Amino imine single metallocene complex and application thereof in preparation of poly (4-methyl-1-pentene) wax

Abstract

The invention discloses an amino imine single metallocene complex and an application of the amino imine single metallocene complex in preparation of poly (4-methyl-1-pentene) wax. The structure of the amino imine single metallocene complex is as shown in a formula (I): # imgabs0 # formula (I); wherein M is Ti, Zr or Hf, and R is H, methyl or isopropyl; the amino imine mono-metallocene complex provided by the invention is used for catalyzing homopolymerization of 4-methyl-1-pentene, poly (4-methyl-1-pentene) wax with low molecular weight, narrow distribution and high melting point can be obtained, and the poly (4-methyl-1-pentene) wax has good lubricating property, temperature resistance and easy stripping property.

Description

Technical Field

[0001] The invention belongs to the technical field of olefin polymerization catalyzed by metallocene complexes, and in particular relates to an aminoimine monometallocene complex and application thereof in the preparation of poly (4-methyl-1-pentene) wax. Background Art

[0002] Polyolefin wax is a low molecular weight polyolefin material, with a molecular weight generally less than 10,000, and is waxy at room temperature. Due to its non-toxic, non-corrosive, wear-resistant, heat-resistant, chemical-resistant, good dispersibility and fluidity, it can be used as a good lubricant, release agent, dispersant, tackifier, matting agent, anti-precipitation agent, leveling agent, etc., and has become an indispensable and important chemical raw material in the rubber, ink, paint, metal casting and other industries. Polyolefin wax generally includes polyethylene wax obtained by homopolymerization of ethylene or propylene, polypropylene wax, ethylene and α -Polyolefin wax obtained by olefin copolymerization.

[0003] At present, there are many relevant literature reports on poly(4-methyl-1-pentene) materials. Among them, Mitsui Chemicals of Japan has used Ziegler-Natta catalysts to achieve industrial production of high molecular weight poly(4-methyl-1-pentene), with the product code TPX. However, there are very few methods for preparing low molecular weight poly(4-methyl-1-pentene). Toyobo Aimuxi Co., Ltd. disclosed a method for preparing low molecular weight poly(4-methyl-1-pentene) wax in patent (CN118076650 A), in which poly(4-methyl-1-pentene) is mixed with other types of polyolefins and then cracked at high temperature, and the cracked product contains low molecular weight poly(4-methyl-1-pentene). The preparation method is achieved by high temperature cracking of high molecular weight products, and the product is cracked wax, which has poor quality and is difficult to control, with high production energy consumption and high cost. Therefore, it is of great significance and practical demand to develop a catalyst with excellent catalytic performance and apply it to the preparation of poly(4-methyl-1-pentene) wax. Summary of the invention

[0004] In order to overcome the deficiencies of the prior art described above, the aminoimine monometallocene complex provided by the present invention is used to catalyze the homopolymerization of 4-methyl-1-pentene to obtain a poly(4-methyl-1-pentene) wax with a low molecular weight, narrow distribution and a high melting point. The poly(4-methyl-1-pentene) wax has good lubricity, temperature resistance and easy stripping properties.

[0005] The object of the present invention is to provide an aminoimine monometallocene complex, the structural formula of the aminoimine monometallocene complex is shown in formula (I):

[0006] Formula (I); Wherein, M is Ti, Zr or Hf, and R is H, methyl or isopropyl.

[0007] In some embodiments of the present invention, in the formula (I), M is Hf, and R is H, methyl or isopropyl.

[0008] In some embodiments of the present invention, in the formula (I), M is Hf and R is isopropyl.

[0009] Another object of the present invention is to provide a method for preparing the aminoimine monometallocene complex, comprising the following steps: S1. α -Diimine compounds Reaction with trimethylaluminum to obtain an aminoimine ligand ; S2. Metal Precursor Compounds With the amino imine ligand reacting to obtain the aminoimine monometallocene complex; Wherein, M is Ti, Zr or Hf, and R is H, methyl or isopropyl.

[0010] In some embodiments of the present invention, in S1, the α The molar ratio of the diimine compound to trimethylaluminum is 1:1.

[0011] In some embodiments of the present invention, in S1, the reaction temperature is 80-120° C. and the reaction time is 4-8 hours.

[0012] In some embodiments of the present invention, in S2, the molar ratio of the metal precursor compound to the aminoimine ligand is 1:1.

[0013] In some embodiments of the present invention, in S2, the reaction temperature is room temperature and the reaction time is 10 to 16 hours.

[0014] Another object of the present invention is to provide the use of the aminoimine monometallocene complex in the preparation of poly(4-methyl-1-pentene) wax or the use of the aminoimine monometallocene complex prepared by the preparation method of the aminoimine monometallocene complex in the preparation of poly(4-methyl-1-pentene) wax.

[0015] Another object of the present invention is to provide a method for preparing poly (4-methyl-1-pentene) wax, comprising the following steps: 4-methyl-1-pentene monomer undergoes polymerization reaction under the action of aminoimine monometallocene catalyst to obtain poly(4-methyl-1-pentene) wax; The aminoimine monometallocene catalyst is composed of the aminoimine monometallocene complex according to claim 1 and a co-catalyst.

[0016] In some embodiments of the present invention, the polymerization reaction is carried out at a temperature of 0 to 80° C. and for a time of 5 to 20 minutes.

[0017] In some embodiments of the present invention, the polymerization reaction is carried out at a temperature of 30-50° C. and for 10 minutes.

[0018] In some embodiments of the present invention, the solvent of the polymerization reaction is at least one of toluene, pentane, hexane, heptane, octane, nonane, and decane.

[0019] In some embodiments of the present invention, the solvent of the polymerization reaction is at least one of toluene, hexane and heptane.

[0020] In some embodiments of the present invention, the molar ratio of the 4-methyl-1-pentene monomer to the aminoimine monometallocene complex is 1000-20000:1.

[0021] In some embodiments of the present invention, the molar ratio of the 4-methyl-1-pentene monomer to the aminoimine monometallocene complex is 4000-10000:1.

[0022] In some embodiments of the present invention, the co-catalyst is an organic boron compound.

[0023] In some embodiments of the present invention, the organic boron compound is at least one of tris(pentafluorophenyl)borane, trityltetrakis(pentafluorophenyl)borate, and N, N-dimethylaniliniumtetrakis(pentafluorophenyl)borate.

[0024] In some embodiments of the present invention, the molar ratio of the co-catalyst to the aminoimine monometallocene complex is 1-2:1.

[0025] In some embodiments of the present invention, the molar ratio of the co-catalyst to the aminoimine monometallocene complex is 1.2-1.8:1.

[0026] Another object of the present invention is to provide a low molecular weight poly (4-methyl-1-pentene) wax, wherein the low molecular weight poly (4-methyl-1-pentene) wax has a structure shown in formula (II):

[0027] Formula (II) Wherein, the weight average molecular weight M of the low molecular weight poly (4-methyl-1-pentene) wax is w Not higher than 20000g / mol, molecular weight distribution index (M w / M n ) is not higher than 3.0, and the melting point is not lower than 180℃.

[0028] In some embodiments of the present invention, the weight average molecular weight M of the low molecular weight poly (4-methyl-1-pentene) wax is w is 2300~20000g / mol, the molecular weight distribution index (M w / M n ) is 1.5~2.5.

[0029] In some embodiments of the present invention, the weight average molecular weight M of the low molecular weight poly (4-methyl-1-pentene) wax is w is 3000~10000g / mol, the molecular weight distribution index (M w / M n ) is 1.8~2.5.

[0030] In some embodiments of the present invention, the melting point of the low molecular weight poly (4-methyl-1-pentene) wax is 180-210°C.

[0031] In some embodiments of the present invention, the melting point of the low molecular weight poly (4-methyl-1-pentene) wax is 200-210°C.

[0032] Compared with the prior art, the present invention has the following beneficial effects: (1) The aminoimine monometallocene complex provided by the present invention is used to catalyze the homopolymerization of 4-methyl-1-pentene to obtain a low molecular weight, narrow distribution, high melting point poly (4-methyl-1-pentene) wax, and the poly (4-methyl-1-pentene) wax has good lubricity, temperature resistance and easy stripping properties.

[0033] (2) The method for preparing the aminoimine monometallocene complex provided by the present invention has the advantages of simple operation, mild reaction conditions and high yield.

[0034] (3) Compared with the cracking method, the preparation method of poly (4-methyl-1-pentene) wax provided by the present invention has the advantages of mild reaction conditions and efficient and controllable entire polymerization reaction. It has the obvious advantage of low energy consumption for realizing industrial production and meets the requirements of low carbon and environmental protection.

[0035] (4) The poly(4-methyl-1-pentene) wax provided by the present invention has a narrow molecular weight distribution. Compared with the cracked wax prepared by the high molecular weight poly(4-methyl-1-pentene) cracking method, the poly(4-methyl-1-pentene) wax of the present invention is a high-end synthetic wax and has indispensable applications in higher-end fields.

[0036] (5) The poly(4-methyl-1-pentene) wax provided by the present invention has a higher melting point than commercially available polyethylene wax and polypropylene wax, and thus has higher temperature resistance and can be used in higher temperature environments; it also has better lubricity and easy stripping properties, and has a wider range of uses than currently commercially available polyethylene wax and polypropylene wax. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 This is a GPC curve of the poly (4-methyl-1-pentene) wax prepared in Example 12 of the present invention; Figure 2 is a DSC curve diagram of the poly(4-methyl-1-pentene) wax prepared in Example 19 of the present invention; Figure 3 This is the NMR carbon spectrum of the poly (4-methyl-1-pentene) wax prepared in Example 19 of the present invention; Figure 4 This is a sample picture of poly (4-methyl-1-pentene) wax prepared in Example 19 of the present invention. DETAILED DESCRIPTION

[0038] In order to enable those skilled in the art to better understand the technical solutions of the present invention, the technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work should fall within the scope of protection of the present invention.

[0039] All raw materials of the present invention can be purchased through commercial channels.

[0040] Testing and characterization methods of the compounds used in the present invention: The nuclear magnetic resonance analysis was performed using Bruker's AVANCE III HD 500, with tetramethylsilane (TMS) as the internal standard, at 25°C to test the structure of the compound. The molecular weight and molecular weight distribution of the polymer were measured using Agilent's PL-GPC220 with trichlorobenzene as the solvent at 150°C (standard sample: PS, flow rate: 1.0 mL / min). The melting point of the polymer was measured using a NETZSCH DSC 204 F1 differential scanning calorimeter (DSC) with nitrogen protection at a temperature change rate of 10°C / min (test temperature range 30~260°C), and the secondary heating curve was recorded. The drop melting point test of the polymer was carried out according to GB / T 8026-2014 "Determination of drop melting point of petroleum wax and petroleum fat".

[0041] The synthetic route of the aminoimine monometallocene complex is as follows:

[0042] In the embodiment, Cp*HfMe3 represents a metal precursor compound .

[0043] The structural formula of the aminoimine monometallocene complex described in the embodiment is shown in formula (I):

[0044] Formula (I); In formula (I), M is Hf, and R is H, methyl or isopropyl.

[0045] In order to more clearly describe the catalyst in the embodiment, the complexes in the embodiment are numbered as follows: Amine monometallocene complex Hf-1, M is Hf, R is H; Amine-imine monometallocene complex Hf-2, M is Hf, R is methyl; Aminimine monometallocene complex Hf-3, M is Hf, and R is isopropyl.

[0046]

[0047] Example 1 This embodiment provides α -Diimine compound A1, the synthesis method thereof is as follows: Under nitrogen atmosphere and room temperature, 30 mL of anhydrous ethanol, aniline (36 mmol), diacetyl (18 mmol), and 0.5 mL of formic acid were added to a 100 mL side-mouth flask in sequence, and the mixture was stirred at 60°C for 12 h. The reaction was terminated by cooling to room temperature. The organic phase was separated by extraction, and the solvent was evaporated to obtain 3.0 g of orange-yellow crystals with a yield of 71.6%.

[0048] 1 H NMR (400 MHz, CDCl3), δ (ppm): 7.28~6.95(m, 10H, Ph), 2.15(s, 6H,C H 3).

[0049] 13 C NMR (100 MHz, CDCl3), δ (ppm): 168.23, 144.27, 135.73, 125.63,120.76, 15.62.

[0050] Example 2

[0051] This embodiment provides α -Diimine compound A2, the synthesis method thereof is as follows: The synthesis method of this embodiment is different from the synthesis method of Example 1 only in that "aniline" in Example 1 is replaced by "2,6-dimethylaniline", and 3.9 g of orange-yellow crystals are obtained with a yield of 73.9%.

[0052] 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).

[0053] 13 C NMR (100 MHz, CDCl3), δ (ppm): 168.23, 144.27, 135.73, 125.63, 120.76, 18.29, 15.62.

[0054] Example 3

[0055] This embodiment provides α -Diimine compound A3, the synthesis method thereof is as follows: The synthesis method of this embodiment is different from the synthesis method of Example 1 only in that "aniline" in Example 1 is replaced by "2,6-diisopropylaniline", and 5.3 g of orange-yellow crystals are obtained with a yield of 73.6%.

[0056] 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).

[0057] 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.

[0058] Example 4

[0059] This embodiment provides an aminoimine ligand B1, and the synthesis method thereof is as follows: The obtained solution in Example 1 was weighed into a 100 mL flask equipped with a reflux condenser and protected by a nitrogen atmosphere. α -diimine compound A1 (8 mmol), then add 10 mL toluene and trimethylaluminum solution (TMA, 4.0 mL, 2M) in sequence, and stir at 100°C for 6 hours. After cooling, terminate with sodium hydroxide / water solution. Extract and separate the organic phase, evaporate the solvent to obtain 1.46 g of colorless crystals with a yield of 72.4%.

[0060] 1 H NMR (400 MHz, CDCl3), δ (ppm): 7.28~6.95(m, 10H, Ph), 4.48 (s, 1H,N H ), 1.84 (s, 3H, C H 3), 1.46(s, 6H, C H 3).

[0061] 13 C NMR (100 MHz, CDCl3), δ (ppm): 168.23, 144.27, 135.73, 125.63, 120.76, 59.82, 26.43, 15.62.

[0062] Example 5

[0063] This embodiment provides an aminoimine ligand B2, and the synthesis method thereof is as follows: The difference between the synthesis method of this embodiment and the synthesis method of embodiment 4 is that the obtained α - diimine compound A2 replaces the one obtained in Example 1 α -diimine compound A1, other operating conditions were the same as in Example 4, and 1.78 g of colorless crystals were obtained with a yield of 70.3%.

[0064] 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 H3), 1.46(s, 6H, C H 3).

[0065] 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.

[0066] Example 6

[0067] This embodiment provides an aminoimine ligand B3, and its synthesis method is as follows: The difference between the synthesis method of this embodiment and the synthesis method of embodiment 4 is that the obtained α - diimide compound A3 replaces the one obtained in Example 1 α -diimine compound A1, other operating conditions were the same as in Example 4, and 2.36 g of colorless crystals were obtained with a yield of 70.1%.

[0068] 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).

[0069] 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.

[0070] Example 7

[0071] This embodiment provides an aminoimine monometallocene complex Hf-1, and the synthesis method thereof is as follows: Under nitrogen atmosphere, the aminoimine ligand B1 (0.75 mmol) and Cp*HfMe3 (0.75 mmol) obtained in Example 4 were weighed and added into a Schlenk flask with a stirrer, and dissolved in 20 mL of anhydrous ether solution. The mixture was stirred at room temperature for 12 h. After the reaction was completed, the solvent was drained, extracted with n-hexane, concentrated, recrystallized, and filtered to obtain 0.33 g of yellow crystals with a yield of 74%.

[0072] 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-C H 3).

[0073] 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.

[0074] Example 8

[0075] This embodiment provides an aminoimine monometallocene complex Hf-2, and the synthesis method thereof is as follows: The synthesis method of this embodiment is different from that of embodiment 7 only in that the aminoimine ligand B2 obtained in embodiment 5 replaces the aminoimine ligand B1 obtained in embodiment 7, and other conditions are the same as those in embodiment 7, to obtain 0.39 g of yellow crystals with a yield of 77%.

[0076] 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 H3), 2.04(s, 6H, C H 3),1.85 (s, 15H, Cp*), 0.34 (s, 6H, Hf-C H 3).

[0077] 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.

[0078] Example 9

[0079] This embodiment provides an aminoimine monometallocene complex Hf-3, and the synthesis method thereof is as follows: The synthesis method of this embodiment is different from that of embodiment 7 only in that the aminoimine ligand B3 obtained in embodiment 6 replaces the aminoimine ligand B1 obtained in embodiment 7, and other conditions are the same as those in embodiment 7, to obtain 0.46 g of yellow crystals with a yield of 78%.

[0080] 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).

[0081] 13C 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.

[0082] Example 10

[0083] This embodiment provides a poly (4-methyl-1-pentene) wax, and the preparation method thereof specifically comprises the following steps: Under anhydrous and oxygen-free conditions, 4 mL of dry toluene and 5 mL of 4-methyl-1-pentene monomer (4M1P / Hf molar ratio = 4000:1) were added to the reaction bottle in sequence and stirred for 10 minutes to make the whole system uniform. Subsequently, 6.11 mg of the main catalyst Hf-1 and 13.8 mg of the co-catalyst triphenyl carbon tetrakis (pentafluorophenyl) boron salt ([Ph3C][B(C6F5)4]), B / Hf molar ratio = 1.5:1) were stirred and activated in 1 mL of toluene for 5 minutes to form a homogeneous solution, which was then added to the reaction bottle to initiate the polymerization of 4-methyl-1-pentene. After the polymerization was carried out at 50°C for 10 minutes, the polymerization reaction was terminated with an ethanol solution acidified with 10% hydrochloric acid by mass, and the polymerization product was separated by filtration, washed three times with ethanol, and dried in a vacuum drying oven at 60°C for 12 h to obtain a poly (4-methyl-1-pentene) wax product.

[0084] Embodiment 11

[0085] This embodiment provides a poly (4-methyl-1-pentene) wax, and the preparation method thereof specifically comprises the following steps: The only difference between the preparation method of this embodiment and the preparation method of Embodiment 10 is that the "main catalyst Hf-1" in Embodiment 10 is replaced by "main catalyst Hf-2".

[0086] Example 12

[0087] This embodiment provides a low molecular weight poly (4-methyl-1-pentene) wax, and the preparation method thereof specifically comprises the following steps: The only difference between the preparation method of this embodiment and the preparation method of Embodiment 10 is that the "main catalyst Hf-1" in Embodiment 10 is replaced by "main catalyst Hf-3".

[0088] The specific polymerization results of Examples 10 to 12 are shown in Table 1: Table 1. Polymerization results of 4-methyl-1-pentene catalyzed by different catalysts.

[0089] Example catalyst <![CDATA[Activity (10 6 g / (mol M · h))]]> <![CDATA[M w (g / mol)]]> <![CDATA[M w / M n ]]> Melting point(℃) Dropping point(℃) Example 10 Hf-1 1.53 5000 1.96 185 188 Embodiment 11 Hf-2 1.59 4800 2.17 184 187 Example 12 Hf-3 1.98 4500 1.92 183 186 Embodiment 13

[0090] This embodiment provides a poly (4-methyl-1-pentene) wax, and the preparation method thereof specifically comprises the following steps: The only difference between the preparation method of this embodiment and the preparation method of Example 12 is that the "promoter catalyst [Ph3C][B(C6F5)4]" in Example 12 is replaced by "promoter catalyst B(C6F5)3".

[0091] Embodiment 14

[0092] This embodiment provides a poly (4-methyl-1-pentene) wax, and the preparation method thereof specifically comprises the following steps: The only difference between the preparation method of this embodiment and the preparation method of Example 12 is that the "co-catalyst [Ph3C][B(C6F5)4]" in Example 12 is replaced by "co-catalyst [HNMe2Ph][B(C6F5)4]".

[0093] The specific polymerization results of Examples 13-14 are shown in Table 2: Table 2. Polymerization results of 4-methyl-1-pentene catalyzed by complex Hf-3 in the presence of different co-catalysts.

[0094]

[0095] Embodiments 15 to 18 Embodiments 15 to 18 provide a poly (4-methyl-1-pentene) wax, and the preparation method thereof specifically comprises the following steps: The difference between Examples 15 to 18 and Example 12 is only the different molar ratios of the main catalyst and the co-catalyst. The specific results are shown in Table 3: Table 3. Polymerization results of 4-methyl-1-pentene catalyzed by complex Hf-3 at different co-catalyst ratios.

[0096]

[0097] Embodiments 19 to 21 Embodiments 19 to 21 provide a poly (4-methyl-1-pentene) wax, and the preparation method thereof specifically comprises the following steps: The difference between Examples 19 to 21 and Example 12 is only the polymerization temperature. The specific results are shown in Table 4: Table 4. Polymerization results of 4-methyl-1-pentene catalyzed by complex Hf-3 at different polymerization temperatures.

[0098] Example T(℃) <![CDATA[Activity (10 6 g / (mol M · h))]]> <![CDATA[M w (g / mol)]]> <![CDATA[M w / M n ]]> Melting point(℃) Dropping point(℃) Embodiment 19 0 1.24 14700 2.83 205 208 Embodiment 20 30 1.36 9600 2.26 194 197 Embodiment 21 80 1.43 6800 2.14 187 190

[0099] Embodiments 22 to 27 Embodiments 22 to 27 provide a poly (4-methyl-1-pentene) wax, and the preparation method thereof specifically comprises the following steps: The difference between Examples 22 to 27 and Example 12 is only that the solvents are different. The specific results are shown in Table 5: Table 5. Polymerization results of 4-methyl-1-pentene catalyzed by complex Hf-3 in different solvents.

[0100] Example Solvents <![CDATA[Activity (10 6 g / (mol M·h))]]> <![CDATA[M w (g / mol)]]> <![CDATA[M w / M n ]]> Melting point(℃) Dropping point(℃) Embodiment 22 n-Pentane 1.51 7300 2.09 188 191 Embodiment 23 n-Hexane 1.46 6200 2.16 186 189 Embodiment 24 n-Heptane 1.42 5900 2.23 186 189 Embodiment 25 n-octane 1.36 5700 2.26 186 189 Embodiment 26 n-nonane 1.34 5700 2.26 186 189 Embodiment 27 n-Decane 1.32 5500 2.29 185 188

[0101] Embodiments 28 to 30 Embodiments 28 to 30 provide a poly (4-methyl-1-pentene) wax, and the preparation method thereof specifically comprises the following steps: The difference between Examples 28 to 30 and Example 12 is only that the molar ratio of 4M1P / Hf is different. The specific results are shown in Table 6: Table 6. Polymerization results of 4-methyl-1-pentene catalyzed by complex Hf-3 at different 4M1P / Hf molar ratios.

[0102] Example 4M1P / Hf molar ratio <![CDATA[Activity (10 6 g / (mol M·h))]]> <![CDATA[M w (g / mol)]]> <![CDATA[M w / M n ]]> Melting point(℃) Dropping point(℃) Embodiment 28 1000 0.23 2300 1.76 180 183 Embodiment 29 10000 3.34 12800 2.56 204 207 Embodiment 30 20000 3.92 20000 2.94 210 213

[0103] Comparative Example 1 This comparative example provides a method for preparing polyethylene wax by catalyzing ethylene polymerization with a Ziegler-Natta catalyst (CN101589072A), invented by V. Schlenk et al. of Evonik Degussa LLC. The method uses a Ziegler-Natta catalyst composed of titanium tetrachloride and a dialkylaluminum halide. Under polymerization conditions such as a polymerization temperature of 185°C, an Al / Ti molar ratio of 1.4, and substantially no solvent in the polymerization system, the obtained polyethylene wax product has 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.

[0104] Comparative Example 2 This comparative example provides a method for preparing polypropylene wax by polymerization of a metallocene compound in the presence of hydrogen (CN1206720A), invented by H.F. Hermann et al. of Clariant Co., Ltd., using ethylene bis-1, l'-(2-methyl-4-phenylindenyl) zirconium dichloride as a catalyst, under polymerization conditions such as 12 mmol triethylaluminum, a polymerization temperature of 70°C, and 2.5 bar hydrogen, the obtained polypropylene wax product has 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.

[0105] Taking the poly (4-methyl-1-pentene) wax prepared in Example 12 as an example, its performance was measured and compared with the polyethylene wax and polypropylene wax in Comparative Examples 1-2. The specific results are shown in Table 7: Table 7. Comparison results of polyolefin wax properties.

[0106] 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 (℃) 117 152 183 Drop melting point (℃) 120 155 186 Surface tension (mN / m) 31 31~33 24 As shown in Table 7, compared with polyethylene wax (Comparative Example 1) and polypropylene wax (Comparative Example 2), the molecular weight distribution of the poly (4-methyl-1-pentene) wax of the present invention is narrower, not higher than 2.0, which makes it have better lubrication performance; in terms of temperature resistance, the melting point and drop melting point of the poly (4-methyl-1-pentene) wax of the present invention are not less than 180°C, which is much greater than the melting point and drop melting point of the polyethylene wax and polypropylene wax in the comparative example, showing better temperature resistance; in terms of stripping performance, the surface tension of the poly (4-methyl-1-pentene) wax of the present invention is extremely low, which is 24 mN / m, which is much less than the surface tension of the polyethylene wax and polypropylene wax in the comparative example, showing better easy stripping performance. The experimental results show that compared with the existing polyethylene wax and polypropylene wax, the poly (4-methyl-1-pentene) wax provided by the present invention has better lubrication performance, temperature resistance and easy stripping performance.

[0107] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the above embodiments, ordinary technicians in the relevant field should understand that after reading the specification of this application, the technicians can still modify or replace the specific implementation mode of the present invention with equivalents, but these modifications or changes do not deviate from the scope of protection of the pending claims of the present application.

Claims

1. An aminoimine monometallocene complex, characterized in that: The structural formula of the aminoimine monometallocene complex is shown in formula (I): Formula (I); Wherein, M is Ti, Zr or Hf, and R is H, methyl or isopropyl.

2. The method for preparing the aminoimine monometallocene complex according to claim 1, characterized in that: The steps include: S1.α-Diimine compounds Reaction with trimethylaluminum to obtain an aminoimine ligand ; S2. Metal Precursor Compounds With the amino imine ligand reacting to obtain the aminoimine monometallocene complex; Wherein, M is Ti, Zr or Hf, and R is H, methyl or isopropyl.

3. The method for preparing an aminoimine monometallocene 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 temperature is 80-120° C. and the reaction time is 4-8 hours.

4. The method for preparing an aminoimine monometallocene complex according to claim 2, characterized in that: In S2, the molar ratio of the metal precursor compound to the aminoimine ligand is 1:1; The reaction temperature is a greenhouse and the reaction time is 10 to 16 hours.

5. Use of the aminoimine metallocene complex according to claim 1 in the preparation of poly(4-methyl-1-pentene) wax or use of the aminoimine metallocene complex obtained by the method for preparing the aminoimine metallocene complex according to any one of claims 2 to 4 in the preparation of poly(4-methyl-1-pentene) wax.

6. The 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 monomer undergoes polymerization reaction under the action of aminoimine monometallocene catalyst to obtain poly(4-methyl-1-pentene) wax; The aminoimine monometallocene catalyst is composed of the aminoimine monometallocene complex according to claim 1 and a co-catalyst.

7. The use according to claim 6, characterized in that: The polymerization reaction temperature is 0-80° C. and the reaction time is 5-20 minutes.

8. The use according to claim 6, characterized in that: The solvent of the polymerization reaction is at least one of toluene, pentane, hexane, heptane, octane, nonane and decane.

9. The use according to claim 6, characterized in that: The molar ratio of the 4-methyl-1-pentene monomer to the aminoimine metallocene complex is 1000-20000:1; The molar ratio of the co-catalyst to the aminoimine monometallocene complex is 1-2:

1.

10. The use according to claim 6, characterized in that: The co-catalyst is an organic boron compound; The organic boron compound is at least one of tris(pentafluorophenyl)borane, trityltetrakis(pentafluorophenyl)borate, and N, N-dimethylaniliniumtetrakis(pentafluorophenyl)borate.

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