An amidoimine monometallic complex and its use in the preparation of poly(4-methyl-1-pentene) waxes

Abstract

The application discloses an amidoimine monometal complex and application thereof in preparation of poly(4-methyl-1-pentene) wax. The structure of the amidoimine monometal complex is shown in formula (I): formula (I); wherein M is Ti, Zr or Hf, and R is H, methyl or isopropyl; the amidoimine monometal complex provided by the application is used for catalyzing homopolymerization of 4-methyl-1-pentene, and low-molecular-weight, narrow-distribution and high-melting-point poly(4-methyl-1-pentene) wax can be obtained; the poly(4-methyl-1-pentene) wax has good lubricating performance, temperature resistance and easy peeling performance.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of metallocene complex catalyzing olefin polymerization, and particularly relates to an amine imine monometallocene complex and application thereof in preparing poly(4-methyl-1-pentene) wax. BACKGROUND

[0002] Polyolefin wax is a low molecular weight polyolefin material, and the molecular weight thereof is generally less than 10000, and the polyolefin wax is in a waxy state at room temperature. The polyolefin wax can be used as a good lubricant, a release agent, a dispersant, a tackifier, a matting agent, an anti-settling agent, a leveling agent and the like due to its non-toxicity, non-corrosiveness, wear resistance, heat resistance, chemical resistance and good dispersibility and flowability, and becomes an important chemical raw material indispensable to the rubber, ink, paint and metal casting industries. The polyolefin wax generally includes polyethylene wax, polypropylene wax, polyolefin wax obtained by copolymerization of ethylene or propylene, and the like. α - polyolefin wax obtained by copolymerization of olefins.

[0003] At present, there are many related literatures about poly(4-methyl-1-pentene) materials, and the Mitsui Chemicals Company in Japan has realized industrial production of high molecular weight poly(4-methyl-1-pentene) by using a Ziegler-Natta catalyst, and the product is a commercial product with a trade name of TPX. However, there are few methods for preparing low molecular weight poly(4-methyl-1-pentene). In a patent (CN118076650 A) disclosed by the Toyo Roshi Kaisha Kabushiki Kaisha, a method for manufacturing low molecular weight poly(4-methyl-1-pentene) wax is provided, and the method is to crack poly(4-methyl-1-pentene) and other types of polyolefins at high temperature, and the cracking product contains low molecular weight poly(4-methyl-1-pentene). The preparation method is realized by high-temperature cracking of high molecular weight products, and the product is a cracking wax, which has poor quality and is difficult to control, and the production has high energy consumption and cost. Therefore, it is of great significance and actual demand to develop a catalyst with excellent catalytic performance and apply the catalyst to preparation of poly(4-methyl-1-pentene) wax. SUMMARY

[0004] In order to overcome the deficiencies of the prior art, the amine imine monometallocene complex provided by the application is used to catalyze homopolymerization of 4-methyl-1-pentene, and low molecular weight, narrow distribution and high melting point poly(4-methyl-1-pentene) wax can be obtained, and the poly(4-methyl-1-pentene) wax has good lubricating performance, temperature resistance and easy peeling performance.

[0005] The application aims to provide an amine imine monometallocene complex, and a structural formula of the amine imine monometallocene complex is shown as formula (I):

[0006]

[0007] Formula (I);

[0008] wherein M is Ti, Zr or Hf, and R is H, methyl or isopropyl.

[0009] In some embodiments of the present application, in the formula (I), M is Hf, and R is H, methyl or isopropyl.

[0010] In some embodiments of the present application, in the formula (I), M is Hf, and R is isopropyl.

[0011] Another object of the present application is to provide a preparation method of the amidoimine monometallic complex, comprising the following steps:

[0012] S1. α - a diimine compound reacting with trimethylaluminum to obtain an amidoimine ligand ;

[0013] S2. a metal precursor compound reacting with the amidoimine ligand to obtain the amidoimine monometallic complex;

[0014] wherein M is Ti, Zr or Hf, and R is H, methyl or isopropyl.

[0015] In some embodiments of the present application, in S1, the α molar ratio of the diimine compound to trimethylaluminum is 1:1.

[0016] In some embodiments of the present application, in S1, the reaction temperature is 80-120℃, and the reaction time is 4-8 hours.

[0017] In some embodiments of the present application, in S2, the molar ratio of the metal precursor compound to the amidoimine ligand is 1:1.

[0018] In some embodiments of the present application, in S2, the reaction temperature is a greenhouse, and the reaction time is 10-16 hours.

[0019] Another object of the present application is to provide the application of the amidoimine monometallic complex in the preparation of poly(4-methyl-1-pentene) wax or the application of the amidoimine monometallic complex prepared by the preparation method of the amidoimine monometallic complex in the preparation of poly(4-methyl-1-pentene) wax.

[0020] Another object of the present application is to provide a preparation method of poly(4-methyl-1-pentene) wax, comprising the following steps:

[0021] 4-methyl-1-pentene monomer is polymerized under the action of the amine imine monometallic catalyst to obtain poly(4-methyl-1-pentene) wax;

[0022] The amine imine monometallic catalyst is composed of the amine imine monometallic complex of claim 1 and a cocatalyst.

[0023] In some embodiments of the present application, the temperature of the polymerization reaction is 0-80℃, and the time is 5-20 minutes.

[0024] In some embodiments of the present application, the temperature of the polymerization reaction is 30-50℃, and the time is 10 minutes.

[0025] In some embodiments of the present application, the solvent of the polymerization reaction is at least one of toluene, pentane, hexane, heptane, octane, nonane, and decane.

[0026] In some embodiments of the present application, the solvent of the polymerization reaction is at least one of toluene, hexane, and heptane.

[0027] In some embodiments of the present application, the molar ratio of the 4-methyl-1-pentene monomer to the amine imine monometallic complex is 1000-20000:1.

[0028] In some embodiments of the present application, the molar ratio of the 4-methyl-1-pentene monomer to the amine imine monometallic complex is 4000-10000:1.

[0029] In some embodiments of the present application, the cocatalyst is an organic boron compound.

[0030] In some embodiments of the present application, the organic boron compound is at least one of tris(pentafluorophenyl)borane, trityl tetra(pentafluorophenyl)borate, and N,N-dimethylanilinium tetra(pentafluorophenyl)borate.

[0031] In some embodiments of the present application, the molar ratio of the cocatalyst to the amine imine monometallic complex is 1-2:1.

[0032] In some embodiments of the present application, the molar ratio of the cocatalyst to the amine imine monometallic complex is 1.2-1.8:1.

[0033] Another object of the present application is to provide a low molecular weight poly(4-methyl-1-pentene) wax, which has a structure shown in formula (II):

[0034]

[0035] Formula (II)

[0036] wherein the low molecular weight poly(4-methyl-1-pentene) wax has a weight average molecular weight M w not higher than 20000 g / mol, a molecular weight distribution index (M w / M n ) not higher than 3.0, and a melting point not lower than 180℃.

[0037] In some embodiments of the present application, the low molecular weight poly(4-methyl-1-pentene) wax has a weight average molecular weight M w of 2300-20000 g / mol, and a molecular weight distribution index (M w / M n ) of 1.5-2.5.

[0038] In some embodiments of the present application, the low molecular weight poly(4-methyl-1-pentene) wax has a weight average molecular weight M w of 3000-10000 g / mol, and a molecular weight distribution index (M w / M n ) of 1.8-2.5.

[0039] In some embodiments of the present application, the low molecular weight poly(4-methyl-1-pentene) wax has a melting point of 180-210℃.

[0040] In some embodiments of the present application, the low molecular weight poly(4-methyl-1-pentene) wax has a melting point of 200-210℃.

[0041] Compared with the prior art, the present application has the following beneficial effects:

[0042] (1) The amine-based imine monometallic complex provided by the present application is used for catalyzing the homopolymerization of 4-methyl-1-pentene, and a low molecular weight, narrow distribution, high melting point poly(4-methyl-1-pentene) wax can be obtained, which has good lubricating performance, temperature resistance and easy peeling performance.

[0043] (2) The preparation method of the amine-based imine monometallic complex provided by the present application has the advantages of simple operation, mild reaction conditions and high yield.

[0044] (3) The preparation method of the poly(4-methyl-1-pentene) wax provided by the present application has the advantages of mild reaction conditions and efficient controllability of the entire polymerization reaction compared with the cracking method, has the obvious advantage of low energy consumption for realizing industrialized production, and meets the requirements of low carbon and environmental protection.

[0045] (4) The poly(4-methyl-1-pentene) wax provided by the application has narrow molecular weight distribution, and compared with the cracked wax prepared by the cracking method of high molecular weight poly(4-methyl-1-pentene), the poly(4-methyl-1-pentene) wax of the application is a high-end synthetic wax, and has indispensable application in a higher-end field.

[0046] (5) The poly(4-methyl-1-pentene) wax provided by the application has higher melting point compared with the commercially available polyethylene wax and polypropylene wax, and thus has higher temperature resistance and can be applied in a higher temperature environment; at the same time, the poly(4-methyl-1-pentene) wax has better lubricating performance and easy peeling performance, and has wider application compared with the commercially available polyethylene wax and polypropylene wax. BRIEF DESCRIPTION OF DRAWINGS

[0047] Figure 1 The GPC curve of the poly(4-methyl-1-pentene) wax prepared in Example 12 of the application;

[0048] Figure 2 The DSC curve of the poly(4-methyl-1-pentene) wax prepared in Example 19 of the application;

[0049] Figure 3 The nuclear magnetic carbon spectrum of the poly(4-methyl-1-pentene) wax prepared in Example 19 of the application;

[0050] Figure 4 The sample picture of the poly(4-methyl-1-pentene) wax prepared in Example 19 of the application. DETAILED DESCRIPTION

[0051] In order to enable the person skilled in the art to better understand the technical solutions in the application, the technical solutions of the application will be described clearly and completely in combination with the embodiments of the application. Obviously, the described embodiments are only some of the embodiments of the application, but not all the embodiments. Based on the embodiments in the application, all other embodiments obtained by the person skilled in the art without creative labor should belong to the protection scope of the application.

[0052] All raw materials of the application can be purchased through commercial channels.

[0053] Test and characterization method of the compound adopted by the application:

[0054] NMR analysis was performed by using AVANCE III HD 500 of Bruker Company, and tetramethylsilane (TMS) was used as an internal standard for testing the structure of the compound at 25°C. The molecular weight and molecular weight distribution of the polymer were determined by using PL-GPC220 of Agilent Company, trichlorobenzene as a solvent, at 150°C (standard sample: PS, flow rate: 1.0 mL / min). The melting point of the polymer was determined by using DSC 204 F1 differential scanning calorimeter (DSC) of NETZSCH Company, under nitrogen protection, at a temperature changing rate of 10°C / min (test temperature range: 30-260°C), and the second heating curve was recorded. The drop melting point of the polymer was determined according to GB / T 8026-2014 “Determination of Drop Melting Point of Petroleum Waxes and Petroleum Fats”.

[0055] The synthesis route of the amido imine monometallic complex is as follows:

[0056]

[0057] In the examples, Cp*HfMe3 represents a metal precursor compound .

[0058] The structure of the amido imine monometallic complex in the examples is shown in formula (I):

[0059]

[0060] Formula (I);

[0061] In formula (I), M is Hf, and R is H, methyl or isopropyl.

[0062] In order to more clearly describe the catalyst in the examples, the complex in the examples is numbered as follows:

[0063] The amido imine monometallic complex Hf-1, M is Hf, and R is H;

[0064] The amido imine monometallic complex Hf-2, M is Hf, and R is methyl;

[0065] The amido imine monometallic complex Hf-3, M is Hf, and R is isopropyl.

[0066]

[0067] Example 1

[0068] The examples provide α The synthesis method of the diimine compound A1 is specifically as follows:

[0069] Into a 100 mL round-bottom flask, anhydrous ethanol 30 mL, aniline (36 mmol), butanedione (18 mmol), formic acid 0.5 mL were added successively under nitrogen atmosphere and room temperature, and the reaction was stirred at 60 °C for 12 h, cooled to room temperature, and terminated. The organic phase was separated by extraction, and the solvent was removed by evaporation to obtain 3.0 g of orange-yellow crystals with a yield of 71.6 %.

[0070] 1 H NMR (400 MHz, CDCl3), δ (ppm): 7.28~6.95(m, 10H, Ph), 2.15(s, 6H,C H 3)。

[0071] 13 C NMR (100 MHz, CDCl3), δ (ppm): 168.23, 144.27, 135.73, 125.63,120.76, 15.62。

[0072] Example 2

[0073] This example provides α - diimine compound A2, the synthesis method of which is specifically as follows:

[0074] The synthesis method of this example is only different from the synthesis method of Example 1 in that “aniline” in Example 1 is replaced by “2,6-dimethylaniline” to obtain 3.9 g of orange-yellow crystals with a yield of 73.9 %.

[0075] 1 H NMR (400 MHz, CDCl3), δ (ppm): 7.17~7.12(m, 6H, Ph), 2.33 (s, 12H,C H 3), 2.15(s, 6H, C H 3)。

[0076] 13 C NMR (100 MHz, CDCl3), δ (ppm): 168.23, 144.27, 135.73, 125.63,120.76, 18.29, 15.62。

[0077] Example 3

[0078] This example provides α - diimine compound A3, the synthesis method of which is specifically as follows:

[0079] The synthesis method of this example is only different from the synthesis method of Example 1 in that "aniline" in Example 1 is replaced by "2,6-diisopropylaniline", to obtain 5.3 g of orange-yellow crystals, with a yield of 73.6 %.

[0080] 1 H NMR (400 MHz, CDCl3), δ (ppm): 7.17~7.12(m, 6H, Ph), 2.72 (septet,4H, J = 6.87 Hz, C H ), 2.10(s, 6H, C H 3), 1.22 (dd, 24H, J 1 = 2.61 Hz, J 2 = 6.87Hz, C H 3)。

[0081] 13 C NMR (100 MHz, CDCl3), δ (ppm): 169.13, 145.21 136.33, 124.43,121.86, 27.54, 23.73, 21.56, 17.25。

[0082] Example 4

[0083] This example provides the amine-based imine ligand B1, and the synthesis method thereof is specifically as follows:

[0084] Into a 100 mL flask equipped with a reflux condenser, nitrogen atmosphere protection, the diimine compound A1 (8 mmol) obtained in Example 1 was weighed, and then 10 mL of toluene and a trimethylaluminum solution (TMA, 4.0 mL, 2M) were sequentially added. The reaction was stirred at 100°C for 6 hours. After cooling, it was terminated with a sodium hydroxide / water solution. The organic phase was separated by extraction, and the solvent was evaporated to obtain 1.46 g of colorless crystals, with a yield of 72.4 %. α 1 H NMR (400 MHz, CDCl3), δ (ppm): 7.28~6.95(m, 10H, Ph), 4.48 (s, 1H,N

[0085] ), 1.84 (s, 3H, C H 3), 1.46(s, 6H, C H 3)。 H

[0086] 13 ​C NMR (100 MHz, CDCl3), δ (ppm): 176.44, 148.36, 133.73, 128.73, 128.36, 125.24, 122.49, 122.26, 62.63, 27.27, 24.37, 20.85, 18.24, 16.28.

[0087] Example 5

[0088] This example provides the synthesis of the amidoimine ligand B2, which is as follows:

[0089] The difference between the synthesis of this example and that of Example 4 is that the diimine compound A2 obtained in Example 2 is used instead of the diimine compound Al obtained in Example 1. α - diimine compound A2 obtained in Example 2 is used instead of the diimine compound Al obtained in Example 1. α - diimine compound A2 obtained in Example 2 is used instead of the diimine compound Al obtained in Example 1.

[0090] 1 H NMR (400 MHz, CDCl3), δ (ppm): 7.00~6.90 (m, 6H, Ph), 4.48 (s, 1H, N H ), 2.33(s, 6H, C H 3), 2.08(s, 6H, C H 3), 1.84 (s, 3H, C H 3), 1.46(s, 6H, C H 3).

[0091] 13 C NMR (100 MHz, CDCl3), δ (ppm): 176.44, 148.36, 133.73, 128.73, 128.36, 125.24, 122.49, 122.26, 62.63, 27.27, 24.37, 20.85, 18.24, 16.28.

[0092] Example 6

[0093] This example provides the synthesis of the amidoimine ligand B3, which is as follows:

[0094] The difference between the synthesis of this example and that of Example 4 is that the diimine compound A3 obtained in Example 3 is used instead of the diimine compound Al obtained in Example 1. α - diimine compound A3 obtained in Example 3 is used instead of the diimine compound Al obtained in Example 1. α - diimine compound A3 obtained in Example 3 is used instead of the diimine compound Al obtained in Example 1.

[0095] 1 H NMR (400 MHz, CDCl3), δ (ppm): 7.15~7.10 (m, 6H, Ph), 4.34 (s, 1H,N H ), 3.54 (septet, 2H, J = 6.74 Hz, C H ), 2.82 (septet, 2H, J = 6.76 Hz, C H ),1.86 (s, 3H, C H 3), 1.36 (s, 6H, C H 3), 1.21~1.18 (m, 24H, C H 3)。

[0096] 13 C NMR (100 MHz, CDCl3), δ (ppm): 178.24, 147.64, 145.06, 142.71,135.62, 124.84, 123.93, 121.87, 59.57, 30.43, 29.65, 27.67, 25.87, 23.64,22.74, 15.28。

[0097] Example 7

[0098] This example provides an amido-imine mono-metallocene complex Hf-1, and the synthesis method is as follows:

[0099] The amido-imine ligand B1 (0.75 mmol) and Cp*HfMe3 (0.75 mmol) obtained in Example 4 were weighed into a Schlenk flask with a stirrer under a nitrogen atmosphere, and dissolved in 20 mL of anhydrous ether solution. Stirring was carried out at room temperature for 12 h, the reaction was completed, the solvent was dried, extracted with n-hexane, concentrated, recrystallized, and filtered to obtain 0.33 g of yellow crystals, with a yield of 74 %.

[0100] 1 H NMR (400 MHz, C6D6), δ (ppm): 8.13~8.00(m, 10H, Ph), 5.28 (s, 1H,N H ), 2.57 (s, 3H, C H 3), 2.13(s, 6H, C H 3), 1.85 (s, 15H, Cp*), 0.34 (s, 6H, Hf-CH 3).

[0101] 13 C NMR (100 MHz, C6D6), δ (ppm): 179.27, 148.31, 139.48, 127.69,122.96, 119.46, 63.87, 55.52, 27.67, 16.38, 11.47.

[0102] Example 8

[0103] This example provides an amine imine monometal complex Hf-2, and the synthesis method is as follows:

[0104] The synthesis method of this example is only different from the synthesis method of Example 7 in that the amine imine ligand B2 obtained in Example 5 is replaced by the amine imine ligand B1 obtained in Example 7, and other conditions are the same as those in Example 7, and 0.39 g of yellow crystals is obtained, with a yield of 77%.

[0105] 1 H NMR (400 MHz, C6D6), δ (ppm): 7.75~7.62 (m, 6H, Ph), 5.03 (s, 1H,N H ), 3.04(s, 6H, C H 3), 2.62(s, 6H, C H 3), 2.24 (s, 3H, C H 3), 2.04(s, 6H, C H 3),1.85 (s, 15H, Cp*), 0.34 (s, 6H, Hf-C H 3).

[0106] 13 C NMR (100 MHz, C6D6), δ (ppm): 180.44, 149.86, 135.96, 130.26,129.16, 126.74, 123.84, 122.86, 116.92, 62.63, 54.94, 28.78, 25.64, 22.94,20.51, 18.57, 11.53.

[0107] Example 9

[0108] This example provides an amine imine monometal complex Hf-3, and the synthesis method is as follows:

[0109] The synthetic method of this example is distinguished from that of Example 7 only in that the amido-imine ligand B3 obtained in Example 6 is used instead of the amido-imine ligand B1 obtained in Example 7, and other conditions are the same as in Example 7, to obtain 0.46 g of yellow crystals, in a yield of 78 %.

[0110] 1 H NMR (400 MHz, C6D6), δ (ppm): 8.00~7.86 (m, 6H, Ph), 5.26 (s, 1H, N H ), 4.35 (septet, 2H, J = 6.74 Hz, C H ), 3.64 (septet, 2H, J = 6.76 Hz, C H ), 2.58 (s, 3H, C H 3), 2.04 (s, 6H, C H 3), 2.00~1.91 (m, 24H, C H 3), 1.80 (s, 15H, Cp*), 0.34 (s, 6H, Hf-C H 3).

[0111] 13 C NMR (100 MHz, C6D6), δ (ppm): 180.21, 149.52, 146.94, 144.26, 136.79, 126.23, 125.47, 123.94, 120.93, 62.95, 56.87, 32.73, 30.46, 28.84, 26.24, 24.51, 23.19, 16.58, 11.67.

[0112] Example 10

[0113] This example provides a poly(4-methyl-1-pentene) wax, and a preparation method thereof specifically includes the following steps:

[0114] Under anhydrous and anaerobic conditions, 4 mL of dry toluene, 5 mL of 4-methyl-1-pentene monomer (4M1P / Hf molar ratio = 4000:1) were sequentially added into a reaction bottle, and stirred for 10 minutes to make the whole system uniform. Then 6.11 mg of the procatalyst Hf-1 and 13.8 mg of the cocatalyst triphenylcarbenium tetrakis(pentafluorophenyl)borate ([Ph3C][B(C6F5)4]), B / Hf molar ratio = 1.5:1) were stirred in 1 mL of toluene for 5 minutes to form a homogeneous solution, which was then added into the reaction bottle to initiate the polymerization of 4-methyl-1-pentene. The polymerization was carried out at 50ºC for 10 minutes, and then terminated by using a 10% hydrochloric acid solution in ethanol. The polymer product was separated by filtration, washed with ethanol three times, and dried in a vacuum drying oven at 60ºC for 12 h to obtain a poly(4-methyl-1-pentene) wax product.

[0115] Example 11

[0116] This example provides a poly(4-methyl-1-pentene) wax, and the preparation method thereof specifically comprises the following steps:

[0117] The preparation method of this example is only different from the preparation method of Example 10 in that the “procatalyst Hf-1” in Example 10 is replaced by “procatalyst Hf-2”.

[0118] Example 12

[0119] This example provides a low molecular weight poly(4-methyl-1-pentene) wax, and the preparation method thereof specifically comprises the following steps:

[0120] The preparation method of this example is only different from the preparation method of Example 10 in that the “procatalyst Hf-1” in Example 10 is replaced by “procatalyst Hf-3”.

[0121] The specific polymerization results of Examples 10-12 are shown in Table 1:

[0122] Table 1. Polymerization results of 4-methyl-1-pentene catalyzed by different catalysts.

[0123] Example Catalyst Activity (10 6 g / (mol M · h)) M w (g / mol)]]> M w / M n ]]> Melting point (°C) Drop point (°C) Example 10 Hf-1 1.53 5000 1.96 185 188 Example 11 Hf-2 1.59 4800 2.17 184 187 Example 12 Hf-3 1.98 4500 1.92 183 186

[0124] Example 13

[0125] This example provides a poly(4-methyl-1-pentene) wax, and the preparation method thereof specifically comprises the following steps:

[0126] The preparation method of this example is only different from the preparation method of Example 12 in that the “cocatalyst [Ph3C][B(C6F5)4]” in Example 12 is replaced by “cocatalyst B(C6F5)3”.

[0127] Example 14

[0128] The present example provides a poly(4-methyl-1-pentene) wax, the preparation method of which specifically comprises the following steps:

[0129] The preparation method of the present example is only different from the preparation method of Example 12 in that the “cocatalyst [Ph3C][B(C6F5)4]” in Example 12 is replaced by “cocatalyst [HNMe2Ph][B(C6F5)4]”.

[0130] The specific polymerization results of Examples 13-14 are shown in Table 2:

[0131] Table 2. Polymerization results of complex Hf-3 catalyzing 4-methyl-1-pentene under different cocatalysts.

[0132]

[0133] Examples 15-18

[0134] The present example provides a poly(4-methyl-1-pentene) wax, the preparation method of which specifically comprises the following steps:

[0135] Examples 15-18 are only different from Example 12 in that the molar ratio of the main catalyst to the cocatalyst is different, and the specific results are shown in Table 3:

[0136] Table 3. Polymerization results of complex Hf-3 catalyzing 4-methyl-1-pentene under different cocatalyst ratios.

[0137]

[0138] Examples 19-21

[0139] The present example provides a poly(4-methyl-1-pentene) wax, the preparation method of which specifically comprises the following steps:

[0140] Examples 19-21 are only different from Example 12 in that the polymerization temperature is different, and the specific results are shown in Table 4:

[0141] Table 4. Polymerization results of complex Hf-3 catalyzing 4-methyl-1-pentene under different polymerization temperatures.

[0142] Example T(℃) Activity (10 6 g / (mol M h) M w (g / mol)]]> M w / M n ]]> Melting point (°C) Drop point (°C) Example 19 0 1.24 14700 2.83 205 208 Example 20 30 1.36 9600 2.26 194 197 Example 21 80 1.43 6800 2.14 187 190

[0143] Examples 22-27

[0144] The present example provides a poly(4-methyl-1-pentene) wax, the preparation method of which specifically comprises the following steps:

[0145] Examples 22-27 differ from Example 12 only in the solvent used, and the results are shown in Table 5.

[0146] Table 5. Polymerization results of complex Hf-3 catalyzing 4-methyl-1-pentene under different solvents.

[0147] Example Solvent Activity (10 6 g / (mol M · h)) M w (g / mol)]]> M w / M n ]]> Melting point (°C) Drop point (°C) Example 22 n-Pentane 1.51 7300 2.09 188 191 Example 23 n-Hexane 1.46 6200 2.16 186 189 Example 24 n-Heptane 1.42 5900 2.23 186 189 Example 25 n-Octane 1.36 5700 2.26 186 189 Example 26 n-Nonane 1.34 5700 2.26 186 189 Example 27 n-Decane 1.32 5500 2.29 185 188

[0148] Examples 28-30

[0149] Examples 28-30 provide a poly(4-methyl-1-pentene) wax, and the method of making the same includes the following steps:

[0150] Examples 28-30 differ from Example 12 only in the 4M1P / Hf molar ratio, and the results are shown in Table 6.

[0151] Table 6. Polymerization results of complex Hf-3 catalyzing 4-methyl-1-pentene under different 4M1P / Hf molar ratios.

[0152] Example 4M1P / Hf molar ratio Activity (10 6 g / (mol M h) M w (g / mol)]]> M w / M n ]]> Melting point (°C) Drop point (°C) Example 28 1000 0.23 2300 1.76 180 183 Example 29 10000 3.34 12800 2.56 204 207 Example 30 20000 3.92 20000 2.94 210 213

[0153] Comparative Example 1

[0154] This comparative example provides a method of preparing a polyethylene wax by polymerizing ethylene with a Ziegler-Natta catalyst (CN101589072A) invented by V. Schlenk et al. of Wincent Dqfasai Co., Ltd., using a Ziegler-Natta catalyst composed of titanium tetrachloride and a dialkyl aluminum halide, under polymerization conditions of a polymerization temperature of 185°C, an Al / Ti molar ratio = 1.4, and a polymerization system substantially free of solvent, to obtain a polyethylene wax product having a weight average molecular weight of 4100 g / mol, a molecular weight distribution index of 3.40, a melting point of 117°C, and a drop melting point of 120°C.

[0155] Comparative Example 2

[0156] This comparative example provides a method of preparing a polypropylene wax by polymerization in the presence of hydrogen with a metallocene compound (CN1206720A) invented by H. F. Hermann et al. of Clariant GmbH, using an ethylene bis-1, l'-(2-methyl-4-phenylindenyl) zirconium dichloride catalyst, under polymerization conditions of 12 mmol of triethylaluminum, a polymerization temperature of 70°C, and 2.5 bar of hydrogen, to obtain a polypropylene wax product having a weight average molecular weight of 5600 g / mol, a molecular weight distribution index of 2.27, a melting point of 152°C, and a drop melting point of 155°C.

[0157] The poly(4-methyl-1-pentene) wax prepared in Example 12 was taken as an example, and its performance was determined and compared with the polyethylene wax and the polypropylene wax in Comparative Examples 1-2, and the specific results are shown in Table 7:

[0158] Table 7. Comparison results of polyolefin wax performance.

[0159] Sample Polyethylene wax (Comparative Example 1) Polypropylene wax (Comparative Example 2) Poly(4-methyl-1-pentene) wax (Example 12) Weight average molecular weight (g / mol) 4100 5600 4500 Molecular weight distribution index 3.40 2.27 1.92 Melting point (°C) 117 152 183 Drop melting point (°C) 120 155 186 Surface tension (mN / m) 31 31~33 24

[0160] As can be seen from Table 7, compared with the polyethylene wax (Comparative Example 1) and the polypropylene wax (Comparative Example 2), the poly(4-methyl-1-pentene) wax has a narrower molecular weight distribution, not more than 2.0, which makes it have more excellent lubricating performance; in terms of temperature resistance, the melting point and the drop melting point of the poly(4-methyl-1-pentene) wax are not less than 180℃, which is much greater than the melting point and the drop melting point of the polyethylene wax and the polypropylene wax in the comparative examples, and it shows more excellent temperature resistance; in terms of peeling performance, the poly(4-methyl-1-pentene) wax has very low surface tension, which is 24 mN / m, much smaller than the surface tension of the polyethylene wax and the polypropylene wax in the comparative examples, and it shows more excellent easy peeling performance. The experimental results show that, compared with the existing polyethylene wax and the polypropylene wax, the poly(4-methyl-1-pentene) wax provided by the present application has better lubricating performance, temperature resistance and easy peeling performance.

[0161] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present application and not to limit it. Although the present application has been described in detail with reference to the above examples, those skilled in the art should understand that the technical personnel can still modify or replace the specific embodiments of the present application after reading the present application. The specification, but these modifications or changes do not deviate from the scope of the present application.

Claims

1. An aminylimine monometallic complex, characterized in that, The amidoimine monometallic complex has a structural formula as shown in formula (I): Formula (I); wherein M is Ti, Zr or Hf, and R is H, methyl or isopropyl.

2. A process for the preparation of the amidoimine monometallic complex according to claim 1, characterized in that, The method comprises the following steps: S1. Alpha-diimine compound reacting with trimethylaluminum to give the amido-imine ligand ; S2. metal precursor compound with said amine-based imine ligand to obtain said amine-based imine monometallic complex; wherein M is Ti, Zr or Hf, and R is H, methyl or isopropyl.

3. The process for the preparation of an amidoimine monometallic complex according to claim 2, characterized in that, In S1, the molar ratio of the α-diimine compound to trimethylaluminum is 1:

1. The reaction is carried out at a temperature of 80-120°C for 4-8 hours.

4. The process for the preparation of an amidoimine monometallic complex according to claim 2, characterized in that, In S2, the molar ratio of the metal precursor compound to the amidoimine ligand is 1:

1. The reaction is carried out for 10-16 hours.

5. Use of the amidoimine monometallic complex of claim 1 in the preparation of poly(4-methyl-1-pentene) wax or use of the amidoimine monometallic complex prepared by the method of any one of claims 2-4 in the preparation of poly(4-methyl-1-pentene) wax.

6. Use according to claim 5, characterized in that, The preparation of the poly(4-methyl-1-pentene) wax comprises the following steps: 4-methyl-1-pentene monomers are subjected to a polymerization reaction under the action of the amidoimine monometallic catalyst to obtain poly(4-methyl-1-pentene) wax; The amidoimine monometallic catalyst is composed of the amidoimine monometallic complex of claim 1 and a cocatalyst; the cocatalyst is an organic boron compound. The organic boron compound is at least one of tris(pentafluorophenyl)borane, triphenylmethyl tetrakis(pentafluorophenyl)borate and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate.

7. Use according to claim 6, characterized in that, The polymerization reaction is carried out at a temperature of 0-80°C for 5-20 minutes.

8. Use according to claim 6, characterized in that, The polymerization reaction is carried out in a solvent selected from at least one of toluene, pentane, hexane, heptane, octane, nonane and decane.

9. Use according to claim 6, characterized in that, The molar ratio of the 4-methyl-1-pentene monomers to the amidoimine monometallic complex is 1000-20000:

1.

10. Use according to claim 6, characterized in that, The molar ratio of the cocatalyst to the amidoimine monometallic complex is 1-2:1.

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