CN101190929A - Ni metal complex and its preparation method and using method in ethene oligomerization - Google Patents

Abstract

The invention discloses a nickel metallic complex which has novel structure, namely 1, 3-propane diamine nickel complex. Moreover, the invention also discloses the preparation method of the novel complex and the usage method which adopts the complex as the activator in ethylene oligomerization, wherein, the 1, 3-propane diamine nickel complex acts as the active constituent of activator components in the ethylene oligomerization. The preparation of the complex of the invention has simple and cheap raw material as the beginning, realizable and high-productivity steps and larger modifiable space of ligand, thus the respective activator components have from middle to high ethylene oligomerization activity, thereby the obtained oligomers are mainly dipolymer and tripolymer of the ethylene.

Description

Ni metal complex, preparation method and use method in ethylene oligomerization

Technical Field

The invention relates to a transition metal catalyst after ethylene oligomerization, in particular to a novel nickel metal complex catalyst, namely a1, 3-propane diamine nickel complex, a preparation method thereof and a use method thereof in ethylene oligomerization.

Background

Polyethylene is the largest variety of synthetic resins in general use, mainly including Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), High Density Polyethylene (HDPE), and some products with special properties ethylene oligomerization is an important means of industrially preparing linear α -olefins linear α -olefins can be used in the preparation of detergents, plasticizers, fine chemicals, and as comonomers in linear low density polyethylene, and thus the production of linear α -olefins has become an independent branch in the petrochemical industry.

Olefin polymerization catalysts are the core of olefin polymerization technology, and the following categories of olefin polymerization catalysts are summarized: metallocene catalysts, non-metallocene catalysts, chromium-based catalysts, ziegler-natta catalysts, bifunctional catalysts, and bimodal or broad molecular weight distribution olefin polymerization composite catalysts.

Since the seventies, the research on the homogeneous catalysis of olefin polymerization and oligomerization by transition metal complexes has been paid attention to, and efforts have been made to research new catalysts and improve the existing catalysts, so as to improve the activity of the catalysts and the selectivity of catalytic products. Among the many metals sought, the early, fast-growing, and more focused research on nickel-based cationic catalyst systems, such as those reported in U.S. patents: U.S. Pat. Nos. 3,686,351, 19720711 and 3,676,523, 19720822, developed the Shell (Shell) company SHOP (Shell) high Olefin process based on this patented technology. The ethylene oligomerization catalytic activity of the P-O bridged ligand catalyst is about 10⁵G ethylene/(mol Ni · h). Subsequently, many patents such as O-O, P-N, P-P type and N-N type coordinated nickel catalysts have been developed, wherein nitrogen atom coordinated nickel catalysts are widely regarded as important, suchas recent patents: jpn. kokai Tokkyo Koho JP11060627, a2 (3 months and 2 days 1999), Heisei; WO9923096a1 (14/5/1999); WO 9951550A 1 (10 months and 14 days 1999). However, most of the reported catalysts have the disadvantages of low selectivity and low activity of oligomerization products, and the ethylene oligomerization industry needs ethylene oligomerization catalysts with better properties. The invention develops a metal nickel complex with simple preparation process, high selectivity and high activityThe ethylene oligomerization catalyst can be applied to the ethylene oligomerization industry.

Disclosure of Invention

The invention aims to provide a novel ethylene oligomerization nickel metal complex catalyst, namely a1, 3-propane diamine nickel complex.

It is still another object of the present invention to provide a method for preparing the above nickel metal complex catalyst.

The invention also aims to provide a use method of the nickel metal complex as a catalyst in ethylene oligomerization, wherein the nickel metal complex catalyst is an active component of the catalyst composition.

The transition metal coordination catalyst after the ethylene oligomerization is a nickel complex with the following structural general formula:

wherein the content of the first and second substances,

the central metal complex ion is nickel, [ Ni (NH]₂CH₂CH₂CH₂NH₂)₃]²⁺Being a coordinating cation, Cl^-As counter anions, the ligandin the complex is three 1, 3-propane diamine which are respectively coordinated with Ni to form three six-membered rings.

The invention also provides a preparation method of the 1, 3-propane diamine nickel complex, and the reaction equation for preparing the 1, 3-propane diamine nickel complex is as follows:

mixing NiCl₂Dissolving in organic solvent, adding 1, 3-propane diamine, stirring, filtering, and layering with diethyl ether to obtain nickel complex crystalMixed organic solvents, e.g. CH₃OH and/or CH₃And (3) a CN solvent.

The yield of the 1, 3-propanediamine nickel complex was between 67% and 90%, the complex was characterized by elemental analysis and infrared spectroscopy, the results of which are given in example 1, and the molecular structure and arrangement of the molecules in the crystal lattice was determined by X-ray single crystal diffraction measurements.

In another aspect, the present invention also provides a method for using the above 1, 3-propanediamine nickel metal complex as a catalyst in ethylene oligomerization, which uses a catalyst composition comprising the above 1, 3-propanediamine nickel metal complex as a catalyst, the catalyst composition comprising a main catalyst and a cocatalyst, i.e., an activator, for activating the main catalyst, i.e., the above 1, 3-propanediamine nickel metal complex.

Alumoxanes may be used as activators and may be Methylalumoxane (MAO), Modified Methylalumoxane (MMAO) and Et₂AICl. Aluminoxanes can be produced by the hydrolysis of various trialkylaluminum compounds. MMAO can be produced by hydrolysis of trimethylaluminum and higher trialkylaluminum's such as triisobutylaluminum.

Other ingredients suitable as activators in the catalyst composition of the invention are alkylaluminum compounds, such as trialkylaluminums and alkylaluminum chlorides. These activators may be trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum chloride, ethylaluminum dichloride, and the like.

Alumoxanes as activators in contrast to alkylaluminum compound catalysts, alumoxanes, especially methylalumoxane, are preferably used as activators.

The aluminum to nickel molar ratio in the catalyst composition of the invention may vary in the range of 200 to 1000. If the ratio of aluminum to nickel is less than 200, the activity is very low; when the aluminum nickel ratio is more than 1000, a decrease in catalytic activity also occurs.

The activator and polymerization catalyst compound may be combined with one or more support materials using any of the methods of support known in the art. In one embodiment, the activator is present in supported form, e.g., the activator is deposited on the support, contacted with the support, vaporized with the support, bound to the support, incorporated into the support, adsorbed or absorbed in or on the support. In another embodiment, the activator and the catalyst compound are deposited together on the support, contacted with the support, vaporized together with the support, bound to the support, incorporated into the support, adsorbed or absorbed in or on the support.

The support material used may be any of the usual support materials. Preferred support materials are porous support materials, such as inorganic oxides and inorganic chlorides. More preferred support materials are inorganic oxides including those of group 2, 3, 4, 5, 13 or 14 metal oxides, specific examples being pyrogenically prepared silica supports, and spherical magnesium chloride. Other usefulsupports may be magnesia, titania, zirconia, montmorillonite, phyllosilicate, zeolite, talc or clay.

The catalyst compositions of the invention, whether supported or not, are suitable for use in any prepolymerization and/or polymerization process over a wide range of temperatures and pressures. Polymerization processes include solution, slurry, gas phase and high pressure processes or combinations thereof. Especially preferred are solution polymerization processes for unsupported catalyst compositions, and slurry polymerization processes for supported catalyst compositions.

In the case of homogeneous solution polymerization, a nonpolar solvent such as toluene, n-hexane or n-heptane is generally selected as a polymerization solvent. When n-hexane or n-heptane is used as the solvent, the activity is lowered due to the decrease in the solubility of the main catalyst, and therefore toluene is preferred as the solvent. The temperature of the polymerization reaction may vary from 0 to 50 ℃ and higher temperatures may result in a decrease in activity. The reaction time is generally 30 to 60 minutes, with the activity decreasing after 60 minutes. After a predetermined time, the reaction was terminated with dilute hydrochloric acid.

In heterogeneous slurry polymerizations, experimental conditions similar to those of solution polymerization were used. The polymerization tests can be carried out at different ethylene pressures, the ethylene pressure employed generally being from 10 to 50 atmospheres, preferably 20 atmospheres.

The invention has the advantages that: the synthesis of the catalyst is started from simple and cheap raw materials, each step is easy to realize, the yield is high, the modifiable space of the ligand is large, and the influence of different ligand environments on the catalytic activity can be conveniently researched.

Drawings

FIG. 1 is a molecular structure diagram of a1, 3-propanediamine nickel complex;

FIG. 2 is a unit cell stacking diagram of a nickel 1, 3-propanediamine complex;

FIG. 3 is a unit cell stacking diagram of a nickel 1, 3-propanediamine complex.

Detailed Description

Example 1: preparation of nickel metal complex, namely 1, 3-propane diamine nickel complex

0.10g of NiCl₂Dissolved in 15ml of CH₃OH and 15ml CH₃CN, 1ml of 1, 3-propanediamine was added, stirred for 12 hours, and filtered. The purple filtrate is layered by ether, and purple Mitsubishi conical crystal, namely the 1, 3-nickel propane diamine complex is obtained after 2 weeks. Yield: 67.3 percent. The molecular structure is shown in figure 1, and the stacking of molecules in the unit cell is shown in figures 2 and 3. IR (KBr): 3479.22, respectively; 3299.82, respectively; 2949.53, 2886.71; 1662.39, respectively; 1606.10, respectively; 1590.66, respectively; 1458.67, respectively; 1329.71, respectively; 1276.27, respectively; 1154.70, respectively; 1028.41, respectively; 984.08, respectively; 664.15, respectively; 523.32, respectively; 499.26cm^-1. Elemental analysis: c₉H₃₀Cl₂N₆Ni: calculated values: c, 30.68; h, 8.52; n, 23.86. Test values are: c, 30.65; h, 8.48; n, 23.81.

TABLE 1 crystallography parameters of 1, 3-propanediamine nickel complexes

TABLE 2 partial bond lengths and bond angles of 1, 3-propanediamine nickel complexes

Example 2: catalytic activity of nickel metal complex, namely 1, 3-propane diamine nickel complex and cocatalyst in ethylene oligomerization

A250 ml polymerization flask with magnetic stirrer was dried continuously at 130 ℃ for 6 hours, evacuated while hot and charged with N₂Replace qi for 3 times. 1, 3-propanediamine nickel complex catalyst (1.8mg, 5. mu. mol) was added, followed by additional vacuum and 2-way replacement with ethylene. A predetermined amount of toluene (26.7ml) was injected into the reactor with a syringe, and a toluene solution (1.54mol/L, 3.3ml) of Methylaluminoxane (MAO) was added thereto to make Al/Ni 1000, and the mixture was vigorously stirred at 25 ℃ for 30 minutes while maintaining an ethylene pressure of 1 atm. The MAO was neutralized with dilute hydrochloric acid at 0 ℃ and the small toluene layer was dried over anhydrous sodium sulfate and the oligomer content and distribution were determined by gas chromatography. Repeating the above steps, selecting different cocatalyst, adjusting and controlling Al/Ni ratio and catalytic environment condition, the obtained oligomerization activity is shown in table 3, and ethylene oligomerization products mainly comprise dimerization and trimerization products.

TABLE 3 ethylene oligomerization catalytic Activity of 1, 3-propanediamine Nickel Complex and cocatalyst

Example 3: one embodiment of the supported ethylene oligomerization catalyst system

In one embodiment of the present invention, a process for carrying an ethylene oligomerization catalyst system is provided. In this process, the catalyst compound is slurried in a liquid, thereby forming a catalyst solution or emulsion. The catalyst compound solution and activator solution are mixed and heated together and added to the heated porous support, or the heated porous support is added to the solution. The content of aluminum and nickel in the supported catalyst is determined by analysis by an ion emission spectroscopy-mass spectrometry method.

Claims (10)

1. A nickel metal complex has a molecular structure shown in formula I,

wherein the content of the first and second substances,

the central metal complex ion is nickel, [ Ni (NH]₂CH₂CH₂CH₂NH₂)₃]²⁺Being a coordinating cation, Cl^-As counter anions, the ligand in the complex is three 1, 3-propane diamine which are respectively coordinated with Ni to form three six-membered rings.

2. The method for producing a Ni complex according to claim 1, characterized in that the synthetic route is as follows:

mixing NiCl₂Dissolving in organic solvent, adding 1, 3-propane diamine, stirring, filtering, and layering with diethyl ether to obtain nickel complex crystal₃OH and/or CH₃And (3) a CN solvent.

3. The use of nickel metal complex as catalyst in oligomerization of ethylene as claimed in claim 1, wherein the nickel metal complex is used as main catalyst and is accompanied by cocatalyst, and the cocatalyst is selected from aluminoxane, alkyl aluminum compound and/or alkyl aluminum chloride.

4. The method of claim 3, wherein the aluminoxane is methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, and/or isobutylaluminoxane.

5. The method of claim 3 wherein said aluminoxane is methylaluminoxane.

6. Use of a nickel metal complex as a catalyst in the oligomerization of ethylene according to claim 3, characterized in that the aluminum alkyl is trimethylaluminum and/or triethylaluminum.

7. Use of a nickel metal complex as a catalyst in the oligomerization of ethylene according to claim 3, characterized in that said alkylaluminum chloride is diethylaluminum chloride.

8. Use of a nickel metal complex as catalyst in oligomerization of ethylene according to claims 3-7, characterized in that the molar ratio of metallic nickel in the procatalyst to metallic aluminum in the cocatalyst is in the range of 200 to 1000.

9. The use of a nickel metal complex as a catalyst in the oligomerization of ethylene as recited in claim 8, characterized in that said catalyst is supported on a support.

10. The use of a nickel metal complex as a catalyst in the oligomerization of ethylene as recited in claim 9, characterized in that said support is silica and/or magnesium chloride spheres.

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