阅读说明：本技术 带有烷氧基硅的α-二亚胺化合物、负载型α-二亚胺化合物、金属配合物及其制备与应用 (Alpha-diimine compound with alkoxy silicon, supported alpha-diimine compound, metal complex and preparation and application thereof ) 是由 韦德帅 侯彦辉 任合刚 赵增辉 宋磊 高宇新 杨国兴 张瑞 张明强 王登飞 闫义 于 2019-03-15 设计创作，主要内容包括：本发明公开了一种带有烷氧基硅的α-二亚胺化合物、负载型α-二亚胺化合物、金属配合物及其制备与应用。该α-二亚胺化合物结构上的烷氧基硅可以与载体发生反应而实现负载,大大增加α-二亚胺化合物负载在载体上的牢固程度,从而得到具有不易脱落的负载型α-二亚胺金属催化剂,并作为主催化剂与助催化剂配合使用将其应用在烯烃的聚合中。另外,此类负载催化剂结构可调范围大,通过改变负载的α-二亚胺化合物结构上的取代基,可以对聚合活性、聚合物的分子链结构、分子量及其分布进行调控。本发明可适用于现有非均相催化剂催化烯烃聚合的气相聚合装置或烯烃单体的液相本体聚合装置或淤浆聚合装置。(The invention discloses an alpha-diimine compound with alkoxy silicon, a supported alpha-diimine compound, a metal complex, and preparation and application thereof. The alkoxy silicon on the alpha-diimine compound structure can react with a carrier to realize loading, so that the firmness of the alpha-diimine compound loaded on the carrier is greatly increased, and the loaded alpha-diimine metal catalyst which is not easy to fall off is obtained and is used as a main catalyst and a cocatalyst to be matched for use and applied to the polymerization of olefins. In addition, the structure of the supported catalyst has a wide adjustable range, and the polymerization activity, the molecular chain structure of the polymer, the molecular weight and the distribution of the molecular chain structure can be adjusted and controlled by changing the substituent on the structure of the supported alpha-diimine compound. The invention can be applied to the existing gas phase polymerization device for catalyzing olefin polymerization by a heterogeneous catalyst or the liquid phase bulk polymerization device or slurry polymerization device for olefin monomers.)

1. An alpha-diimine compound with silicon alkoxide, which has the following structural formula:

wherein X is-CH₂-or-OCH₂CH₂-；

R₁Ar is respectively substituted or unsubstituted C₆-C₆₀Aryl radical, C₃-C₆₀One of the heterocyclic aromatic hydrocarbon groups of (1);

n is any integer between 0 and 30;

A. b is the same or different hydrogen, C₁-C₁₅Alkyl or C₆-C₃₀Or A, B together with the adjacent carbon atom form acenaphthyl, phenanthryl or C₄-C₃₀A cycloalkyl group;

R₂、R₃are identical or different C₁-C₂₀One of the hydrocarbon groups of (1);

m is any integer between 3 and 20.

2. A method for preparing the α -diimine compound of claim 1, which comprises the steps of:

1) ortho-diketones with aromatic amines and R-NH having hydroxyl groups₂Reacting under the action of p-toluenesulfonic acid in sequence to obtain a compound A;

2) the compound A reacts with trialkoxy (3-isocyanopropyl) silicon or dialkoxy monoalkyl (3-isocyanopropyl) silicon or monoalkoxydialkyl (3-isocyanopropyl) silicon in a system after being vacuumized and replaced by nitrogen to obtain the corresponding alpha-diimine compound shown in formula 1, formula 2 or formula 3.

3. A supported alpha-diimine compound, comprising: the α -diimine compound of claim 1 and a carrier, the α -diimine compound being supported on the carrier;

the carrier is SiO₂、MgCl₂Clay, diatomite, montmorillonite, Al₂O₃、Fe₃O₄Carbon black, carbon nanotube, graphene, SiO₂/MgCl₂Composite Carrier, SiO₂/diatomite composite carrier, montmorillonite/MgCl₂Composite support, diatomaceous earth/MgCl₂Composite carrier or Fe₃O₄/MgCl₂And (3) a composite carrier.

4. A method for preparing the supported α -diimine compound of claim 3, which comprises the steps of:

adding alpha-diimine compound solution with the concentration of 0.001 to 0.1mmol/mL into the carrier solution with the concentration of 0.1 to 0.01g/mL under stirring for reaction; after the reaction is finished, carrying out post-treatment and purification to obtain the supported alpha-diimine compound.

5. The method according to claim 4, wherein the solvent of the carrier solution and the α -diimine compound solution is C₁-C₂₀Chlorinated alkane of (C)₆-C₂₀Chlorinated aromatic hydrocarbons of (2), C₆-C₂₀Of aromatic hydrocarbons or C₂-C₂₀And (3) one or more of the oxygen-containing alkanes.

6. The method according to claim 4, wherein the ratio of the α -diimine compound to the support is 1 to 10mmol of the α -diimine compound per gram of the support.

7. The method according to claim 4, wherein the reaction time is 1 to 72 hours and the reaction temperature is 0 to 200 ℃.

8. The method of claim 5, wherein the post-treatment purification comprises: and after the reaction is finished, carrying out suction filtration on the system, washing the obtained solid by using a solvent which is the same as the system, and drying to obtain the supported alpha-diimine compound.

9. A preparation method of a supported alpha-diimine metal complex is characterized by comprising the following steps:

adding the supported alpha-diimine compound and a metal compound of claim 3 into an organic solvent under anhydrous and oxygen-free conditions for reaction, and after the reaction is finished, carrying out post-treatment and purification to obtain the supported alpha-diimine metal complex.

10. The method according to claim 9, wherein a molar ratio of the α -diimine compound to the metal compound contained in the supported α -diimine compound is 1: 1.

11. The method according to claim 9, wherein the concentration of the metal compound is 0.01 to 1 mmol/mL.

12. The method according to any one of claims 9 to 11, wherein the metal compound is one of nickel, palladium and iron.

13. The method according to claim 12, wherein the metal compound is (DME) NiBr₂、(DME)NiCl₂、Ni(CH₃COO)₂、(COD)PdCl₂、(COD)PdClCH₃Or (COD) PdMe (NCMe).

14. The method according to claim 9, wherein the organic solvent is C₁-C₂₀Chlorinated alkane of (C)₆-C₂₀Chlorinated aromatic hydrocarbons of (2), C₆-C₂₀Of aromatic hydrocarbons or C₂-C₂₀And (3) one or more of the oxygen-containing alkanes.

15. The method according to claim 14, wherein the organic solvent is one or more selected from dichloromethane, chloroform, 1, 2-dichloroethane, chlorobenzene, dichlorobenzene, toluene, tetrahydrofuran, and 1, 4-dioxane.

16. The method according to claim 9, wherein the reaction is carried out at a temperature of 0 to 200 ℃ for 16 to 24 hours.

17. The method of claim 9, wherein the post-treatment purification comprises: and after the reaction is finished, carrying out suction filtration on the system, washing the obtained solid by using an organic solvent which is the same as the system, and drying to obtain the supported alpha-diimine metal complex.

18. The method of claim 9, wherein the post-treatment purification comprises: after the reaction is finished, carrying out reduced pressure concentration on the system to obtain a concentrated solution, and adding a precipitator with volume ten times to fifty times that of the concentrated solution for precipitation; and after the precipitation is finished, carrying out suction filtration, washing the obtained solid by using a precipitator, and drying to obtain the supported alpha-diimine metal complex.

19. The method of claim 18, wherein the precipitating agent is C₅-C₂₀Alkane or C₅-C₂₀And (3) one or more of cycloalkanes.

20. The preparation method of claim 19, wherein the precipitant is one or more of n-pentane, n-hexane, n-heptane, n-octane and cyclohexane.

21. A supported α -diimine metal complex, prepared by the process of any one of claims 9 to 20.

22. Use of the supported α -diimine metal complex of claim 21 as a procatalyst in the gas phase polymerization of ethylene or propylene, the liquid phase bulk polymerization of olefin monomers or slurry polymerization.

23. Use according to claim 22, characterized in that it comprises the following reaction conditions: the polymerization reaction temperature is-20-120 ℃; the pressure is 0.1-10MPa when the olefin monomer is gas;

the olefin monomer is one or more of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-decene, norbornene, vinyl norbornene, ethylidene norbornene, dicyclopentadiene, 1, 4-butadiene, styrene, alpha-methyl styrene and divinylbenzene.

Technical Field

The invention relates to the field of olefin catalytic polymerization, in particular to an alpha-diimine compound with alkoxy silicon, a supported alpha-diimine compound, a metal complex, and preparation and application thereof.

Background

Brookhart et al, 1995, reported that this class of late transition metal catalysts was of interest to researchers after such nickel, palladium alpha-diimines were able to catalyze ethylene polymerization (J Am ChemSoc,1995,117:6414) (WO 96/23010; US 6103658; CN 201010177711.8; CN 201210051457.6; CN 201210276331.9; CN 201010572741.9). Long et al reported 2014 a nickel alpha-diimine with large steric groups (ACSCatal.2014,4,2501-2504), which still has good catalytic activity for ethylene polymerization at 90 ℃. This finding has made such catalysts show great promise for their industrial applications.

Although homogeneous alpha-diimine late transition metal catalysts have many advantages, there are many problems in practical industrial applications, such as sticking phenomenon generated in the catalytic olefin polymerization process, and the reaction heat is difficult to withdraw; the morphology of the polymer is difficult to control; the consumption of the cocatalyst methylaluminoxane is more, and the cost is high; the thermal stability is poor and it is not suitable for the polymerization apparatus currently used in industry. One important approach to solve these problems is to support an α -diimine late transition metal catalyst.

Generally, olefin catalyst supporting methods are largely classified into three types: (1) the catalyst is directly loaded on the carrier magnesium chloride or silica gel through physical adsorption, although the method is simple and convenient, the acting force of the catalyst and the carrier is weak, and the active center of the catalyst is easy to fall off in the catalytic polymerization process. (2) The modified supported catalyst (CN 200810025909.7; CN201210051947.6) was modified with a cocatalyst or other compound. (3) The functional group contained on the catalyst and the carrier are subjected to chemical reaction, and the catalyst is loaded on the carrier through a covalent bond formed between the functional group and the carrier, so that the catalyst can be firmly combined with the carrier in a loading mode, and the catalyst is prevented from falling off from the carrier. For example, the literature (Macromolecules,2002,35: 6074; Macromolecules,2006,39: 6341; J Mol Catal A: Chem,2008,287: 57; ApplCatal A: Gen,2004,262: 13; Polymer,2010,51:2271) introduces functional groups on anilines in the alpha-diimine ligand structure, and the covalent bonds formed by the reaction of the functional groups with the active groups on the support graft support the catalyst. Patent CN201510217041.0 discloses an α -diimine ligand with an alkoxy silicon group introduced in the acenaphthenequinone unit, and the loading is achieved by reacting alkoxy silicon with a carrier. However, the synthesis of the ligand is complex and the cost is high, so that the ligand is not beneficial to industrialization.

Disclosure of Invention

The invention aims to synthesize novel alpha-diimine compounds with alkoxy silicon, supported alpha-diimine compounds and supported alpha-diimine metal complexes. The alkoxy silicon can be connected with a carrier through a chemical bond, so that a ligand is firmly loaded on the carrier, and the loaded alpha-diimine metal catalyst which is not easy to fall off is obtained and is applied to olefin polymerization. The alpha-diimine compound may also have two reactive groups, silicon alkoxides, in the structure, which greatly increases the firmness of the alpha-diimine compound loaded on the carrier.

The invention also applies the supported alpha-diimine metal complex to olefin polymerization reaction, and the obtained polymer is greatly different from the polymer obtained by the catalysis of the existing catalyst in branching degree and polymer properties. The supported alpha-diimine metal complex has high catalytic activity, simple synthesis and low cost, so that the catalyst can realize industrialization.

In order to achieve the purpose, the invention adopts the following technical scheme:

the invention provides in a first aspect an alpha-diimine compound with silicon alkoxide, the compound having the following structural formula:

wherein X is-CH₂-or-OCH₂CH₂-；

R₁Ar is respectively substituted or unsubstituted C₆-C₆₀Aryl radical, C₃-C₆₀One of the heterocyclic aromatic hydrocarbon groups of (1);

n is any integer between 0 and 30;

A. b is the same or different hydrogen, C₁-C₁₅Alkyl or C₆-C₃₀Or A, B together with the adjacent carbon atom form acenaphthyl, phenanthryl or C₄-C₃₀A cycloalkyl group;

R₂、R₃are identical or different C₁-C₂₀One of the hydrocarbon groups of (1);

m is any integer between 3 and 20.

Preferably, the structural formula of the silicon alkoxide-containing α -diimine compound is as follows:

the second aspect of the present invention provides a method for preparing the above α -diimine compound, comprising the steps of:

1) ortho-diketones with aromatic amines and R-NH having hydroxyl groups₂Reacting under the action of p-toluenesulfonic acid in sequence to obtain a compound A;

2) the compound A reacts with trialkoxy (3-isocyanopropyl) silicon or dialkoxy monoalkyl (3-isocyanopropyl) silicon or monoalkoxydialkyl (3-isocyanopropyl) silicon in a system after being vacuumized and replaced by nitrogen to obtain the corresponding alpha-diimine compound shown in formula 1, formula 2 or formula 3.

In a third aspect, the present invention provides a supported α -diimine compound, which comprises: the above α -diimine compound and a carrier, the α -diimine compound being supported on the carrier;

the carrier is SiO₂、MgCl₂Clay, diatomite, montmorillonite, Al₂O₃、Fe₃O₄Carbon black, carbon nanotube, graphene, SiO₂/MgCl₂Composite Carrier, SiO₂/diatomite composite carrier, montmorillonite/MgCl₂Composite support, diatomaceous earth/MgCl₂Composite carrier or Fe₃O₄/MgCl₂And (3) a composite carrier.

The fourth aspect of the present invention provides a method for preparing the supported alpha-diimine compound, comprising the steps of:

adding alpha-diimine compound solution with the concentration of 0.001 to 0.1mmol/mL into the carrier solution with the concentration of 0.1 to 0.01g/mL under stirring for reaction; after the reaction is finished, carrying out post-treatment and purification to obtain the supported alpha-diimine compound.

Preferably, the solvent of the carrier solution and the α -diimine compound solution is C₁-C₂₀Chlorinated alkane of (C)₆-C₂₀Chlorinated aromatic hydrocarbons of (2), C₆-C₂₀Of aromatic hydrocarbons or C₂-C₂₀And (3) one or more of the oxygen-containing alkanes.

Preferably, the ratio of the α -diimine compound to the support is such that 1 to 10mmol of the α -diimine compound are added per gram of support.

Preferably, the reaction time is 1 to 72 hours and the reaction temperature is 0 to 200 ℃.

Preferably, the post-treatment purification comprises: and after the reaction is finished, carrying out suction filtration on the system, washing the obtained solid by using a solvent which is the same as the system, and drying to obtain the supported alpha-diimine compound.

The fifth aspect of the invention provides a preparation method of a supported alpha-diimine metal complex, which comprises the following steps:

under the anhydrous and anaerobic conditions, adding a supported alpha-diimine compound and a metal compound into an organic solvent for reaction, and after the reaction is finished, carrying out post-treatment and purification to obtain a supported alpha-diimine metal complex.

Preferably, the molar ratio of the α -diimine compound to the metal compound contained in the supported α -diimine compound is 1: 1.

Preferably, the concentration of the metal compound is 0.01 to 1 mmol/mL.

Preferably, the metal compound is one of nickel, palladium or iron.

Preferably, the metal compound is (DME) NiBr₂、(DME)NiCl₂、Ni(CH₃COO)₂、(COD)PdCl₂、(COD)PdClCH₃Or (COD) PdMe (NCMe). Wherein DME is ethylene glycol dimethyl ether, and COD is 1, 5-cyclooctadiene.

Preferably, the organic solvent is C₁-C₂₀Chlorinated alkane of (C)₆-C₂₀Chlorinated aromatic hydrocarbons of (2), C₆-C₂₀Of aromatic hydrocarbons or C₂-C₂₀And (3) one or more of the oxygen-containing alkanes.

Preferably, the organic solvent is one or more of dichloromethane, trichloromethane, 1, 2-dichloroethane, chlorobenzene, dichlorobenzene, toluene, tetrahydrofuran or 1, 4-dioxane.

Preferably, the reaction temperature is 0-200 ℃ and the reaction time is 16-24 hours.

Preferably, the post-treatment purification comprises: and after the reaction is finished, carrying out suction filtration on the system, washing the obtained solid by using an organic solvent which is the same as the system, and drying to obtain the supported alpha-diimine metal complex.

Preferably, the post-treatment purification comprises: after the reaction is finished, carrying out reduced pressure concentration on the system to obtain a concentrated solution, and adding a precipitator with volume ten times to fifty times that of the concentrated solution for precipitation; and after the precipitation is finished, carrying out suction filtration, washing the obtained solid by using a precipitator, and drying to obtain the supported alpha-diimine metal complex.

Preferably, the precipitant is C₅-C₂₀Alkane or C₅-C₂₀And (3) one or more of cycloalkanes.

Preferably, the precipitant is one or more of n-pentane, n-hexane, n-heptane, n-octane and cyclohexane.

The sixth aspect of the invention provides a supported alpha-diimine metal complex prepared by the preparation method.

The seventh aspect of the present invention provides the use of the supported alpha-diimine metal complex as a procatalyst in gas phase polymerization of ethylene or propylene or liquid phase bulk polymerization or slurry polymerization of olefin monomers.

Preferably, the application comprises the following reaction conditions: the polymerization reaction temperature is-20-120 ℃; the pressure is 0.1-10MPa when the olefin monomer is gas;

the olefin monomer is one or more of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-decene, norbornene, vinyl norbornene, ethylidene norbornene, dicyclopentadiene, 1, 4-butadiene, styrene, alpha-methyl styrene and divinylbenzene.

The invention has the beneficial effects that:

the alkoxy silicon on the alpha-diimine compound structure can react with the carrier to realize loading, so that the firmness of the alpha-diimine compound loaded on the carrier is greatly increased, and the loaded alpha-diimine metal catalyst which is not easy to fall off is obtained and is used as a main catalyst and a cocatalyst to be matched for use and applied to the polymerization of olefins. In addition, the structure of the supported catalyst has a wide adjustable range, and the polymerization activity, the molecular chain structure of the polymer, the molecular weight and the distribution of the molecular chain structure can be adjusted and controlled by changing the substituent on the structure of the supported alpha-diimine compound. The invention can be applied to the existing gas phase polymerization device for catalyzing olefin by heterogeneous catalyst or the liquid phase bulk polymerization device or slurry polymerization device for olefin monomer.

Detailed Description

In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.

The invention relates to a preparation method of an alpha-diimine compound and a supported metal complex thereof, which comprises the following steps:

(1) reacting aromatic amine with hydroxyl with an o-diketone compound to obtain a compound A;

(2) respectively reacting the compound A prepared in the step (1) with trialkoxy (3-isocyanatopropyl) silicon, dialkoxy monoalkyl (3-isocyanatopropyl) silicon and monoalkoxydialkyl (3-isocyanatopropyl) silicon in a system after vacuumizing and nitrogen replacement to respectively obtain an alpha-diimine compound with dialkoxy silicon, wherein the structure of the alpha-diimine compound is B, C, D;

(3) respectively reacting the compound B, C, D prepared in the step (2) with a carrier to obtain a corresponding alpha-diimine compound loaded substance E, F, G;

(4) and (4) respectively reacting the alpha-diimine compound load prepared in the step (3) with a metal compound under the anhydrous and oxygen-free conditions to obtain the supported alpha-diimine metal complex.

Synthesis of supported mono-or alpha-diimine compounds