A phosphazene mono-metallocene catalyst, its preparation method and application

Abstract

The present invention discloses a phosphazene mono-metallocene catalyst, a preparation method thereof and an application thereof. The phosphazene mono-metallocene catalyst has a structural expression shown by the following formula. The phosphazene mono-metallocene catalyst proposed by the present invention has very excellent polymerization activity in catalyzing the copolymerization of cycloolefins, and at the same time has good copolymerization performance, a high cycloolefin insertion rate, and the polyolefin product has an ultra-high molecular weight, having significant application advantages. #imgabs0#

Description

Technical Field

[0001] The present invention relates to a polyolefin catalyst, and particularly to a phosphazene mono-metallocene catalyst and its preparation method and application. Background Art

[0002] Cycloolefin copolymer, abbreviated as COC, is a kind of high-value-added thermoplastic engineering plastic formed by copolymerization of ethylene and cycloolefin, and has advantages such as high transparency, low dielectric constant, excellent heat resistance, chemical resistance, melt fluidity, barrier property and dimensional stability. Cycloolefin copolymers are widely used in the manufacture of various optical lens prisms, automobile headlights, optical films for liquid crystal displays, contact lenses, etc. In addition, cycloolefin copolymer resins also have extremely low dielectric constants and can be used in the manufacture of electronic and electrical components, and also become emerging pharmaceutical and food packaging materials due to their good moisture barrier properties. The catalysts used for synthesizing cycloolefin copolymers mainly include metallocene catalysts (Macromolecules 1998, 31, 4669-4673), constrained geometry catalysts (Macromolecules 1999, 32, 2816-2825), mono-metallocene catalysts (Polym. Chem. 2020, 11, 5590-5600), and transition metal complex catalysts developed in recent years (Coord. Chem. Rev. 2008, 252, 1842-1869), which have high polymerization activity and copolymerization performance, but the polymers prepared by them have relatively low molecular weights, only in the range of 10-500 kg·mol -1 , and improving product added value and preparing high-end polyolefin products are important means to break the current predicament.

[0003] The purpose of the present invention is to provide a cycloolefin copolymerization catalyst with high activity and high copolymerization ability, which is beneficial to the preparation of polyolefin products with ultra-high molecular weight. Summary of the Invention

[0004] To solve the above technical problems, the present invention proposes a phosphazene mono-metallocene catalyst and its preparation method and application.

[0005] Based on the first aspect of the present invention, the present invention first proposes a phosphazene mono-metallocene catalyst. By changing the electronic effect and steric effect between the metallocene ring structure and the phosphazene imine ligand structure in the mono-metallocene catalyst containing a phosphazene ligand, the activity of the catalyst is adjusted to catalytically prepare high-performance cycloolefin polymer materials.

[0006] Based on the second aspect of the present invention, the present invention also proposes a preparation method of a phosphazene mono-metallocene catalyst, which can generate catalyst ligands only through two-step reactions, and has the advantages of simple process flow, saving production lines and production cycles, and low cost in industrial production.

[0007] Based on the third aspect of the present invention, the present invention also provides an application of the aforementioned phosphazene mono-metallocene catalyst in the preparation of ultra-high molecular weight cycloolefin copolymer. The resulting polyolefin has a higher molecular weight and comonomer insertion rate, and good application performance.

[0008] To achieve the above object, the technical solution adopted by the present invention is as follows:

[0009] A phosphazene mono-metallocene catalyst having a structural expression shown in Formula I:

[0010]

[0011] In Formula I, R 1 -R 5 are each independently selected from hydrogen, C1-C 20 alkyl, C1-C 20 alkoxy, C6-C 20 aryl, C6-C 20 arylalkyl, C1-C 20 alkyl-substituted silyl or cyclopentadienyl, a ring containing 4-20 carbon atoms formed by any adjacent carbon atoms and surrounding substituents;

[0012] R 6 -R 7 、R 6’ -R 7’ 、R 6” -R 7” are each independently selected from hydrogen, halogen, amino, benzyl, C1-C 20 alkyl, C1-C 20 alkoxy, C1-C 20 alkylamino, C6-C 20 aryl, C6-C 20 arylalkyl;

[0013] M is selected from Group IVB elements, preferably selected from titanium, zirconium, hafnium;

[0014] R 8 is selected from C1-C6 alkyl or alkoxy, C2-C 10 unsaturated hydrocarbon group, C6-C 20 aryl or arylalkyl, C3-C 12 silyl or siloxanyl.

[0015] As a preferred embodiment of the present invention, in Formula I, R 1 -R 5 are each independently selected from any one of hydrogen, methyl, tert-butyl, trimethylsilyl, phenyl.

[0016] As a preferred embodiment of the present invention, in formula I, R 6 -R 7 、R 6’ -R 7’ 、R 6” -R 7” are each independently selected from hydrogen, bromine, fluorine, chlorine, methyl, isopropyl, amino, benzyl.

[0017] As a preferred embodiment of the present invention, in formula I, R 6 -R 7 are respectively the same as R 6’ -R 7’ 、R 6” -R 7” .

[0018] As a preferred embodiment of the present invention, in formula I, R 8 is selected from methyl, ethyl, n-propyl, n-butyl, isobutyl, n-pentyl, n-hexyl, methoxy, ethoxy, n-propoxy, n-butoxy, vinyl, propenyl, butenyl, phenyl, biphenyl, 1-naphthyl, benzyl, 2-methylphenyl, 3-methylphenyl, 2,4-dimethylphenyl, 2,6-dimethylphenyl, 2-ethylphenyl, 4-ethylphenyl, 3-ethylphenyl, trimethylsilyl, ethyldimethylsilyl, methoxydimethylsilyl;

[0019] Preferably, R 8 is selected from methyl, ethyl, n-propyl, vinyl, phenyl, trimethylsilyl.

[0020] A method for preparing the phosphazene single metallocene catalyst as described above, comprising the following steps:

[0021] Mix and stir the ligand shown in formula II and the metal organic compound shown in formula III in an anhydrous solvent, react for 2 - 24 h to form the structure shown in formula IV; then continue to react with at least one of the compounds shown in formula V and formula VI for 2 - 24 h to form the single metallocene catalyst shown in formula I; preferably, at least one of the compounds shown in formula V and formula VI is mixed with the solution of the structure shown in formula IV by dropwise addition under low temperature or ultra-low temperature conditions, and then slowly heated to the reaction temperature. The low temperature or ultra-low temperature conditions are, for example, -78 °C to 25 °C, preferably -78 °C to -5 °C.

[0022]

[0023] R 8 -Li Formula V

[0024] R 8 -MgBr Formula VI

[0025] Wherein, R 1 -R5 and R 6 -R 7 and R 6’ -R 7’ and R 6” -R 7” and R 8 The selection of M is the same as defined in any one of claims 1-5; X is selected from halogens, preferably Cl;

[0026] Preferably, the molar ratio of the ligand shown in formula II to the metal organic compound shown in formula III is 1:(1-1.5);

[0027] Preferably, the molar ratio of the structure shown in formula IV to at least one of the compounds shown in formula V and formula VI is 1:(2-3).

[0028] Preferably, the metal organic compound shown in formula III is, for example but not limited to: pentamethylcyclopentadienyltitanium trichloride, pentamethylcyclopentadienylzirconium trichloride, pentamethylcyclopentadienylhafnium trichloride, cyclopentadienyltitanium trichloride, cyclopentadienylzirconium trichloride, cyclopentadienylhafnium trichloride, indenylhafnium trichloride, indenylzirconium trichloride, indenyltitanium trichloride, etc.

[0029] For the metal organic compound shown in formula III, pentamethylcyclopentadienyltitanium trichloride (Cas: 12129-06-5), pentamethylcyclopentadienylzirconium trichloride (Cas: 75181-07-6), pentamethylcyclopentadienylhafnium trichloride (Cas: 75181-08-7), cyclopentadienyltitanium trichloride (Cas: 1270-98-0), cyclopentadienylzirconium trichloride (Cas: 34767-44-7), cyclopentadienylhafnium trichloride (Cas: 61906-04-5), indenylhafnium trichloride (Cas: 336102-54-6), indenylzirconium trichloride (Cas: 82161-76-0), indenyltitanium trichloride (Cas: 84365-55-9) can be directly purchased as commercially available products.

[0030] Preferably, the compound shown in formula V is selected from one or more of methyllithium, ethyllithium, n-butyllithium, tert-butyllithium, phenyllithium, benzyllithium;

[0031] Preferably, the compound shown in formula VI is selected from one or more of methylmagnesium bromide, ethylmagnesium bromide, n-butylmagnesium bromide, tert-butylmagnesium bromide, benzylmagnesium bromide;

[0032] Preferably, the anhydrous solvent can be one or more of ultra-dry toluene, xylene, pentane, cyclopentane, n-hexane, cyclohexane, n-heptane, methylcyclohexane, octane, isooctane, tetrahydrofuran, diethyl ether; preferably toluene, n-hexane.

[0033] As a preferred embodiment of the present invention, the preparation method of the ligand shown in Formula II is as follows:

[0034]

[0035] In the formula, R 6 -R 7 、R 6’ -R 7’ 、R 6” -R 7” are selected in the same definition as in any one of Claims 1-5;

[0036] Under anhydrous and anaerobic conditions, the compound of Formula VII is reacted with a halogen-containing phosphide for 12-48 h to form a compound of Formula VIII, and then it is continuously heated and reacted with trimethylsilyl azide for 12-48 h to form the ligand shown in Formula II.

[0037] As a preferred embodiment of the present invention, the molar ratio of the compound of Formula VII, the halogen-containing phosphide, and trimethylsilyl azide is 3:1:(1-2);

[0038] Preferably, the halogen-containing phosphide is selected from one or more of phosphorus trichloride, phosphorus tribromide, and phosphorus pentachloride.

[0039] Furthermore, the compound of Formula VII can be, for example, one of the compounds shown by at least one of the following structural expressions:

[0040]

[0041] The reaction solvent applicable to the above system can be one or more of tetrahydrofuran, toluene, dioxane, and n-hexane.

[0042] As a preferred embodiment of the present invention, the reaction temperature of Formula VII and the halogen-containing phosphide is 25-120 °C;

[0043] Preferably, the reaction temperature of the compound of Formula VIII and trimethylsilyl azide is 25-120 °C.

[0044] After the reaction is completed, the reaction solution is cooled, the solvent is drained, and the crude product is separated by rectification at 50-220 °C to obtain a purified product.

[0045] Application of a phosphazene mono-metallocene catalyst as described above or a phosphazene mono-metallocene catalyst prepared by the method as described above in the production of cycloolefin copolymers.

[0046] In a preferred embodiment of the present invention, the phosphazene mono-metallocene catalyst is used to catalyze the polymerization reaction of C2-C 10 olefins and cycloolefins to obtain cycloolefin copolymers.

[0047] The cycloolefin is preferably one or more of norbornene (NBE), cyclopentene (CPE), cyclohexene (CHE), cyclooctene (COE), tricycloundecene (TCUE), dicyclopentadiene (DCPD), and tetracyclododecene (TCD). The C2-C 10 olefin is one or more of ethylene, propylene, styrene, 1-butene, 1-hexene, and 1-octene.

[0048] The polymerization reaction is carried out in the presence of an organoaluminum co - agent and an optional boronating co - agent;

[0049] Preferably, the ratio of the organoaluminum co - agent to the phosphazene mono - metallocene catalyst is 1 - 2000, preferably 2 - 800, based on the metal molar ratio;

[0050] Preferably, the ratio of the boronating co - agent to the phosphazene mono - metallocene catalyst is 0 - 60, preferably 0 - 10, based on the molar ratio of boron element to metal element;

[0051] Preferably, the organoaluminum co - agent is selected from one or more of aluminoxanes, alkylaluminum compounds, and alkylaluminum chlorides;

[0052] Preferably, the aluminoxane is one or more of methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, n - propylaluminoxane, isopropylaluminoxane, n - butylaluminoxane, isobutylaluminoxane, neopentylaluminoxane, n - hexylaluminoxane, and n - octylaluminoxane;

[0053] Preferably, the alkylaluminum compound is one or more of triethylaluminum, triisobutylaluminum, trioctylaluminum, trimethylaluminum, triisohexylaluminum, tripropylaluminum, triisopropylaluminum, tri - n - hexylaluminum, tri - n - butylaluminum, triisobutylaluminum, and tri - n - octylaluminum;

[0054] Preferably, the alkylaluminum chloride is one or more of dichloromethylaluminum, dichloroethylaluminum, monochlorodimethylaluminum, monochlorodiethylaluminum, monochlorodi - n - butylaluminum, monochlorodiisobutylaluminum, dichloro - n - butylaluminum, dichloro - isobutylaluminum, sesqui - n - butylaluminum chloride, sesqui - ethylaluminum chloride, sesqui - methylaluminum chloride, and sesqui - isobutylaluminum chloride.

[0055] Preferably, the boronating co - agent is selected from one or more of tris(pentafluorophenyl)borane, trityltetrakis(pentafluorophenyl)borate, N,N - dimethylanilinium tetrakis(pentafluorophenyl)borate, and N,N - dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate;

[0056] Preferably, the polymerization reaction temperature is 0 - 100 °C, preferably 20 - 70 °C; the polymerization reaction pressure is 1 - 5 atm, preferably 1 - 4 atm;

[0057] Preferably, the amount of the phosphazene monometallocene catalyst added is 0.05-6 μmol / L based on the molar concentration of the metal element in the organic solvent.

[0058] The beneficial effects of the present invention are:

[0059] The phosphazene metallocene catalyst proposed in the present invention has very excellent polymerization activity in catalyzing cycloolefin copolymerization, and has good copolymerization performance, high cycloolefin insertion rate, and the polyolefin product has an ultra-high molecular weight, which has significant application advantages. DETAILED DESCRIPTION

[0060] The present invention is further described below by means of specific examples. The examples described in the present invention are only used to illustrate the present invention and do not limit the scope of the present invention.

[0061] The main raw material information used in the following examples:

[0062] Pyrrolidine: CAS 123-75-1, Beijing Yinuokai Technology Co., Ltd.

[0063] 2-Pyrrolidone: CAS 616-45-5, Anhui Zesheng Technology Co., Ltd.

[0064] (S)-2-Methylpyrrolidine: CAS 59335-84-1, Shanghai MacLean Biochemical Technology Co., Ltd.

[0065] 2,5-Dimethylpyrrolidine: CAS 3378-71-0, Beijing Yinuokai Technology Co., Ltd.

[0066] Pentamethylcyclopentadienyltitanium trichloride: CAS: 12129-06-5, Shanghai Aladdin Biochemical Technology Co., Ltd.

[0067] Cyclopentadienyltitanium trichloride: CAS: 1270-98-0, Shanghai Aladdin Biochemical Technology Co., Ltd.

[0068] Indenylzirconium trichloride: CAS: 82161-76-0, Shanghai Aladdin Biochemical Technology Co., Ltd.

[0069] Methylaluminoxane (MAO): Beijing Bailingwei Technology Co., Ltd.

[0070] Diethylaluminum monochloride (AlEt2Cl): Shanghai Aladdin Biochemical Technology Co., Ltd. Triisobutylaluminum (Al i Bu3): Shanghai Myrel Biochemical Technology Co., Ltd.

[0071] Trityl tetrakis(pentafluorophenyl)borate ([Ph3C][B(C6F5)4]): Shanghai Enfujia Technology Co., Ltd.

[0072] N,N-Dimethylanilinium tetrakis(pentafluorophenyl)borate ([ANMe2][B(C6F5)4]): Shanghai Aladdin Biochemical Technology Co., Ltd.

[0073] Tris(pentafluorophenyl)boron (B(C6F5)3): Shanghai Haohong Biopharmaceutical Technology Co., Ltd. Other raw materials and reagents were purchased from commercial products unless otherwise specified.

[0074] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0075] The compounds in the following examples were characterized by nuclear magnetic resonance (Brucker ARX-400).

[0076] The polymerization activities of the polymers described in the following examples are calculated according to the following formula: polymerization activity = polymer mass / (metal content in catalyst × polymerization time). The melting point of the polymer is measured by conventional DSC (Q2000) method. The weight average molecular weight Mw of the polymer is measured by PL-GPC220 at 160°C. The calculation method of the comonomer insertion rate is referenced to (Macromolecules 1999, 32, 3817).

[0077] In all the following examples and comparative examples, the chemical reactions involved were carried out after nitrogen substitution.

[0078] [Example 1]

[0079]

[0080] The preparation method of phosphazene metallocene catalyst IA is as follows:

[0081] Anhydrous and oxygen-free pyrrolidine (60 mmol) was dissolved in 40 mL of anhydrous and oxygen-free tetrahydrofuran, and phosphorus trichloride (20 mmol) was slowly added dropwise at -78°C. The mixture was reacted at room temperature for 12 hours. The reaction solution was filtered, the filtrate was concentrated and distilled under reduced pressure, and the 140°C fraction was collected to obtain tripyrrolidinophosphorus; tripyrrolidinophosphorus (15 mmol) was dissolved in 20 mL of anhydrous and oxygen-free toluene, and trimethylsilyl azide (22.5 mmol) was added under a nitrogen atmosphere. The mixture was refluxed at 110°C for 12 hours, the solvent was drained, 15 mL of n-hexane was added, and a clear liquid was obtained by filtration. The filtrate was drained, and distilled under reduced pressure. The 137°C fraction was collected to obtain ligand II-A.

[0082] 1 H NMR (400MHz, C6D6): δ3.05(m,12H),1.67–1.27(m,12H),0.43(s,9H).

[0083] Ligand II-A (5.1 mmol) was dissolved in 20 mL of anhydrous toluene, and pentamethylcyclopentadienyltitanium trichloride (5 mmol) was added to obtain a clear solution. The solution was stirred at room temperature for 12 hours to obtain the compound shown in Formula IV-A.

[0084] 1 H NMR (400 MHz, CDCl3): δ 3.25–3.17 (m, 12H), 2.14 (s, 15H), 1.88–1.79 (m, 12H).

[0085] At -78 °C, an ether solution of methyllithium (11 mmol, 1.6 mol / L) was slowly added dropwise to the toluene solution of the compound shown in Formula IV-A. The temperature was slowly raised to room temperature, and the mixture was stirred for 12 hours to obtain a suspension. The solvent was dried by suction, 15 mL of n-hexane was added to extract the product, and the solution was filtered to obtain a clear solution. The solution was dried by suction to obtain a solid powder, namely catalyst I-A (0.62 g, yield 63%).

[0086] 1 H NMR (400 MHz, C6D6): δ 3.32–3.02 (m, 12H), 2.13 (s, 15H), 1.66–1.46 (m, 12H), 0.50 (s, 6H).

[0087]

Example 2

[0088]

[0089] The preparation method of the phosphazene mono-metallocene catalyst I-B is as follows:

[0090] Anhydrous and oxygen-free 2,5-dimethylpyrrolidine (60 mmol) was dissolved in 80 mL of anhydrous and oxygen-free tetrahydrofuran. PCl3 (20 mmol) was slowly added dropwise at -78 °C, and the reaction was carried out at room temperature for 24 hours. The reaction solution was filtered, the filtrate was concentrated and then distilled under reduced pressure, and the fraction at 115 °C was collected to obtain tris(2,5-dimethyl)pyrrolidinylphosphine. Tris(2,5-dimethyl)pyrrolidinylphosphine (15 mmol) was dissolved in 20 mL of anhydrous and oxygen-free toluene, and azidotrimethylsilane (22.5 mmol) was added under a nitrogen atmosphere. The mixture was refluxed at 110 °C for 24 hours. The solvent was dried under reduced pressure, 15 mL of n-hexane was added, and the solution was filtered to obtain a clear liquid. The filtrate was dried under reduced pressure and rectified under reduced pressure, and the fraction at 167 °C was collected to obtain ligand II-B. Ligand II-B (5.1 mmol) was dissolved in 20 mL of anhydrous toluene, and pentamethylcyclopentadienyltitanium trichloride (5 mmol) was added. The mixture was stirred at room temperature for 24 hours. An ethereal solution of methylmagnesium bromide (4.5 mmol, 1 mol / L) was slowly added dropwise at -78 °C, and the temperature was slowly raised to room temperature and stirred for 24 hours to obtain a suspension. The solvent was dried under reduced pressure, 15 mL of n-hexane was added to extract the product, and the solution was filtered to obtain a clear solution. The solution was dried under reduced pressure to obtain a solid powder, which was catalyst I-B (0.74 g, yield 67%).

[0091] 1 H NMR (400 MHz, C6D6): δ 3.51–3.22 (m, 6H), 2.61 (d, J = 8.6 Hz, 9H), 2.57–2.41 (m, 3H), 2.39 (s, 15H), 1.84 (d, J = 8.6 Hz, 9H), 1.51–1.35 (m, 6H), 1.37–1.25 (m, 3H), 1.03 (s, 6H).

[0092]

Example 3

[0093]

[0094] Ligand II-A was prepared in the same manner as in Example 1, and then the phosphazene mono-metallocene catalyst I-C was prepared according to the following method:

[0095] The ligand of formula II-A (5.1 mmol) was dissolved in 20 mL of anhydrous toluene, and cyclopentadienyltitanium trichloride (5 mmol) was added to obtain a clear solution. The mixture was stirred at room temperature for 18 hours. A hexane solution of butyllithium (4.2 mmol, 2.7 mol / L) was slowly added dropwise at -78 °C, and the temperature was slowly raised to room temperature and stirred for 6 hours. The solvent was dried under reduced pressure, 10 mL of n-hexane was added for extraction, and the product was concentrated and recrystallized to obtain a solid powder, which was catalyst I-C (2.12 g, yield 83%).

[0096] 11H NMR (400 MHz, C6D6): δ 6.37 (s, 5H), 3.46–3.16 (m, 12H), 1.82–1.62 (m, 12H), 1.48–1.32 (m, 4H), 1.29–1.22 (m, 4H), 0.98 (m, 4H), 0.90 (t, J = 6.5 Hz, 6H).

[0097]

Example 4

[0098] The ligand II-A was prepared in the same manner as in Example 1, and then the phosphazene mono-metallocene catalyst I-D was prepared according to the following method:

[0099]

[0100] The ligand of formula II-A (5.1 mmol) was dissolved in 20 mL of anhydrous toluene, and zirconium trimethylsilylindenyl trichloride (5 mmol) was added to obtain a clear solution. After stirring at room temperature for 18 hours, a hexane solution of benzyllithium (11 mmol, 1.6 mol / L) was slowly added dropwise at -78 °C, and the temperature was slowly raised to room temperature and stirred for 18 hours to obtain a suspension. The solvent was dried by suction, 15 mL of hexane was added to extract the product, and the solution was filtered to obtain a clear solution. The solution was dried by suction to obtain a solid powder, which was the catalyst I-D (1.8 g, yield 63%).

[0101] 1 1H NMR (400 MHz, C6D6): δ 7.87–7.80 (m, 2H), 7.59–7.48 (m, 2H), 7.28–7.19 (m, 8H), 7.17–7.15 (m, 4H), 7.13 (t, J = 3.4 Hz, 1H), 3.38 (dt, J = 3.9, 1.9 Hz, 12H), 2.81 (dt, J = 11.2, 1.1 Hz, 2H), 2.72 (dd, J = 11.3, 1.1 Hz, 2H), 1.79 (m, 12H).

[0102]

Example 5

[0103] The ligand II-B was prepared in the same manner as in Example 1, and then the phosphazene mono-metallocene catalyst I-E was prepared according to the following method:

[0104]

[0105] The ligand of formula II-B (5.1 mmol) was dissolved in 20 mL of anhydrous toluene, and pentamethylcyclopentadienyl hafnium trichloride (5 mmol) was added to obtain a clear solution. The solution was stirred at room temperature for 18 hours, and then a solution of benzylmagnesium bromide (11 mmol, 1.6 mol / L) in diethyl ether was slowly added dropwise at -78 °C. The temperature was slowly raised to room temperature and stirred for 18 hours to obtain a suspension. The solvent was evaporated, 15 mL of n-hexane was added to extract the product, and the solution was filtered to obtain a clear solution. The solution was evaporated to dryness to obtain a solid powder, which was catalyst I-E (1.91 g, yield 56%).

[0106] 1 1H NMR (400 MHz, C6D6): δ 7.24 (dt, J = 5.3, 1.6 Hz, 6H), 7.17 (m, 4H), 3.67 (t, J = 1.1 Hz, 4H), 3.79–3.65 (m, 3H), 3.62–3.51 (m, 3H), 2.78 (d, J = 6.6 Hz, 9H), 2.72–2.56 (m, 6H), 2.47 (s, 15H), 1.96 (d, J = 6.8 Hz, 9H), 1.69–1.53 (m, 6H).

[0107]

Comparative Example 1

[0108] The following catalyst F was prepared by referring to the method provided in Macromolecules, 1998, 31, 7588–7597.:

[0109]

[0110] 2,2,4,4-Tetramethyl-3-pentanone imine (5 mmol) was dissolved in 50 ml of tetrahydrofuran, and a solution of butyllithium (5.5 mmol, 2.5 mol / L) in n-hexane was slowly added at -78 °C. The temperature was slowly raised to room temperature and stirred for 4 hours. The solvent was evaporated to obtain substance A.

[0111] Substance A was dissolved in 20 mL of toluene and slowly added to a solution of cyclopentadienyl titanium trichloride (4.5 mmol) in 15 mL of anhydrous toluene at -78 °C. The temperature was slowly raised to room temperature and stirred for 12 hours to obtain a suspension. The suspension was filtered, the filtrate was concentrated to 10 mL, 15 mL of n-hexane was added, and recrystallization was carried out at -30 °C to obtain a solid powder, which was catalyst F.

[0112] 1 1H NMR (400 MHz, C6D6): δ 6.12 (s, 5H, C5H5), δ 1.19 (s, 9H) 1.04 (s, 18H, C(CH3)3).

[0113]

Application Example 1

[0114] Add 2 μmol of catalyst I-A, 0.04 mmol of methylaluminoxane (MAO), and 2 μmol of tris(pentafluorophenyl)borate into a 350 mL glass reactor containing a magnetic stir bar in a glove box. Then connect the glass reactor to the polymerization pipeline, purge with nitrogen, evacuate to vacuum, and displace with ethylene gas three times. Adjust the oil bath temperature of the magnetic stirrer in advance to the polymerization temperature of 25 °C. At the reaction temperature, add 30 mL of a 2 mol / L toluene solution of norbornene into the polymerization flask, then introduce ethylene gas, and maintain the reaction pressure at 4 atm by continuously introducing ethylene gas during the polymerization process. After reaching the set reaction time of 1 min, vent the glass reactor, inject 5 mL of acidified ethanol, then pour all the mixed solution in the glass reactor into a large amount of ethanol to precipitate the polymer. Filter to obtain the polymer, wash with a small amount of ethanol, and finally dry under vacuum overnight and weigh.

[0115]

Application Example 2-17

[0116] Prepare polymers respectively by referring to the method substantially the same as that in Application Example 1, with the difference only being the different reaction conditions shown in Table 1. Among them, the molar ratio of Al in the organoaluminum co-catalyst to the metal in the phosphazene mono-cyclopentadienyl metal catalyst is denoted as "Ratio 1", and the molar ratio of B in the optionally added boronated co-catalyst to the metal in the phosphazene mono-cyclopentadienyl metal catalyst is denoted as "Ratio 2".

[0117]

Comparative Application Example 1

[0118] Prepare a polymer by referring to the method substantially the same as that in Application Example 3, with the difference only being that phosphazene mono-cyclopentadienyl metal catalyst A is replaced with catalyst F of the same molar amount.

[0119]

Comparative Application Example 2

[0120] Prepare a polymer by referring to the method substantially the same as that in Application Example 3, with the difference only being that phosphazene mono-cyclopentadienyl metal catalyst A is replaced with catalyst G of the same molar amount.

[0121] Test the polymerization performance in each application example, and the results are shown in Table 2.

[0122] Table 1. Different reaction conditions in Application Examples 1-17 and Comparative Application Examples 1-2

[0123]

[0124]

[0125] Table 2. Performance test results of each application example

[0126] <![CDATA[Polymerization activity (g·mol -1 (M)·h -1 )]]> <![CDATA[Polymer molecular weight Mw (kg·mol -1 )]]> Molecular weight distribution Mw / Mn Copolymer monomer insertion rate (%) Polymer Tg (°C) Application Example 1 <![CDATA[2.91×10 7 > 4860 1.9 26.6 105 Application Example 2 <![CDATA[2.18×10 7 > 5130 1.8 31.2 108 Application Example 3 <![CDATA[1.65×10 7 > 5890 1.8 45.7 145 Application Example 4 <![CDATA[8.94×10 6 > 4420 1.9 28.7 106 Application Example 5 <![CDATA[7.68×10 6 > 2840 2.0 19.8 83 Application Example 6 <![CDATA[6.19×10 6 > 3260 2.0 21.4 92 Application Example 7 <![CDATA[4.59×10 6 > 3740 1.9 23.9 99 Application Example 8 <![CDATA[3.26×10 6 > 4060 1.8 25.1 102 Application Example 9 <![CDATA[2.84×10 6 > 2690 2.1 37.6 121 Application Example 10 <![CDATA[2.64×10 6 > 3070 2.5 39.2 125 Application Example 11 <![CDATA[3.00×10 6 > 1980 1.6 23.2 95 Application Example 12 <![CDATA[3.92×10 6 > 2150 1.5 21.4 91 Application Example 13 <![CDATA[3.48×10 6 > 3570 2.4 41.1 139 Application Example 14 <![CDATA[1.24×10 6 > 5120 1.7 37.6 121 Application Example 15 <![CDATA[3.68×10 6 > 3190 1.65 40.6 138 Application Example 16 <![CDATA[1.32×10 6 > 2790 1.9 24.3 97 Application Example 17 <![CDATA[4.16×10 6 > 2530 2.35 27.5 105 Comparative Application Example 1 <![CDATA[6.21×10 6 > 562 1.7 36.2 119

Claims

1. A phosphazene mono-metallocene catalyst, characterized in that, It has the structural expression shown in Formula I: In formula I, R 1 -R 5 each independently selected from hydrogen, C1-C 20 alkyl, a ring containing 4-20 carbon atoms formed by any adjacent carbon atoms and surrounding substituents; R 6 -R 7 、R 6’ -R 7’ 、R 6” -R 7” Each independently selected from hydrogen, C1-C 20 alkyl; R 8 An alkyl group selected from C1-C6, an aryl or aralkyl group of C6-C 20 ; M is selected from Group IVB elements.

2. The phosphazene mono-metallocene catalyst according to claim 1, wherein In Formula I, M is selected from titanium, zirconium, and hafnium.

3. The phosphazene mono-metallocene catalyst according to claim 1, wherein In Formula I, R 1 -R 5 each independently selected from any one of hydrogen, methyl, and tert-butyl.

4. The phosphazene mono-metallocene catalyst according to claim 3, characterized in that, In Formula I, R 6 -R 7 、R 6’ -R 7’ 、R 6” -R 7” are each independently selected from hydrogen, methyl, and isopropyl.

5. The phosphazene mono-metallocene catalyst according to claim 4, characterized in that, In formula I, R 6 -R 7 are respectively the same as R 6’ -R 7’ , R 6” -R 7” respectively.

6. The phosphazene mono-metallocene catalyst according to any one of claims 1-5, characterized in that, In formula I, R 8 is selected from methyl, ethyl, n-propyl, n-butyl, isobutyl, n-pentyl, n-hexyl, benzyl, 2-methylphenyl, 3-methylphenyl, 2,4-dimethylphenyl, 2,6-dimethylphenyl, 2-ethylphenyl, 4-ethylphenyl, 3-ethylphenyl.

7. The phosphazene mono-metallocene catalyst according to claim 6, characterized in that In formula I, R 8 is selected from methyl, ethyl, and n-propyl.

8. A method for preparing a phosphazene mono-metallocene catalyst according to any one of claims 1-7, characterized in that, It includes the following steps: Mix and stir the ligand shown in Formula II and the metal organic compound shown in Formula III in an anhydrous solvent, react for 2 - 24 h to form the structure shown in Formula IV; then continue to react it with at least one of the compounds shown in Formula V and Formula VI for 2 - 24 h to form the single metallocene catalyst shown in Formula I. R 8 -Li type V R 8 -MgBr, Formula VI Among them, R 1 -R 5 、R 6 -R 7 、R 6’ -R 7’ 、R 6” -R 7” 、R 8 ; the selection of M is the same as defined in any one of claims 1-7; X is selected from halogens.

9. The preparation method of the phosphazene mono-metallocene catalyst according to claim 8, characterized in that, X is Cl.

10. The preparation method of the phosphazene mono-metallocene catalyst according to claim 8, wherein The molar ratio of the ligand shown in Formula II to the metal organic compound shown in Formula III is 1:(1 - 1.5).

11. The preparation method of the phosphazene mono-metallocene catalyst according to claim 8, characterized in that, The molar ratio of the structure shown in Formula IV to at least one of the compounds shown in Formula V and Formula VI is 1:(2 - 3).

12. The preparation method of the phosphazene mono-metallocene catalyst according to claim 8, characterized in that, The preparation method of the ligand shown in Formula II is: wherein, R 6 -R 7 、R 6’ -R 7’ 、R 6” -R 7” are selected in the same definition as any one of claims 1-5; Under anhydrous and anaerobic conditions, react the compound shown in Formula VII with a halogen-containing phosphide for 12 - 48 h to form the compound shown in Formula VIII, and then continue to heat-react it with trimethylsilyl azide for 12 - 48 h to form the ligand shown in Formula II.

13. The preparation method of the phosphazene mono-metallocene catalyst according to claim 12, characterized in that, The molar ratio of the compound shown in Formula VII, the halogen-containing phosphide, and trimethylsilyl azide is 3:1:(1 - 2).

14. The preparation method of the phosphazene mono-metallocene catalyst according to claim 13, characterized in that, The said halogen-containing phosphide is selected from one or more of phosphorus trichloride, phosphorus tribromide, and phosphorus pentachloride.

15. The preparation method of the phosphazene mono-metallocene catalyst according to claim 13, wherein The reaction temperature of the compound shown in Formula VII and the halogen-containing phosphide is 25 - 120 °C.

16. The preparation method of the phosphazene mono-metallocene catalyst according to claim 15, characterized in that, The reaction temperature of the compound shown in Formula VIII and trimethylsilyl azide is 25 - 120 °C.

17. Application of the phosphazene single metallocene catalyst as described in any one of claims 1 - 7 or the phosphazene single metallocene catalyst prepared by the method as described in any one of claims 8 - 16 in the production of cycloolefin copolymers.

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