl)；Anal.Calcd.(％)for C27H24Cl2CeF6P(704):C,46.03；H,3.43；found:C,46.00；H,3.45。
(3) Ethylene polymerization:
a2 liter stainless steel autoclave was fully replaced with nitrogen under anhydrous and oxygen-free conditions, 1L of toluene was added to the autoclave, 5mg of catalyst (7), 2mL (10 wt%) of MAO solution, 1mL (1.5M hexane solution) of triisobutylaluminum was added, 0.1L of hydrogen was charged, ethylene was charged to a pressure of 0.6MPa, stirring was performed, the temperature was raised to 100 ℃ for reaction for 2 hours, and 294 g of a polymerization product was collected.
(4) Ethylene copolymerization:
a2 liter stainless steel autoclave was fully replaced with nitrogen under anhydrous and oxygen-free conditions, 1L of toluene was added to the autoclave, 5mg of catalyst (19), 2mL (10 wt%) of MAO solution, 1mL (1.5M hexane solution) of triisobutylaluminum, 95mL of 3-methyl-1-butene was added, 0.1L of hydrogen was charged, ethylene was charged to a pressure of 0.6MPa, stirring was carried out, the temperature was raised to 100 ℃ for reaction for 2 hours, and 266 g of polymerization product was collected.
Comparative example 1
A2L stainless steel autoclave is fully replaced by nitrogen under anhydrous and anaerobic conditions, 1L toluene is added into the autoclave, 10mg of dimethylsilicon-bridged bisindenyl zirconium dichloride metallocene catalyst and 15mL (10 wt%) of MAO solution are added, 0.1L hydrogen is filled, ethylene is filled to the pressure of 0.8MPa, the mixture is stirred, the temperature is raised to 130 ℃ and the reaction is carried out for 2 hours, and no polymer is generated.
Comparative example 2
Under the anhydrous and anaerobic condition, a 2L stainless steel autoclave is fully replaced by nitrogen, 1L xylene is added into the reaction kettle, 8mg of dimethyl silicon bridged cyclopentadienyl tert-butylamino titanium dichloride metallocene catalyst, 10mL (10 wt%) of MAO solution and 30mL of 1-hexene are added, 0.15L hydrogen is filled, ethylene is filled to the pressure of 0.7MPa, the mixture is stirred, the temperature is raised to 130 ℃ for reaction for 2 hours, and 68 g of polymerization product is collected.
Comparative example 3
Under the anhydrous and anaerobic condition, a 2L stainless steel autoclave is fully replaced by nitrogen, 1L toluene is added into the autoclave, 5mg cyclopentadienyl titanium trichloride metallocene catalyst and 5mL (10 wt%) MAO solution and 20mL 1-octene are added, 0.1L hydrogen is filled, the pressure of ethylene is filled to 0.8MPa, the mixture is stirred, the temperature is increased to 110 ℃ for reaction for 2 hours, and 39 g polymerization product is collected.
The results are shown in Table 1.
TABLE 1
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