A metallocene compound containing heteroatoms and its preparation method and use

Abstract

The present invention provides a heteroatom-containing metallocene compound and a preparation method and use thereof, wherein the general structural formula of the heteroatom-containing metallocene compound is shown in the following formula I. The heteroatom-containing metallocene compound of the present invention has a structure with a larger sterically hindered ligand, which gives the metallocene compound a specific space, and the catalyst combination formed by the heteroatom-containing metallocene compound can effectively improve the olefin copolymerization reaction ability and the high temperature resistance of the catalyst.

Description

Technical Field

[0001] The present invention relates to the field of metal organic compounds, in particular to a metallocene compound containing heteroatoms and a preparation method and application thereof. Background Art

[0002] Polyolefin thermoplastic elastomer is a high-performance polyolefin product that is rubber elastic at room temperature and has the characteristics of low density, large bending, high low-temperature impact resistance, easy processing, and reusability. Most elastomers are prepared using bridged metallocene compounds, because the bridged structure gives a specific spatial structure, promotes the coordination and insertion of α-olefins, completes olefin copolymerization, and thus gives the polymer a branched structure, weakens the polyethylene chain crystal area, and becomes an amorphous area with rubber elasticity, so it has the properties of an elastomer.

[0003] In 1993, DOW Chemical Company announced a constrained geometry metallocene compound, which is essentially to give the metallocene compound a specific space. Patent CN93105687 reported that the compound can catalyze ethylene / 1-octene copolymerization.

[0004] In 2001, Exxon reported hafnium metal compounds of carbon-bridged cyclopentadienylfluorene in patent CN1138796C. In 2009, Mitsui Chemicals reported carbon-bridged cyclopentadienylfluorene zirconium metal compounds in patent CN104254546B. Both compounds can efficiently catalyze ethylene-octene copolymerization, and the polymers have excellent properties.

[0005] Similarly, non-bridged metallocenes can also be used to prepare elastomers. As described in the above mechanism, to catalyze the coordination insertion of α-olefins, the metallocene compound must have a specific space, that is, a large steric hindrance ligand structure is used to limit the free rotation of metal atoms, which is beneficial to the preparation of elastomers.

[0006] In 2000, patent WO0005238 reported a bisphosphinimine non-bridged titanocene catalyst for catalytic ethylene-octene copolymerization with a catalytic activity of 10 6 (g polymer / (moL·Ti·h)), the molecular weight is between 20,000 and 60,000, which means that the catalytic activity is not high and the polymer molecular weight is not high, which makes it difficult to process.

[0007] In 2018, patent CN105566530 reported a non-bridged phenol oxide titanocene catalyst for catalyzing ethylene-octene copolymerization with a catalytic activity of 10 6 (g / (moL·Ti·h)), and the octene insertion content is between 10wt% and 16wt%, indicating that the catalyst has certain copolymerization ability but cannot meet the requirements for preparing elastomers. The patent discloses that the catalyst activity is not high and no information on the molecular weight of the polymer is reported.

[0008] The above research shows that compared with bridged metallocene catalysts, in non-bridged metallocene catalysts, the steric hindrance structure of the ligand is not large, and the metal atoms can rotate freely, showing disadvantages such as low copolymerization catalytic activity and poor high temperature resistance. Summary of the invention

[0009] In view of the above-mentioned shortcomings of the prior art, the object of the present invention is to provide a heteroatom-containing metallocene compound and a preparation method and use thereof for the preparation of elastomers to solve the problem of poor copolymerization ability of non-bridged metallocene compounds.

[0010] To achieve the above objectives and other related objectives, the present invention is achieved through the following technical solutions.

[0011] The first aspect of the present invention provides a heteroatom-containing metallocene compound, the general structural formula of which is shown in the following formula I:

[0012]

[0013] Among them, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 Each is independently hydrogen, or a C1-C50 substituted or unsubstituted hydrocarbon group, a silane group, an alkoxy group, a silaneoxy group, an aromatic group, or an aryloxy group;

[0014] Each X is independently a halogen atom or a C1-C50 substituted or unsubstituted hydrocarbon group, hydrogen group, amino group, alkoxythio group, phosphorus group; or two Xs are connected to form a metal ring; or two Xs are connected to form a chelate ligand, a diene ligand or a forked alkyl group;

[0015] n is 1, 2, or 3;

[0016] m is 0, 1, 2, or 3;

[0017] The t value is 0, 1, 2, or 3;

[0018] M is one selected from Ti, Zr, and Hf;

[0019] A is one selected from N, P, and As;

[0020] D is one selected from N, P, As, O, and S;

[0021] E is one selected from N, P, As, O, and S;

[0022] F is one selected from C, Si, and Ge.

[0023] Preferably, selected from R 1 and R 2 , R 2 and R 3 , `R 3 and R 4 , R 4 and R 5 , R 6 and R 7 , R 8 and R 9 One or more of the groups are connected to form a cyclic saturated or unsaturated ring.

[0024] Preferably, the hydrocarbon group is selected from one of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl.

[0025] Preferably, the alkoxy group is one selected from the group consisting of methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy and decyloxy.

[0026] Preferably, the aromatic group is one selected from phenyl, methylphenyl, dimethylphenyl, ethylphenyl, methylethylphenyl, propylphenyl, tetramethylphenyl, dimethylethylphenyl, methylpropylphenyl, diethylphenyl, butylphenyl, naphthyl and methylnaphthyl.

[0027] Preferably, the aryloxy group is one selected from phenoxy, methylphenoxy, dimethylphenoxy, ethylphenoxy, trimethylphenoxy, methylethylphenoxy, propylphenoxy, tetramethylphenoxy, dimethylethylphenoxy, methylpropylphenoxy, diethylphenoxy, butylphenoxy, naphthoxy and methylnaphthoxy.

[0028] Preferably, the cyclic saturated or unsaturated ring is selected from a fused five-membered, six-membered or seven-membered non-aromatic carbocyclic group. More preferably, the non-aromatic carbocyclic group is selected from one or more of a substituted indenyl, a substituted fluorenyl, a substituted pyridyl or a substituted pyrrolyl.

[0029] Preferably, X is a chloro group, a methyl group, or a diamine group.

[0030] Preferably, the structural formula of the heteroatom-containing metallocene compound includes:

[0031]

[0032]

[0033]

[0034] The second aspect of the present invention also discloses a method for preparing the above-mentioned heteroatom-containing metallocene compound, comprising:

[0035] 1) The heteroatom ligand reacts with an alkali metal hydrocarbon compound to obtain a salt;

[0036]

[0037] Wherein, RN is an alkali metal hydrocarbon compound;

[0038] 2) reacting a salt of a heteroatom ligand with a single metallocene compound to obtain the heteroatom-containing metallocene compound;

[0039]

[0040] The alkali metal hydrocarbyl compounds include alkyl alkali metal compounds and aryl alkali metal compounds.

[0041] The third aspect of the present invention further discloses a catalyst combination, which comprises the heteroatom-containing metallocene compound and an activator as described above, wherein the heteroatom-containing metallocene compound and the activator can interact with each other to form an ion pair compound.

[0042] Preferably, the molar ratio of the heteroatom-containing metallocene compound to the activator is 5 to 1000. For example, it may be 5 to 10, 10 to 20, 20 to 30, 30 to 40, 40 to 50, 50 to 60, 60 to 70, 70 to 80, 80 to 90, 90 to 100, 100 to 200, 200 to 300, 300 to 400, 400 to 500, 500 to 600, 600 to 700, 700 to 800, 800 to 900, 900 to 1000.

[0043] Preferably, the activator contains aluminum and / or boron elements.

[0044] Preferably, the activator containing aluminum element is a substituted or unsubstituted hydrocarbyl aluminum compound and / or hydrocarbyl aluminoxane.

[0045] More preferably, the hydrocarbon group includes an alkyl group and an aryl group.

[0046] Preferably, the hydrocarbyl aluminum compound is an alkyl aluminum or an aryl aluminum. More preferably, the alkyl aluminum compound is selected from one or more of trimethyl aluminum, triethyl aluminum, tripropyl aluminum, tri-n-butyl aluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, triisopropylaluminum, triisobutylaluminum, tri-tert-butylaluminum, tricyclohexylaluminum, tricyclooctylaluminum, triphenylaluminum and tritolylaluminum.

[0047] Preferably, the hydrocarbyl aluminoxane is an alkyl aluminoxane or an aryl aluminoxane. More preferably, the substituted or unsubstituted alkyl aluminoxane is selected from one or more of methyl aluminoxane, triisobutyl dialuumoxane, polyisobutyl aluminoxane, tetraethyl dialuumoxane, pentaisobutyl trialuminoxane, 1,3-dichloro-1,3-diethyl dialuumoxane and 1,3-dichloro-1,3-dimethyl dialuumoxane.

[0048] Preferably, the boron element is introduced by borate. More preferably, the cation in the borate is lithium ion, sodium ion, potassium ion, carbon cation, or ammonium cation.

[0049] More preferably, the carbon cation is a triphenylmethyl cation, a tritolylmethyl cation, or a tri(xylyl)methyl cation.

[0050] More preferably, the ammonium cation is a trimethylammonium cation, a triethylammonium cation, a tripropylammonium cation, a tributylammonium cation, a triisobutylammonium cation, an N,N-dimethylanilinium cation, an N,N-diethylanilinium cation, an N,N-diisopropylanilinium cation, an N,N-2,4,6-pentamethylanilinium cation, a diisopropylammonium cation, or a cyclohexylammonium cation.

[0051] More preferably, the anion in the borate is tetrafluoroboron anion, tetraphenylboron anion, tetrakis(4-fluorophenyl)boron anion, tetrakis(3.5-difluorophenyl)boron anion, tetrakis(4-fluoromethylphenyl)boron anion, tetrakis(pentafluorophenyl)boron anion, tetrakis(3.5-dimethylphenyl)boron anion.

[0052] The fourth aspect of the present invention also discloses the use of the catalyst combination as described above in elastomer polymerization reaction.

[0053] Preferably, the elastomer is an olefin polymer.

[0054] The fifth aspect of the present invention also discloses a method for polymerizing an elastomer, wherein the elastomer reaction monomer is polymerized in the presence of the catalyst combination as described above.

[0055] Preferably, the reactive monomer is an olefin. More preferably, the olefin is selected from one or more of 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, and 1-octene.

[0056] More preferably, the polymerization reaction is a copolymerization reaction of ethylene or propylene with an α-olefin.

[0057] Preferably, the polymerization reaction adopts a batch solution polymerization method.

[0058] Preferably, the polymerization reaction is carried out in the presence of a polymerization solvent. More preferably, the polymerization solvent is an alkane, a cycloalkane, or an aromatic compound.

[0059] More preferably, the alkane is selected from hexane and heptane.

[0060] More preferably, the aromatic compound is selected from benzene, toluene, xylene, and substituted toluene.

[0061] Preferably, the polymerization reaction temperature is 80-250°C. For example, it may be 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, 160°C, 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, 195°C, 200°C, 20 ℃, 5℃, 210℃, 215℃, 140℃, 145℃, 150℃, 155℃, 160℃, 165℃, 170℃, 175℃, 180℃, 185℃, 190℃, 195℃, 200℃, 205℃, 210℃, 215℃, 220℃, 225℃, 230℃, 235℃, 240℃, 245℃ or 250℃.

[0062] Preferably, the polymerization reaction pressure is 0.1-10 MPa, such as 0.5 MPa, 1 MPa, 1.5 MPa, 2 MPa, 2.5 MPa, 3 MPa, 3.5 MPa, 4 MPa, 4.5 MPa, 5 MPa, 5.5 MPa, 6 MPa, 6.5 MPa, 7 MPa, 7.5 MPa, 8 MPa, 8.5 MPa, 9 MPa, 9.5 MPa, or 10 MPa.

[0063] The sixth aspect of the present invention also discloses a polymer formed by the above polymerization method.

[0064] Preferably, the polymer has a melting point of 30°C-180°C and a weight average molecular weight (M w ) is 10000-600000Da, and the ratio of weight average molecular weight to number average molecular weight (M w / M n ) is 1.5~3.7.

[0065] The heteroatom-containing metallocene compound of the present invention has a structure with a larger sterically hindered ligand, which gives the metallocene catalyst a specific space, and the catalyst combination formed by the heteroatom-containing metallocene compound can effectively promote the olefin copolymerization reaction ability and the high temperature resistance of the catalyst. DETAILED DESCRIPTION

[0066] The following is a description of the implementation of the present invention by means of specific embodiments. Those skilled in the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification.

[0067] Before further describing the specific embodiments of the present invention, it should be understood that the scope of protection of the present invention is not limited to the specific embodiments described below; it should also be understood that the terms used in the examples of the present invention are intended to describe specific embodiments, rather than to limit the scope of protection of the present invention. The test methods in the following examples without specifying specific conditions are generally carried out under conventional conditions or under conditions recommended by the manufacturers.

[0068] When the embodiments give numerical ranges, it should be understood that, unless otherwise specified in the present invention, both endpoints of each numerical range and any numerical value between the two endpoints can be selected. Unless otherwise defined, all technical and scientific terms used in the present invention have the same meaning as those generally understood by those skilled in the art. In addition to the specific methods, equipment, and materials used in the embodiments, according to the grasp of the prior art by those skilled in the art and the record of the present invention, any methods, equipment, and materials of the prior art similar or equivalent to the methods, equipment, and materials described in the embodiments of the present invention can also be used to realize the present invention.

[0069] Unless otherwise specified, the reagents used in the examples of the present invention were purchased directly from the market without any special treatment. The anhydrous and anaerobic conditions were prepared using the Schlenk technique known to those skilled in the art. The water and oxygen content of the solvent involved in the anhydrous and anaerobic reaction must be controlled within 10 ppm, and the dissolved oxygen must be fully replaced with nitrogen.

[0070] Example 1: Preparation of I-52 ligand

[0071] The specific synthetic route is as follows:

[0072]

[0073] Under nitrogen protection, add toluene (400 mL) and hexamethyldisilazane (0.2119 mol; 34.20 g) to a 1000 mL three-necked reaction bottle. Take diphenylphosphine chloride (0.4230 mol; 93.3 g) and slowly drop it into the toluene solution. After the dropwise addition, raise the temperature to 80°C and react for 3 hours.

[0074] After 3 hours, the by-product trimethylchlorosilane and unreacted hexamethyldisilazane were distilled off under reduced pressure, and after distillation, acetonitrile (150.0 mL) was added, and the mixture was stirred at room temperature for 12 hours and then filtered to obtain 36.75 g of a white solid with a yield of 45.0%.

[0075] The characterization results are as follows:

[0076] 1 HNMR (600MHz, CDCl 3 )δ:7.5-7.2(m,20H).4.9-4.3(br,1H).

[0077] 31 PNMR (600MHz,CDCl 3 )δ:45.5(s).

[0078] ESI MS: m / z 386.1 ([M+H] + )

[0079] Example 2: Preparation of I-52 Ligand Lithium Salt

[0080] The specific synthetic route is as follows

[0081]

[0082] Under nitrogen protection, I-52 ligand (19.98 mmol; 7.70 g) and n-hexane (100.0 mL) were added to a 250 mL three-necked reaction bottle. The mixture was stirred thoroughly until the ligand was completely dissolved. The temperature was lowered to -10°C, and n-butyl lithium (20.99 mmol; 5.75 g) was added dropwise. The temperature was controlled to be less than 0°C, and then the temperature was restored to room temperature for reaction. After 24 hours, the mixture was filtered and dried to obtain a white solid (4.93 g) with a yield of 63.0%.

[0083] 1 HNMR(600MHz,THF-D8)δ:7.5-7.2(m,20H).

[0084] Example 3: Preparation of I-52 Chloroform (I-1)

[0085] Under nitrogen protection, add ether (80.0mL) and I-52 ligand lithium salt (5.000mmoL; 1.96g) to a 250mL three-necked reaction bottle, cool to -10°C, take trichloromonocene titanocene (5.000mmoL; 1.10g), slowly add to the lithium salt, control the temperature below 0°C, and after adding, raise the temperature to 25-28°C and react for 12h. After 12h, remove the ether under reduced pressure, add toluene (80.0mL) after distillation, stir well and filter to remove the insoluble salt lithium chloride, distill the filtrate under reduced pressure to remove the toluene, then reduce to 25-28°C, add n-pentane (50mL), stir well and filter to obtain a brown solid (1.50g), with a yield of 52.8%.

[0086] 1 HNMR (600MHz, C 6 D 6)δ:7.5-7.3(m,20H),6.5-6.3(m,3H),6.50-6.20(m,2H).

[0087] Theoretical valueAnal.Calcd.For TiC 29 H 25 Cl 2 NP 2 :C(61.30),H(4.43),N(2.46),Ti(8.42).

[0088] Measured values: C (61.50), H (4.53), N (2.48), Ti (8.45).

[0089] Example 4: Preparation of I-52

[0090] The synthetic route is as follows

[0091]

[0092] Under nitrogen protection, I-52 chloride (1.000mmoL; 0.57g) and ether (40mL) were added to a 100mL three-necked reaction bottle, the temperature was lowered to 0°C, methylmagnesium bromide ether solution (3M; 5mmoL; 1.72g) was added dropwise, and the temperature was raised to room temperature to react for 24h after the addition was complete. Then, low-boiling substances were removed by distillation under reduced pressure, and the crude product was extracted into pentane. The filtrate was collected by filtration, the solvent was concentrated, and recrystallization was performed to obtain an off-white solid (0.33g) with a yield of 63.0%.

[0093] 1 HNMR (600MHz, C 6 D 6 )δ:7.7-7.4(m,20H),6.8-6.7(m,3H),6.5-6.4(m,2H),-1.5(s,3H),-1.7(s,3H).

[0094] Anal.Calcd.For TiC 31 H 31 NP 2 :C(70.60),H(5.92)N(2.66),Ti(9.08).

[0095] Measured values: C (70.80), H (5.95), N (2.69), Ti (9.13).

[0096] Example 5: Preparation of I-53 ligand

[0097]

[0098] Under nitrogen protection, diethylphosphine (9.00g; 0.1moL) and n-hexane (200.0mL) were taken, stirred thoroughly and cooled to 0°C, n-butyllithium (28.77g; 0.105moL) was added dropwise, the temperature was controlled to be less than 10°C, and then stirred at room temperature for 12h. N, N-di(2-chloroethyl)-N-(trimethylsilyl)amine (21.4g; 0.10moL) was dissolved in 50mL tetrahydrofuran, and then slowly added to lithium phosphine, the temperature was controlled to be less than 0°C, and then raised to room temperature for reaction for 16h. After the reaction was completed, the reaction solution was slowly poured into water, tetrabutylammonium fluoride was added, the temperature was raised to 60°C, and the reaction was carried out for 8h. Toluene was then added for extraction, and the low-boiling point solvent was removed to obtain 20.7g of gray viscous liquid with a yield of 83.0%.

[0099] 1 HNMR (600MHz, CDCl 3 )δ:2.80.5-2.60(m,4H),1.60-1.50(m,4H),1.40-1.30(m,8H),1.10-0.90(m,12H).

[0100] ESI MS: m / z 250.18 ([M+H] + )

[0101] Example 6: Preparation of I-53 Ligand Lithium Salt

[0102]

[0103] Under nitrogen protection, take I-53 ligand (4.99 g; 0.02 moL) and toluene (100.0 mL), stir thoroughly, cool to -10°C, add n-butyl lithium (5.75 g; 0.021 moL) dropwise, control the temperature below 0°C, then return to room temperature and react for 24 hours. After 24 hours, filter and dry to obtain a gray solid (4.13 g) with a yield of 81.0%.

[0104] 1 HNMR(600MHz,THF-D8)δ:2.90.5-2.80(m,4H),1.80-1.70(m,4H),1.60-1.50(m,8H),1.30-1.10(m,12H).

[0105] Example 7: Preparation of I-53 Chloroform (I-31)

[0106]

[0107] Under nitrogen protection, add ether (80.0mL) and I-53 ligand lithium salt (10.00mmoL; 2.55g) to a 250mL three-necked reaction bottle, cool to -10°C, take trichloromonocene titanocene (10.00mmoL; 2.20g), slowly add to the lithium salt, control the temperature below 0°C, and after adding, raise the temperature to 25-28°C for reaction. After 12h, remove the ether under reduced pressure, add toluene (80.0mL) after distillation, stir well and filter to remove the insoluble salt lithium chloride, distill the filtrate under reduced pressure to remove the toluene, then cool to 25-28°C, add n-pentane (50mL), stir well and filter to obtain a brown solid (1.60g), with a yield of 37.0%.

[0108] 1 HNMR (600MHz, C 6 D 6 )δ:6.60-6.45(m,3H),6.40-6.25(m,2H),2.90.5-2.80(m,4H),1.80-1.70(m,4H),1.60-1.50(m,8H),1.30-1.10(m,12H).

[0109] Anal.Calcd.For TiC 17 H 33 Cl 2 NP 2 :C(47.25),H(7.70),N(3.36),Ti(11.48).

[0110] Measured values: C (47.50), H (8.00), N (3.39), Ti (11.50).

[0111] Example 8: Preparation of I-53

[0112]

[0113] Under nitrogen protection, I-53 chloride (2.000mmoL; 0.86g) and ether (40mL) were added to a 100mL three-necked reaction bottle, the temperature was lowered to 0°C, methylmagnesium bromide ether solution (3M; 10mmoL; 3.44g) was added dropwise, and the temperature was raised to room temperature for 24h after the addition was complete. Then, low-boiling substances were removed by distillation under reduced pressure, and the crude product was extracted into pentane. The filtrate was collected by filtration, the solvent was concentrated, and recrystallization was performed to obtain a gray solid (0.50g) with a yield of 64.0%.

[0114] 1 HNMR (600MHz, C 6 D 6)δ:6.7-6.5(m,3H),6.4-6.2(m,2H),2.90-2.70(m,4H),1.80-1.60(m,4H),1.50-1.40(m,8H),1.30-1.10(m,12H),

[0115] -1.5(s,3H),-1.7(s,3H).

[0116] Anal.Calcd.For TiC 19 H 39 NP 2 :C(58.31),H(10.05)N(3.58),Ti(12.23).

[0117] Measured values: C (58.51), H (10.30), N (3.60), Ti (12.25).

[0118] Example 9: Preparation of I-54 ligand

[0119]

[0120] Under nitrogen protection, sodium hydroxide (18.0 g; 0.45 moL) and dodecanethiol (60.72 g; 0.3 moL) were added to the reaction bottle, and then ethanol (400.0 mL) was added, and the mixture was stirred thoroughly, and then the temperature was lowered to 0°C. Chlorodiethylamine hydrochloride (27.0 g; 0.15 moL) was dissolved in ethanol (300 mL), and then the ethanol solution was slowly added to dodecanethiol. After the addition was complete, the mixture was warmed to room temperature and reacted overnight. The filtrate was collected by filtration, and the solvent in the filtrate was removed. Ether (300.0 mL) was added, and the filtrate was collected by filtration. The solvent in the filtrate was removed, and a pink solid (34.12 g) was obtained with a yield of 48.0%.

[0121] 1 HNMR (600MHz, CDCl 3 )δ:2.85(t,4H),2.70(t,4H),2.65(t,4H),1.95-1.90(br,1H),1.60-1.65(m,4H),1.40-1.20(m,36H),0.90-0.88(m,6H).

[0122] ESI MS: m / z 474.41 ([M+H] + )

[0123] Example 10: Preparation of I-54 Ligand Lithium Salt

[0124]

[0125] Under nitrogen protection, take I-54 ligand (9.48 g; 0.02 moL) and toluene (100.0 mL), stir thoroughly, cool to -10°C, add n-butyl lithium (5.75 g; 0.021 moL) dropwise, control the temperature below 0°C, then return to room temperature and react for 24 hours. After 24 hours, filter and dry to obtain a gray solid (7.20 g) with a yield of 75.0%.

[0126] 1 HNMR(600MHz,THF-D8)δ:2.95(t,4H),2.80(t,4H),2.75(t,4H),1.75-1.70(m,4H),1.60-1.55(m,36H),0.95-0.90(m,6H).

[0127] Example 11: Preparation of I-54 Chloroform (I-51)

[0128]

[0129] Under nitrogen protection, add ether (80.0mL) and I-54 ligand lithium salt (110.00mmoL; 4.80g) to a 250mL three-necked reaction bottle, cool to -10°C, take trichloromonocene titanocene (10.00mmoL; 2.20g), slowly add to the lithium salt, control the temperature below 0°C, and after adding, raise the temperature to 25-28°C to react for 12h. After 12h, remove ether under reduced pressure, add toluene (80.0mL) after distillation, stir well and filter to remove insoluble salt lithium chloride, distill the filtrate under reduced pressure to remove toluene, then reduce to 25-28°C, add n-pentane (50mL), stir well and filter to obtain a brown solid (3.15g), with a yield of 48.0%.

[0130] 1 HNMR (600MHz, C 6 D 6 )δ:6.5-6.3(m,3H),6.4-6.20(m,2H),2.95(t,4H),2.80(t,4H),2.75(t,4H),1.75-1.70(m,4H),1.60-1.55(m,36H),0.95-0.90(m,6H).

[0131] Anal.Calcd.For TiC 33 H 63 Cl 2 NS 2 :C(61.35),H(9.67)N(2.13),Ti(7.29.

[0132] Measured values: C (61.40), H (9.71) N (2.15), Ti (7.32).

[0133] Example 12: Preparation of I-54

[0134]

[0135] Under nitrogen protection, I-54 chloride (2.000mmoL; 1.31g) and ether (40mL) were added to a 100mL three-necked reaction bottle, the temperature was lowered to 0°C, methylmagnesium bromide ether solution (3M; 10mmoL; 3.44g) was added dropwise, and the temperature was raised to room temperature to react for 24h after the addition was complete. Then, low-boiling substances were removed by distillation under reduced pressure, and the crude product was extracted into pentane. The filtrate was collected by filtration, the solvent was concentrated, and recrystallization was performed to obtain an off-white solid (0.69g) with a yield of 56.0%.

[0136] 1 HNMR (600MHz, C 6 D 6 )δ:6.6-6.4(m,3H),6.3-6.1(m,2H),2.95(t,4H),2.80(t,4H),2.75(t,4H),1.8 0-1.75(m,4H),1.65-1.60(m,36H),0.95-0.90(m,6H),-1.5(s,3H),-1.7(s,3H).

[0137] Anal.Calcd.For TiC 35 H 69 NS 2 :C(68.25),H(11.29),N(2.27),Ti(7.77).

[0138] Measured values: C (68.45), H (11.39), N (2.30), Ti (7.80).

[0139] Example 13: Synthesis of diphenyl nitrogen chloride

[0140]

[0141] Diphenylamine (0.5 mol; 84.62 g) and dichloromethane (500.0 mL) were added to a 1L three-necked reaction flask, and chlorine gas was continuously introduced. The mixture was stirred at room temperature for 24 h, and then the chlorine gas was washed off with water. After drying and removing the solvent, 48.9 g of a light yellow liquid was obtained with a yield of 48.9%.

[0142] The characterization results are as follows:

[0143] 1HNMR (600MHz, CDCl 3 )δ:7.6-7.4(m,10H).

[0144] ESI MS: m / z 204.6; 206.6 ([M+H] + )

[0145] Example 14: Preparation of I-10 ligand

[0146]

[0147] Hexamethyldisilaphosphine (0.1 mol; 17.8 g) and toluene (300.0 mL) were added to a 1L three-necked reaction flask, and diphenyl nitrogen chloride (0.2 mol; 40.7 g) was slowly added dropwise to the toluene solution. After the addition was complete, the temperature was raised to 80°C and the reaction was continued for 5 hours. Then, the by-product trimethylsilyl chloride and the unreacted raw materials were evaporated under reduced pressure, and acetonitrile (100.0 mL) was added. After sufficient stirring, the mixture was filtered to obtain a gray solid (14.7 g) with a yield of 40.0%.

[0148] The characterization results are as follows:

[0149] 1 HNMR (600MHz, CDCl 3 )δ:7.6-7.4(m,20H).3.5-3.(br,1H).

[0150] 31 PNMR (600MHz,CDCl 3 )δ:37.5(s).

[0151] ESI MS: m / z 369.1 ([M+H] + )

[0152] Example 15: Preparation of I-10 Ligand Lithium Salt

[0153]

[0154] Under nitrogen protection, I-10 ligand (30.0 mmol; 11.00 g) and n-hexane (150.0 mL) were added to a 500 mL three-necked reaction bottle. The mixture was stirred thoroughly until the ligand was completely dissolved. The temperature was lowered to -10 °C, and n-butyl lithium (33.0 mmol; 9.10 g) was added dropwise. The temperature was controlled to be less than 0 °C, and then the temperature was restored to room temperature for reaction. After 24 h, the mixture was filtered and dried to obtain a white solid (7.86 g) with a yield of 70.0%.

[0155] 1 HNMR(600MHz,THF-D8)δ:7.6-7.3(m,20H).

[0156] Example 16: Preparation of I-10

[0157]

[0158] Under nitrogen protection, add ether (100.0mL) and I-10 ligand lithium salt (10.00mmoL; 3.74g) to a 250mL three-necked reaction bottle, cool to -10°C, take trichloromonocene titanocene (10.00mmoL; 2.20g), slowly add to the lithium salt, control the temperature below 0°C, and after adding, raise the temperature to 25-28°C to react for 12h. After 12h, remove ether under reduced pressure, add toluene (100.0mL) after distillation, stir well and filter to remove insoluble salt lithium chloride, distill the filtrate under reduced pressure to remove toluene, then cool to 25-28°C, add n-pentane (60mL), stir well and filter to obtain a brown solid (2.76g), with a yield of 50.0%.

[0159] 1 HNMR (600MHz, C 6 D 6 )δ:7.6-7.4(m,20H),6.6-6.4(m,3H),6.40-6.20(m,2H).

[0160] Theoretical valueAnal.Calcd.For TiC 29 H 25 Cl 2 N 2 P 1 :C(63.18),H(4.57),N(5.08),Ti(8.68).

[0161] Measured values: C (63.58), H (4.87), N (5.38), Ti (8.98).

[0162] Example 17: Preparation of I-25 ligand

[0163]

[0164] Under nitrogen protection, ether (400.0 mL) and benzenesulfonyl chloride (0.5 mol; 72.31 g) were added to a 1L three-necked reaction bottle. Ammonia was continuously introduced at room temperature for 24 h. The unreacted ammonia was then washed away with water. After drying, the solvent was removed to obtain 35.00 g of a light yellow liquid with a yield of 60.0%.

[0165] The characterization results are as follows:

[0166] 1 HNMR (600MHz, CDCl 3)δ:7.4-7.2(m,10H).3.5-3.3(br,1H).

[0167] ESI MS: m / z 396.0 ([M+H] + )

[0168] Example 18: Preparation of I-25 Ligand Lithium Salt

[0169]

[0170] Under nitrogen protection, I-25 ligand (100.0 mmoL; 23.93 g) and n-hexane (200.0 mL) were added to a 5000 mL three-necked reaction bottle. The mixture was stirred thoroughly until the ligand was completely dissolved. The temperature was lowered to -10°C, and n-butyl lithium (110.0 mmoL; 30.14 g) was added dropwise. The temperature was controlled to be less than 0°C, and then the temperature was restored to room temperature for reaction. After 24 hours, the mixture was filtered and dried to obtain a white solid (16.75 g) with a yield of 70.0%.

[0171] 1 HNMR(600MHz,THF-D8)δ:7.5-7.2(m,10H).

[0172] Example 19: Preparation of I-25

[0173]

[0174] Under nitrogen protection, add ether (100.0mL) and I-25 ligand lithium salt (20.00mmoL; 4.79g) to a 500mL three-necked reaction bottle, cool to -10°C, take trichloromonocene titanocene (20.00mmoL; 4.40g), slowly add to the lithium salt, control the temperature below 0°C, and after adding, raise the temperature to 25-28°C to react for 12h. After 12h, remove ether under reduced pressure, add toluene (200.0mL) after distillation, stir well and filter to remove insoluble salt lithium chloride, distill the filtrate under reduced pressure to remove toluene, then cool to 25-28°C, add n-pentane (100mL), stir well and filter to obtain a brown solid (2.50g), with a yield of 30.0%.

[0175] 1 HNMR (600MHz, C 6 D 6 )δ:7.5-7.3(m,10H),6.5-6.3(m,3H),6.30-6.10(m,2H).

[0176] Theoretical valueAnal.Calcd.For TiC 17 H 15 Cl 2NS 2 :C(49.06),H(3.63),N(3.37),Ti(11.50).

[0177] Measured values: C(49.36, H(4.13), N(3.67), Ti(11.70).

[0178] Example 20: Preparation of I-40 ligand

[0179]

[0180] In a 1L three-necked reaction bottle, add n-hexane (400.0mL), di, 2-bromoaniline (0.5moL; 163.51g), cool to 0°C, add butyl lithium (1.10moL; 301.40g), and control the temperature to less than 5°C. After the addition, react at room temperature for 48h, then cool to 0°C, add diphenylphosphine chloride (1.10moL; 242.70g), and react at room temperature for 24h, then add water to quench the reaction, extract with dichloromethane, remove the low boiling point solvent after drying, add acetonitrile (300.0mL), and stir well to obtain 107.52g of white solid, with a yield of 40.0%.

[0181] The characterization results are as follows:

[0182] 1 HNMR (600MHz, CDCl 3 )δ:7.8-7.7(m,8H),7.6-7.4(m,20H),4.5-4.1(br,1H).

[0183] 31 PNMR (600MHz,CDCl 3 )δ:40.5(s).

[0184] ESI MS: m / z 538.58 ([M+H] + )

[0185] Example 21: Preparation of I-40 Ligand Lithium Salt

[0186]

[0187] Under nitrogen protection, I-40 ligand (100.0 mmol; 53.76 g) and toluene (200.0 mL) were added to a 500 mL three-necked reaction bottle. The mixture was stirred thoroughly until the ligand was completely dissolved. The temperature was lowered to -10°C, and n-butyl lithium (110.0 mmol; 30.14 g) was added dropwise. The temperature was controlled to be less than 0°C, and then the temperature was restored to room temperature for reaction. After 24 hours, the mixture was filtered and dried to obtain a white solid (24.46 g) with a yield of 45.0%.

[0188] 1 HNMR(600MHz,THF-D8)δ:7.8-7.6(m,8H),7.6-7.4(m,20H).

[0189] Example 22: Preparation of I-40

[0190]

[0191] Under nitrogen protection, add ether (100.0mL) and I-40 ligand lithium salt (10.00mmoL; 5.43g) to a 250mL three-necked reaction bottle, cool to -10°C, take trichloromonocene titanate (10.00mmoL; 2.20g), slowly add to the lithium salt, control the temperature below 0°C, and after adding, raise the temperature to 25-28°C to react for 12h. After 12h, remove ether under reduced pressure, add toluene (100.0mL) after distillation, stir well and filter to remove insoluble salt lithium chloride, distill the filtrate under reduced pressure to remove toluene, then cool to 25-28°C, add n-pentane (60mL), stir well and filter to obtain a brown solid (2.74g), with a yield of 38.0%.

[0192] 1 HNMR (600MHz, C 6 D 6 )δ:7.8-7.6(m,8H),7.6-7.3(m,20H),6.5-6.4(m,3H),6.40-6.10(m,2H).

[0193] Theoretical valueAnal.Calcd.For TiC 41 H 33 Cl 2 NP 2 :C(68.35),H(4.62),N(1.94),Ti(6.64).

[0194] Measured values: C (68.65), H (4.92), N (2.34), Ti (7.04).

[0195] Examples 23 to 41 are polymerization experiments, in which the metallocene compounds obtained in Examples 4, 8, and 12 are used as the main catalyst, and common methylaluminoxane or borate is used as the activator. In specific solvents such as pentane, hexane, heptane and other inert solvents, ethylene and α-olefin copolymerization, such as ethylene and butene, ethylene and 1-hexene, ethylene and 1-octene, are catalyzed to obtain an elastomer.

[0196] Example 13

[0197] Fully dry a 1L stainless steel kettle with mechanical stirring. Under nitrogen protection at room temperature, add n-hexane (500mL), a certain amount of 1-octene and an impurity remover (triethylaluminum; 0.25g) through a metering pump, add hydrogen (50mL) through a hydrogen flowmeter, raise the temperature to 140°C, and fill with ethylene. Take a certain amount of main catalyst (I-52), co-catalyst methylaluminoxane (MAO) and borate in toluene in a glove box and mix them thoroughly for 1h. Then take them out and add them to a pressure tube, press them into the reactor to start the polymerization reaction, and the total reaction time is 10min. After the polymerization is completed, turn off the ethylene gas source, cool to 80°C, and slowly press the polymer into ethanol to quench the reaction. Collect the polymer, dry it in vacuum to constant weight, and weigh it.

[0198] The polymerization methods of Example 13 to Example 31 are basically the same, and the main changes are ethylene pressure, the amount of 1-octene, the amount of methylaluminoxane (MAO), and the amount of borate. Me1 represents catalyst I-52, Me2 represents catalyst I-53, Me3 represents catalyst I-54, B represents borate trityltetrakis(pentafluorophenyl)borate, Al / M represents the molar ratio of aluminum element to metal compound, and B / M represents the molar ratio of boron compound to metal compound.

[0199] Table 1 Polymerization raw materials

[0200]

[0201] Table 2 Aggregation results

[0202]

[0203] The insertion rate of 1-octene was 13 C-NMR (Bruker ADVANCE III400M) was used for measurement. The polymer was prepared into a deuterated 1,2-o-dichlorobenzene solution of about 100 mg / mL at 150°C. The instrument parameters were a pulse angle of 30 degrees, full decoupling, a pulse delay time of 3s, and the sample was scanned continuously for more than 3000 times to obtain its high-temperature NMR spectrum. The 1-octene insertion amount was obtained by analyzing the spectrum.

[0204] In the present application, the molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the polymer are measured by high temperature gel permeation chromatography (PL-GPC220) with 1,2,4-trichlorobenzene as the mobile phase and polystyrene as the standard at 150°C.

[0205] The melting point of the polymer (T m ) was measured using a differential scanning calorimeter (METTLER, DSC-1).

[0206] The octene insertion rates of Examples 26, 29, and 39 were 6.32%, 4.14%, and 4.60%, respectively, and the polymerization activities (kg / mmoL.cat.h) were 42.3, 47.3, and 41.8, respectively. The above data show that the catalytic system has a high copolymerization ability and can efficiently promote the copolymerization of ethylene and octene. The melting points (°C) of Examples 36, 37, and 38 were 93.4, 50.3, and 63.2, respectively, and the octene insertion rates were 6.32%, 13.98%, and 11.69, respectively. Under the condition of low ethylene pressure and high octene content, polymers with moderate melting points and high octene insertion content can be obtained. On the contrary, polymers with high melting points and high ethylene content can be obtained, such as Examples 23, 24, 25, 29, 30, and 31. The dosage (Al / M) of methylaluminoxane in Examples 32, 33, 26, 34, and 35 was 300, 400, 500, 600, and 700, respectively, and the polymerization activities (kg / mmoL.cat.h) were 23.4, 37.6, 42.3, 43.5, and 35.4, respectively, and the octene insertion rates were 7.37, 5.97, 6.32, 4.55, and 5.49, respectively; the dosage (B / M) of borate in Examples 36, 26, 37, 38, and 39 was 1.5, 2.5, 3.5, 4.5, and 5.5, respectively, and the polymerization activities (kg / mmoL.cat.h) were 32.3, 42.3, respectively. , 35.4, 39.3, 41.8, and the octene insertion rates were 8.13, 6.32, 5.49, 5.97, 4.60, respectively. From the above data, it can be seen that increasing the dosage of methylaluminoxane or borate in a certain amount can significantly improve the polymerization activity, and the amount of 1-octene insertion does not change much. It can be inferred that it fully quenches the moisture in the solvent, so that the system can better catalyze the polymerization reaction. However, when its amount exceeds a certain amount, such as in Example 35, the dosage of methylaluminoxane (Al / M) is 700, and the activity (kg / mmoL.cat.h) is reduced to 35.3. It can be inferred that at this time, the chain transfer increases and the active species are deactivated.

[0207] Me1 has the highest catalytic activity and 1-octene insertion, indicating that the ligand structure has a large steric hindrance, which affects the rotation of the metal center, thereby giving the catalyst a specific space and good copolymerization ability.

[0208] The above embodiments are merely illustrative of the principles and effects of the present invention, and are not intended to limit the present invention. Anyone familiar with the art may modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by a person of ordinary skill in the art without departing from the spirit and technical concept disclosed by the present invention shall still be covered by the claims of the present invention.

Claims

1. A heteroatom-containing metallocene compound, characterized in that: The general structural formula of the heteroatom-containing metallocene compound is shown in the following formula I: ； Among them, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 Each is independently hydrogen, or a C1-50 unsubstituted hydrocarbon group, or a phenyl group; Each X is independently a halogen atom or a methyl group; n is 1, 2, or 3; m is 0, 1, 2, or 3; The t value is 0, 1, 2, or 3; M is one selected from Ti, Zr, and Hf; A is one selected from N and P; D is one selected from P, O, and S; E is one selected from P, O, and S; F is C.

2. The heteroatom-containing metallocene compound according to claim 1, characterized in that The hydrocarbon group is selected from one of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl.

3. The heteroatom-containing metallocene compound according to claim 1, characterized in that The structural formula of the heteroatom-containing metallocene compound is one of the following: ； ； 。 4. A method for preparing a heteroatom-containing metallocene compound according to any one of claims 1 to 3, comprising: 1) The heteroatom ligand reacts with the alkali metal hydrocarbon compound to obtain a salt; ； 2) reacting a salt of a heteroatom ligand with a single metallocene compound to obtain the heteroatom-containing metallocene compound; 。 5. A catalyst combination, characterized in that: The catalyst combination comprises the heteroatom-containing metallocene compound as claimed in any one of claims 1 to 3 and an activator, wherein the heteroatom-containing metallocene compound and the activator can interact with each other to form an ion pair compound.

6. The catalyst combination according to claim 5, characterized in that The molar ratio of the heteroatom-containing metallocene compound to the activator is 5 to 1000; and / or the activator contains aluminum and / or boron.

7. The catalyst combination according to claim 6, characterized in that The activator containing aluminum element is alkyl aluminum and / or aryl aluminum and / or alkyl aluminumoxane and / or aryl aluminumoxane; the boron element is introduced by borate.

8. Use of the catalyst combination according to any one of claims 5 to 7 in elastomer polymerization.

9. The use according to claim 8, characterized in that The elastomer reaction monomer is polymerized in the presence of the catalyst combination as claimed in any one of claims 5 to 7; and / or, the elastomer has a melting point of 30°C-180°C; and / or, the weight average molecular weight of the elastomer is 10000-600000Da; And / or, the ratio of the weight average molecular weight to the number average molecular weight of the elastomer is 1.5-3.

7.

10. The use according to claim 8, characterized in that The reactive monomer is an olefin; And / or, the polymerization reaction adopts an intermittent solution polymerization method; And / or, the polymerization reaction temperature is 80 to 250°C; And / or, the polymerization reaction pressure is 0.1-10 MPa.

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