CN114230702B - Olefin polymerization catalyst with naphthoxy skeleton, preparation method and application - Google Patents

Abstract

The invention discloses an olefin polymerization catalyst with a naphthoxy skeleton, a preparation method and application thereof. The olefin polymerization catalyst comprises a metal complex of a naphthyloxy backbone, an alkyl aluminum co-agent, and optionally a borate. The catalyst has good high-temperature catalytic activity and stereotactic capability, and is particularly suitable for preparing polyolefin products with narrow molecular weight distribution.

Description

Olefin polymerization catalyst with naphthoxy skeleton, preparation method and application

Technical Field

The invention relates to an olefin polymerization catalyst, in particular to an olefin polymerization catalyst with a naphthoxy skeleton, a preparation method and application thereof.

Background

The polyolefin elastomer is a high-end polyolefin material with extremely wide application, the structure of the polyolefin elastomer is mainly ethylene/alpha-olefin copolymer, the product performance gradually changes from thermoplastic plastics to thermoplastic elastomers along with the increase of the content of alpha-olefin comonomer in the copolymer, and the polyolefin elastomer has excellent tensile strength, tearing strength, impact strength and environmental stress cracking resistance, and can be widely applied to the fields of films, fibers, pipes, cables, mechanical tools, sealing elements, hot melt adhesives and the like.

Exxon patent EP0468537B2 discloses for the first time a metallocene catalyst for the industrial production of ethylene/1-octene copolyolefins, dow patent EP 041685B 1 reports a class of constrained geometry catalysts for the random copolymerization of ethylene/1-octene, mitsui patent EP0874005B1 discloses a catalyst based on an aryloxyimine ligand, but with low activity at high temperatures.

In view of the above problems in the prior art, there is a need to develop an olefin copolymerization catalyst having excellent catalytic activity.

Disclosure of Invention

In order to solve the technical problems, the invention provides an olefin polymerization catalyst with a naphthoxy skeleton, a preparation method and application thereof. The olefin polymerization catalyst comprises a complex catalyst of a naphthoxy skeleton, wherein an oxygen atom of the naphthoxy is coordinated with metal, the catalyst has a limited space structure and higher stereospecificity, and an [ O, O, O ] tridentate coordination structure is formed by the bridging action of ether bonds, so that the stability of the catalyst skeleton is improved, an electron donor is further introduced into the ether bonds, and the bonding capacity of the coordination bonds is enhanced, so that the metal complex still maintains higher polymerization activity at high temperature. The catalyst has higher catalytic activity and stereotactic capability, and is particularly suitable for preparing polyolefin products with narrow molecular weight distribution.

In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:

an olefin polymerization catalyst having a naphthoxy skeleton, comprising the following components:

a. a metal complex represented by formula I;

wherein R is ₁ –R ₆ Identical to or different from each other, are each independently selected from hydrogen, halogen or optionally the following groups: C1-C24 alkyl, C1-C24 alkoxy, C1-C12 alkyl substituted amino, C6-C30 aryl, C6-C30 aralkyl, C6-C18 aryloxy, C1-C12 perfluoroalkyl, C12-C40 optionally substituted or unsubstituted carbazolyl, and derivatives thereof;

e1 and E2 are electron donors selected from any of the following groups: a C1-C18 linear or non-linear alkyl group, a C1-C18 alkoxy group, a C1-C16 alkyl substituted amino group, a C6-C24 aryl group, a C6-C18 aryloxy group, a silyl group, a C12-C40 optionally substituted or unsubstituted carbazolyl group, and derivatives thereof;

x is selected from halogen or other monovalent ligand groups having 1 to 20 atoms, or divalent ligand groups having 1 to 40 atoms;

m is selected from titanium, zirconium and hafnium;

b. an alkyl aluminum auxiliary;

c. optionally borates.

Further, in formula I, R ₁ –R ₆ Identical to or different from each other, are each independently selected from hydrogen, halogen or optionally the following groups: C1-C10 alkyl, C1-C10 alkoxy, C1-C8 alkyl substituted amino, C6-C24 aryl, C6-C24 aralkyl, C6-C18 aryloxy, C1-C6 perfluoroalkyl, C12-C24 aryl substituted or halogen substituted carbazolyl;

E ₁ 、E ₂ an electron donor selected from any of the following groups: a C1-C18 linear or non-linear alkyl group, a C1-C18 alkoxy group;

x is selected from halogen, alkyl and aryl;

m is selected from titanium, zirconium and hafnium.

Further, the metal complex represented by formula I is selected from the group consisting of the substances represented by the following structural expressions:

x is selected from halogen, alkyl and aryl;

m is selected from titanium, zirconium and hafnium.

Further, the alkyl aluminum auxiliary agent is selected from the group consisting of C-containing ₁ -C ₈ One or more of alkyl aluminoxanes or modified aluminoxanes;

preferably, the aluminoxane or modified aluminoxane is selected from one or more of methylaluminoxane, ethylaluminoxane, propylaluminoxane, t-butylaluminoxane, pentylaluminoxane, hexylaluminoxane, heptylaluminoxane, octylaluminoxane, methyl modified alkylaluminoxane, ethyl modified alkylaluminoxane, t-butyl modified alkylaluminoxane, amyl modified alkylaluminoxane, hexyl modified alkylaluminoxane, heptyl modified alkylaluminoxane, octyl modified alkylaluminoxane, preferably methylaluminoxane or t-butyl modified methylaluminoxane;

preferably, the borate is selected from one or more of trityl tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate-methyl dioctadecyl ammonium salt, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.

Further, the molar ratio of the alkyl aluminum auxiliary agent to the metal complex shown in the formula I is 3-450, preferably 40-250, calculated by the molar ratio of metal Al to metal M;

the molar ratio of borate to metal complex of formula I is 0 to 30, preferably 0 to 16, calculated as the molar ratio of element B to metal M.

A process for the preparation of a polyolefin by copolymerizing an olefin/α -olefin, comprising polymerizing an olefin/α -olefin in the presence of the olefin polymerization catalyst described above to prepare a polyolefin; the alpha-olefin is 1-propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene or 1-decene.

Preferably, the polymerization temperature is 30 to 250 ℃, preferably 80 to 220 ℃; the polymerization pressure is 0.1-50 MPa, preferably 1-10 MPa;

preferably, the dosage of the olefin polymerization catalyst is 0.1-10 mu mol/L based on the molar concentration of the metal M in the metal complex shown in the formula I in the reaction solvent;

preferably, the reaction solvent is one or more of Isopar E, isopar G, isopar H, isopar L, isopar M, more preferably Isopar E.

When the olefin polymerization catalyst is applied to olefin copolymerization, the polymerization method is as follows: packaging the metal complex shown in the formula I in an ampere bottle under anhydrous and anaerobic conditions, transferring into a high-pressure reaction kettle, heating to 120 ℃, fully replacing the reaction kettle with argon, and slowly cooling to 25 ℃. Sequentially adding an aluminum alkyl auxiliary agent, optionally borate and a comonomer solution, heating to a required temperature, introducing ethylene monomer, crushing an ampere bottle, and starting the polymerization reaction. In the whole polymerization process, the polymerization pressure is kept constant, and after the reaction is finished, 5% of acidified ethanol is used for neutralizing the reaction liquid, so that polymer precipitate is obtained, washed for a plurality of times, and vacuum-dried to constant weight of the polymer.

A method for preparing the naphthoxy skeleton olefin polymerization catalyst, which comprises a method for preparing a metal complex shown in a formula I, specifically comprises the following steps:

in the presence of a hydrogen extracting reagent, the ligand structure shown in the formula II and a metal salt MX ₄ Carrying out complexation reaction;

in formula II, R ₁ –R ₆ 、E ₁ 、E ₂ Definition of (2) and R in the foregoing ₁ –R ₆ 、E ₁ 、E ₂ Is the same as defined in the specification;

preferably, the ligand of formula II is a metal salt MX ₄ The molar ratio of (2) is 1 (0.4-0.6); the mol ratio of the ligand shown in the formula II to the hydrogen drawing reagent is 1 (2-6);

preferably, the metal salt MX ₄ Wherein M is titanium, zirconium or hafnium, X is halogen; metal salt MX ₄ Preferably selected from titanium tetrachloride, zirconium tetrachloride, hafnium tetrachloride, titanium tetrabromide, zirconium tetrabromide, hafnium tetrabromide;

preferably, the hydrogen extracting reagent is one or more of alkyl lithium, phenyl lithium, sodium hydride and Grignard reagent, and preferably n-hexyl lithium.

Further, the preparation method of the ligand shown in the formula II comprises the following steps:

wherein R is ₁ –R ₆ 、E ₁ 、E ₂ Definition of (2) and R in the foregoing ₁ –R ₆ 、E ₁ 、E ₂ Is the same as defined in the specification; r is selected from hydrogen,Boric acid, hydroxy or carboxy;

1) Reacting a compound of formula III with a brominating reagent to produce a bromination product of formula IV;

preferably, the reaction conditions are: the reaction temperature is-20 to 25 ℃ and the reaction time is 1 to 8 hours;

2) Reacting a compound of formula IV and a compound of formula V in the presence of a palladium catalyst and a base to form a compound of formula VI;

preferably, the reaction conditions are: the reaction temperature is 25-150 ℃ and the reaction time is 1-36 h;

3) Further reacting the compounds of formula VI, VII in the presence of a tin halide catalyst to form the compound of formula VIII;

preferably, the reaction conditions are: the reaction temperature is-40 to 50 ℃ and the reaction time is 1 to 10 hours.

Further, in the step 1), the compound of the formula III is selected from one or more of 3-methylnaphthalene-1-ol, 1, 8-dihydroxynaphthalene and 1-hydroxymethyl-4-methylnaphthalene, and the brominating reagent is liquid bromine;

in the step 2), the compound shown in the formula V is selected from one or more of 3, 5-di-tert-butylphenylboronic acid, 7H-dibenzocarbazole and 3, 6-dichloro carbazole, and the palladium catalyst is one or more of tetra (triphenylphosphine) palladium, 1' -bis (diphenylphosphino) ferrocene palladium (II) dichloride, palladium chloride, bis (triphenylphosphine) palladium dichloride, bis (tri-tert-butylphosphine) palladium, triphenylphosphine palladium acetate, bis (tricyclohexylphosphine) palladium (0), benzyl (chloro) bis (triphenylphosphine) palladium (II), tris (dibenzylidene-base acetone) dipalladium (0) and palladium acetate; the alkali is one or more of potassium carbonate, sodium carbonate, potassium phosphate, rubidium carbonate, cesium fluoride, sodium bicarbonate, sodium hydroxide, barium hydroxide and francium carbonate;

in the step 3), the compound of formula VII is selected from bis (1-methyl-2-hydroxyethyl) ether, diethylene glycol and 2- (2-hydroxy propoxy) -1-propanol, and the tin halide catalyst is one or more of tin tetrabromide, tin dibromide, tin diiodide, tin tetraiodide, tin dichloride and tin tetrachloride.

Further, in the step 1), the molar ratio of the compound of the formula III to the brominating reagent is 1 (1-2);

in the step 2), the mol ratio of the compound shown in the formula IV to the compound shown in the formula V to the palladium catalyst to the alkali is 1 (1-1.5): 0.1-1): 0.2-3;

in the step 3), the mol ratio of the compound of the formula VI, the compound of the formula VII and the tin halide catalyst is 1 (1-1.5) to 0.1-2.

The olefin polymerization catalyst with the naphthoxy skeleton provided by the invention has good high-temperature catalytic activity and stereotactic capability, and is particularly suitable for preparing polyolefin products with narrow molecular weight distribution.

Detailed Description

The invention will now be further illustrated by means of specific examples which are given solely by way of illustration of the invention and do not limit the scope thereof.

The main materials, the main sources of reagents used in the examples below are as follows:

3-methylnaphthalen-1-ol: AR, shanghai Jizhi Biochemical technology Co., ltd

1, 8-dihydroxynaphthalene: AR, hubei Kang Mingde pharmaceutical chemical Co., ltd

1-hydroxymethyl-4-methylnaphthalene: AR, ala-dine

3, 5-di-tert-butylphenylboronic acid: AR, ala-dine

Bis (1-methyl-2-hydroxyethyl) ether: AR, shanghai Yi En chemical technologies Co., ltd

Diethylene glycol: AR, ala-dine

3, 6-dichloro carbazole: AR, (alpha) Zhengzhou Convergence chemical Co., ltd

7H-dibenzocarbazole: AR, (alpha) Zhengzhou Convergence chemical Co., ltd

2- (2-hydroxypropoxy) -1-propanol: AR, hubei Xin chemical industry Co., ltd

Ethylene glycol dimethyl ether: AR, aladin

Tin tetrabromide: AR, sigma-Aldrich

Sodium carbonate: AR, innochem

Potassium hydroxide: AR, innochem

Liquid bromine: AR, innochem

Iron tribromide: AR, innochem

Dichloromethane: AR, innochem

Tetraphenylphosphine palladium: AR, innochem

TiCl ₄ : tokyo chemical industry Co Ltd

ZrCl ₄ : tokyo chemical industry Co Ltd

HfCl ₄ : tokyo chemical industry Co Ltd

Trityl tetrakis (pentafluorophenyl) borate: AR, aladin

Zirconocene dichloride: AR, aladin

Isopar E: exxon Mobil Corp

Methylaluminoxane (MAO): albemarle

Ethylene: 99.9% of Peking Yanshan petrochemical Co

1-hexene: 98%, beijing Yanshan petrochemical Co Ltd

Other materials and reagents were obtained commercially, unless otherwise specified.

The experimental methods used in the following examples are conventional methods unless otherwise specified.

The polymerization activities of the polymers described in the examples below were all calculated according to the following formulas: polymerization activity = polymer mass/(metal content in catalyst time of polymerization). The weight average molecular weight Mw of the polymer was determined by PL-GPC220 at 160℃using three PLgel 10 μm MIXED-B separation columns in series, 1,2, 4-trichlorobenzene as solvent. Methods for calculating comonomer insertion rate are referred to (Macromolecules 1999, 32, 3817).

In all examples and comparative examples below, chemical reactions were carried out after nitrogen substitution.

Preparation of Metal Complex M1 [ example 1 ]

The ligand and metal complex M1 were prepared according to the following synthetic route:

(1) 1mol of 3-methylnaphthalene1-alcohol (Compound 1), 0.2mol FeBr ₃ Adding into 600ml of dichloromethane, moving into water bath at 0 ℃, slowly dripping 1.5mol of Br under the stirring condition ₂ After 3h the reaction was ended. After extraction with water, the organic phase is concentrated and purified by column chromatography on silica gel (petroleum ether: ethyl acetate=150:1 (v/v)), giving compound 2.

The nuclear magnetic data of compound 2 are as follows:

¹ H NMR(CDCl ₃ ,400MHz,TMS):δ8.13(m,H),7.87(m,H),7.59(m,2H),7.33(m,1H),2.30(s,3H).

(2) 1mol of compound 2 and 1.2mol of 3, 5-di-tert-butyl phenylboronic acid (compound 3) are respectively dissolved in 2L of ethylene glycol dimethyl ether, then 1mol of aqueous solution (3 mol/L) of sodium carbonate is added, liquid nitrogen is frozen for deoxidization for three times, 0.5mol of tetraphenylpalladium phosphate is added under the protection of nitrogen, and the mixture is heated to 90 ℃ for reflux reaction for 6 hours. After extraction with water and ethyl acetate, the organic phase is concentrated and purified by column chromatography on silica gel (petroleum ether: ethyl acetate=200:1 (v/v)), giving compound 4.

The nuclear magnetic data of compound 4 are as follows:

¹ H NMR(CDCl ₃ ,400MHz,TMS):δ8.16(m,H),7.91(m,H),7.76(d,2H),7.62(d,1H),7.48(m,2H),7.34(t,1H),2.56(s,3H),1.31(s,18H).

(3) 1mol of compound 4 and 1mol of bis (1-methyl-2-hydroxyethyl) ether (compound 5) are dissolved in 600ml of dichloromethane, placed in an ice-water bath, fully stirred uniformly, and then 1mol of SnBr is slowly added dropwise ₄ After 5 hours, the reaction was completed. Quenched by addition of 50ml of saturated aqueous sodium bicarbonate, extracted with water, and the organic phase concentrated and purified by column chromatography on silica gel (petroleum ether: ethyl acetate=200:1 (v/v)) to give compound 6.

The nuclear magnetic data of compound 6 are as follows:

¹ H NMR(CDCl ₃ ,400MHz,TMS):δ7.85(m,2H),7.73(m,4H),7.61(m,2H),7.38(m,4H),6.87(m,2H),3.31(m,2H),3.14(m,4H),2.54(s,6H),1.31(s,36H),1.12(s,6H)

(4) In a glove box, 1mol of Compound 6 was dissolved in 1L of dry toluene, 4mol of n-butyllithium (2 mol/L) was slowly added dropwise thereto, and the mixture was reacted at 25℃for 2After h, the toluene was drained, dried n-hexane was added, stirred for 10min, and then allowed to stand, washed with dried n-hexane and filtered to collect the solid product. It was then dissolved in 1L of dry toluene and 1mol TiCl was added ₄ Heating to 130 ℃, carrying out reflux reaction for 7h, cooling to 25 ℃ after the reaction is finished, filtering to obtain filtrate, pumping the filtrate, adding 0.4L of dry n-hexane, stirring for 15min, standing for recrystallization, filtering, and drying to obtain a solid product which is marked as a metal complex M1.

Preparation of metal Complex M2 [ example 2 ]

The ligand and metal complex M2 were prepared according to the following synthetic route:

(1) 1mol of 3-methylnaphthalen-1-ol (Compound 1), 0.2mol of FeBr ₃ Adding into 600ml of dichloromethane, moving into water bath at 0 ℃, slowly dripping 1.3mol of Br under the stirring condition ₂ After 5h the reaction was ended. After addition of water extraction, the organic phase is concentrated and purified by column chromatography on silica gel (petroleum ether: ethyl acetate=150:1 (v/v)) to give compound 2.

The nuclear magnetic data of compound 2 are as follows:

¹ H NMR(CDCl ₃ ,400MHz,TMS):δ8.13(m,H),7.87(m,H),7.58(m,2H),7.36(m,1H),2.30(s,3H).

(2) 1mol of compound 2 and 1mol of 7H-dibenzocarbazole (compound 3) are dissolved in 500ml of acetone respectively, 2mol of aqueous solution of potassium hydroxide (1 mol/L) is added, the oxygen is removed three times by freezing liquid nitrogen, 1mol of tetraphenylpalladium phosphate is added under the protection of nitrogen, the temperature is heated to 55 ℃, and reflux reaction is carried out for 8 hours. The organic phase was concentrated after extraction with water and ethyl acetate and purified by silica gel column chromatography (petroleum ether: ethyl acetate=150:1 (v/v)), to give compound 4.

The nuclear magnetic data of compound 4 are as follows:

¹ H NMR(CDCl ₃ ,400MHz,TMS):δ8.43(m,2H),8.16(m,3H),8.02(m,H),7.88(m,2H),7.51(m,9H),1.98(s,3H).

(3) 1mol of compound 4 and 1.5mol of bis (1-methyl-2-hydroxyethyl) ether (compound 5) are dissolved in 600ml of dichloromethane, placed in an ice-water bath, fully stirred uniformly, and then 0.3mol of SnBr is slowly added dropwise ₄ After 5 hours, the reaction was completed. After quenching by adding 50ml of saturated aqueous sodium bicarbonate, the organic phase is concentrated after extraction and purified by silica gel column chromatography (petroleum ether: ethyl acetate=180:1 (v/v)), to give compound 6.

The nuclear magnetic data of compound 6 are as follows:

¹ H NMR(CDCl ₃ ,400MHz,TMS):δ8.43(m,4H),8.16(m,4H),7.80(m,6H),7.58(m,14H),7.35(m,2H)，7.01(m,2H)，3.34(m,2H)3.11(m,4H)，1.98(s,6H)，1.15(d,6H).

(4) In a glove box, anhydrous and anaerobic operation is carried out, 1mol of compound 6 is dissolved in 1L of dry toluene, 4mol of n-butyllithium (2 mol/L) is slowly added dropwise, after reaction for 2 hours at 25 ℃, toluene is pumped down, dry n-hexane is added, and after stirring for 10 minutes, standing is carried out, and the solid product is collected by washing and filtering with the dry n-hexane. Then it was dissolved in 1L of dry toluene and 1mol of ZrCl was added ₄ Heating to 130 ℃, carrying out reflux reaction for 7h, cooling to 25 ℃ after the reaction is finished, filtering to obtain filtrate, pumping the filtrate, adding 0.4L of dry n-hexane, stirring for 15min, standing for recrystallization, filtering, and drying to obtain a solid product which is marked as a metal complex M2.

Preparation of Metal Complex M3 [ example 3 ]

The ligand and metal complex M3 were prepared according to the following synthetic route:

(1) 1mol of 3-methylnaphthalene-1-Alcohol (Compound 1), 0.2mol FeBr ₃ Adding into 600ml of dichloromethane, transferring into water bath at 5 ℃, slowly dropwise adding 2mol of Br under stirring ₂ After 2h the reaction was ended. The organic phase was concentrated after extraction with water and purified by column chromatography on silica gel (petroleum ether: ethyl acetate=150:1 (v/v)) to give compound 2.

The nuclear magnetic data of compound 2 are as follows:

¹ H NMR(CDCl ₃ ,400MHz,TMS):δ8.13(m,H),7.88(m,H),7.58(m,2H),7.36(m,H),2.30(s,3H).

(2) 1mol of compound 2 and 1.5mol of 3, 6-dichloro carbazole (compound 3) are respectively dissolved in 500ml of acetone, 1mol of potassium hydroxide aqueous solution (2 mol/L) is added, liquid nitrogen is frozen for deoxidization three times, 0.5mol of tetraphenylpalladium phosphate is added under the protection of nitrogen, the temperature is heated to 60 ℃, and reflux reaction is carried out for 6 hours. Ethyl acetate and water were added, and the organic phase was concentrated and purified by silica gel column chromatography (petroleum ether: ethyl acetate=150:1 (v/v)), to give compound 4.

The nuclear magnetic data of compound 4 are as follows:

¹ H NMR(CDCl ₃ ,400MHz,TMS):δ8.31(d,H),8.16(m,H),8.02(m,2H),7.57(m,3H),7.35(m,2H),6.94(m,2H),1.98(s,3H).

(3) 1mol of compound 4 and 1.2mol of diethylene glycol (compound 5) are dissolved in 600ml of dichloromethane, placed in an ice-water bath, fully and uniformly stirred, and then 1.5mol of SnBr is slowly added dropwise ₄ After 6 hours of reaction, the reaction was completed. After quenching by adding 50ml of saturated aqueous sodium bicarbonate, the organic phase is concentrated after extraction and purified by silica gel column chromatography (petroleum ether: ethyl acetate=180:1 (v/v)), to give compound 6.

The nuclear magnetic data of compound 6 are as follows:

¹ H NMR(CDCl ₃ ,400MHz,TMS):δ8.33(d,2H),8.06(d,2H),7.85(m,2H),7.58(m,2H),7.36(m,6H)，6.97(d,6H)，3.51(t,4H)3.11(t,4H)，1.98(s,6H).

(4) In a glove box, 1mol of compound 6 is dissolved in 1L of dry toluene, 4mol of n-butyllithium (2 mol/L) is slowly added dropwise, the mixture is reacted for 2 hours at 25 ℃, the toluene is pumped down, the dry n-hexane is added, and the mixture is stirred for 10 minutes and then is calmAfter standing, the mixture was washed with dry n-hexane and filtered to collect a solid product. Then it was dissolved in 1L of dry toluene and 1mol of HfCl was added ₄ Heating to 130 ℃, carrying out reflux reaction for 7h, cooling to 25 ℃ after the reaction is finished, filtering to obtain filtrate, pumping the filtrate, adding 0.4L of dry n-hexane, stirring for 15min, standing for recrystallization, filtering, and drying to obtain a solid product which is marked as a metal complex M3.

Preparation of Metal Complex M4 [ comparative example 1 ]

The ligand and metal complex M4 were prepared according to the following synthetic route:

(1) 1mol of 1-hydroxymethyl-4-methylnaphthalene (Compound 1), 0.2mol of FeBr ₃ Adding into 1L of dichloromethane, moving into water bath at 0 ℃, slowly dropwise adding 1.5mol of Br under the stirring condition ₂ After 3h the reaction was ended. After extraction with water, the organic phase is concentrated and purified by column chromatography on silica gel (petroleum ether: ethyl acetate=150:1 (v/v)), giving compound 2.

The nuclear magnetic data of compound 2 are as follows:

¹ H NMR(CDCl ₃ ,400MHz,TMS):δ8.13(m,H),7.92(m,H),7.78(s,H),7.45(m,2H),4.8(s,2H),2.33(s,3H)。

(2) 1mol of compound 2 and 1.2mol of 3, 5-di-tert-butyl phenylboronic acid (compound 3) are respectively dissolved in 2L of ethylene glycol dimethyl ether, then 1mol of aqueous solution (3 mol/L) of sodium carbonate is added, liquid nitrogen is frozen for deoxidization for three times, 0.5mol of tetraphenylpalladium phosphate is added under the protection of nitrogen, and the mixture is heated to 90 ℃ for reflux reaction for 6 hours. Ethyl acetate and water were added, and the organic phase was concentrated and purified by silica gel column chromatography (petroleum ether: ethyl acetate=200:1 (v/v)), to give compound 4.

The nuclear magnetic data of compound 4 are as follows:

¹ H NMR(CDCl ₃ ,400MHz,TMS):δ8.13(m,H),7.92(m,H),7.88(s,H),7.75(s,2H),7.46(s,2H),7.36(s,H),4.97(s,2H),2.5(s,3H),1.32(s,18H).

(3) 1mol of compound 4 and 1mol of bis (1-methyl-2-hydroxyethyl) ether (compound 5) are dissolved in 1L of dichloromethane, placed in an ice-water bath, fully stirred uniformly, and then 1mol of SnBr is slowly added dropwise ₄ After 5 hours, the reaction was completed. Quenched by addition of 50ml of saturated aqueous sodium bicarbonate, extracted with water, and the organic phase concentrated and purified by column chromatography on silica gel (petroleum ether: ethyl acetate=200:1 (v/v)) to give compound 6.

The nuclear magnetic data of compound 6 are as follows:

¹ H NMR(CDCl ₃ ,400MHz,TMS):δ7.76(m,8H),7.34(m,4H),6.91(m,2H),4.97(s,4H),3.33(m,2H),3.21(m,4H),2.65(s,6H),1.32(s,36H),1.15(s,6H).

(4) In a glove box, anhydrous and anaerobic operation is carried out, 1mol of compound 6 is dissolved in 1L of dry toluene, 4mol of n-butyllithium (2 mol/L) is slowly added dropwise, after reaction for 2 hours at 25 ℃, toluene is pumped down, dry n-hexane is added, and after stirring for 10 minutes, standing is carried out, and the solid product is collected by washing and filtering with the dry n-hexane. It was then dissolved in 1L of dry toluene and 1mol TiCl was added ₄ Heating to 130 ℃, carrying out reflux reaction for 7h, cooling to 25 ℃ after the reaction is finished, filtering to obtain filtrate, pumping the filtrate, adding 0.4L of dry n-hexane, stirring for 15min, standing for recrystallization, filtering, and drying to obtain a solid product which is marked as a metal complex M4.

Preparation of metal Complex M5 [ comparative example 2 ]

The ligand and metal complex M5 were prepared according to the following synthetic route:

(1) 1mol of 1, 8-dihydroxynaphthalene (Compound1)、0.2mol FeBr ₃ Adding into 1L of dichloromethane, moving into water bath at 0 ℃, slowly dropwise adding 1.5mol of Br under the stirring condition ₂ After 3h the reaction was ended. After extraction with water, the organic phase is concentrated and purified by column chromatography on silica gel (petroleum ether: ethyl acetate=150:1 (v/v)), giving compound 2.

The nuclear magnetic data of compound 2 are as follows:

¹ H NMR(CDCl ₃ ,400MHz,TMS):δ7.68(d,2H),7.40(t,2H),6.57(m,H).

(2) 1mol of compound 2 and 1.2mol of 3, 5-di-tert-butyl phenylboronic acid (compound 3) are respectively dissolved in 2L of ethylene glycol dimethyl ether, then 1mol of aqueous solution (3 mol/L) of sodium carbonate is added, liquid nitrogen is frozen for deoxidization for three times, 0.5mol of tetraphenylpalladium phosphate is added under the protection of nitrogen, and the mixture is heated to 90 ℃ for reflux reaction for 6 hours. Ethyl acetate and water were added, and the organic phase was concentrated and purified by silica gel column chromatography (petroleum ether: ethyl acetate=200:1 (v/v)), to give compound 4.

The nuclear magnetic data of compound 4 are as follows:

¹ H NMR(CDCl ₃ ,400MHz,TMS):δ7.78(m,5H),7.28(m,2H),6.58(m,H),1.32(s,18H).

(3) 1mol of Compound 6 (1-hydroxy-8-bromonaphthalene), 0.2mol of FeBr ₃ Adding into 1L of dichloromethane, moving into water bath at 0 ℃, slowly dropwise adding 1.5mol of Br under the stirring condition ₂ After 3h the reaction was ended. After extraction with water, the organic phase is concentrated and purified by column chromatography on silica gel (petroleum ether: ethyl acetate=150:1 (v/v)), giving compound 7.

The nuclear magnetic data for compound 7 are as follows:

¹ H NMR(CDCl ₃ ,400MHz,TMS):δ8.02(m,2H),7.55(s,2H),7.46(t,H).

(4) 1mol of compound 7 and 1.2mol of 3, 5-di-tert-butylphenyl boric acid (compound 5) are respectively dissolved in 2L of ethylene glycol dimethyl ether, then 1mol of aqueous solution (3 mol/L) of sodium carbonate is added, liquid nitrogen is frozen for deoxidization for three times, 0.5mol of tetraphenylpalladium phosphate is added under the protection of nitrogen, and the mixture is heated to 90 ℃ for reflux reaction for 6 hours. Ethyl acetate and water were added, and the organic phase was concentrated and purified by silica gel column chromatography (petroleum ether: ethyl acetate=200:1 (v/v)), to give compound 8.

The nuclear magnetic data for compound 8 are as follows:

¹ H NMR(CDCl ₃ ,400MHz,TMS):δ8.01(m,2H),7.85(m,H),7.78(m,3H),7.37(m,2H),1.31(s,18H).

(5) 1mol of compound 4 and 1mol of compound 8 are dissolved in 1L of acetone, 2mol of KOH is added, the mixture is fully stirred, the temperature is raised to 60 ℃, the reaction is carried out for 8 hours, ethyl acetate and water are added for extraction, the organic phase is concentrated, and the organic phase is purified by silica gel column chromatography (petroleum ether: ethyl acetate=200:1 (v/v)), so as to obtain compound 9.

The nuclear magnetic data of compound 9 are as follows:

¹ H NMR(CDCl ₃ ,400MHz,TMS):δ7.75(m,8H),7.63(m,2H)，7.34(m,4H),6.61(m,2H),1.31(s,36H).

(6) In a glove box, anhydrous and anaerobic operation is carried out, 1mol of compound 9 is dissolved in 1L of dry toluene, 4mol of n-butyllithium (2 mol/L) is slowly added dropwise, after reaction for 2 hours at 25 ℃, toluene is pumped down, dry n-hexane is added, and after stirring for 10 minutes, standing is carried out, and the solid product is collected by washing and filtering with the dry n-hexane. It was then dissolved in 1L of dry toluene and 1mol TiCl was added ₄ Heating to 130 ℃, carrying out reflux reaction for 7h, cooling to 25 ℃ after the reaction is finished, filtering to obtain filtrate, pumping the filtrate, adding 0.4L of dry n-hexane, stirring for 15min, standing for recrystallization, filtering, and drying to obtain a solid product which is marked as a metal complex M5.

[ application examples 1 to 6 and comparative application examples 1 to 3 ]

The polymerization of ethylene/1-hexene was carried out using the metal complexes prepared in the foregoing examples, comparative examples, and a commercially available olefin polymerization catalyst, zirconocene dichloride, as a main catalyst, respectively, according to the following method and the raw materials, parameters, etc. shown in table 1 to prepare polyolefin:

an amp bottle containing a weighed main catalyst (1. Mu. Mol), a temperature sensor, a cooling reflux device and a mechanically stirred 1L autoclave were continuously dried at 120℃for 2 hours, evacuated and gradually cooled to 25 ℃. 400ml Isopar E, 100ml 1-hexene, methylaluminoxane (MAO) and trityl tetrakis (pentafluorophenyl) borate were successively added, wherein the molar ratio of methylaluminoxane to the metal element of the main catalyst was designated as Al/M, the molar ratio of B element in the trityl tetrakis (pentafluorophenyl) borate to the metal element M in the main catalyst was designated as B/M, and the amounts of methylaluminoxane and trityl tetrakis (pentafluorophenyl) borate added were as shown in Table 1, respectively. Heating to the reaction temperature of 80-220 ℃, introducing ethylene monomer of 1-10MPa to adjust the reaction pressure, crushing an ampere bottle, and starting the polymerization reaction. The stirring rate, polymerization temperature and ethylene pressure remained unchanged throughout the polymerization. And after the reaction is finished for 5min, evacuating the gas in the kettle, neutralizing the reaction liquid by using an industrial alcohol solution acidified by 5% hydrochloric acid to obtain polymer precipitate, washing for several times, and vacuum drying to constant weight for weighing to obtain the polymer.

TABLE 1 reaction conditions for each application example

Metal complex

Al/M

B/M

Reaction temperature/. Degree.C

Reaction pressure/MPa

Reaction time/min

Application example 1

M1

40:1

0：1

80

1

5

Application example 2

M2

250:1

2：1

100

3

5

Application example 3

M3

200:1

8：1

150

5

5

Application example 4

M1

100:1

16：1

220

10

5

Application example 5

M2

80:1

16：1

150

8

5

Application example 6

M3

150:1

8：1

190

10

5

Comparative application example 1

M4

100:1

8：1

190

10

5

Comparative application example 2

M5

100:1

8：1

190

10

5

Comparative example application example 3

Zirconocene dichloride

100:1

8：1

190

10

5

The polyolefin products prepared in each application example were subjected to the performance test in table 2, and the results are as follows:

TABLE 2 Performance test results

The data of the above examples and comparative examples show that the catalyst of the present invention has excellent catalytic performance, and can maintain high polymerization activity at high temperature when applied to the copolymerization of olefin/1-hexene, and is particularly suitable for preparing polyolefin products with narrow molecular weight distribution.

The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and additions may be made to those skilled in the art without departing from the method of the present invention, which modifications and additions are also to be considered as within the scope of the present invention.

Claims (24)

1. An olefin polymerization catalyst having a naphthoxy skeleton, comprising the following components:

a. a metal complex represented by formula I;

wherein R is ₁ An optionally substituted or unsubstituted carbazolyl group selected from the group consisting of C6 to C30 aralkyl groups and C12 to C40; r is R ₂ –R ₆ Are the same or different from each other, and are each independently selected from hydrogen, C1-C24 alkyl;

E ₁ 、E ₂ a linear or non-linear alkyl group selected from C1 to C18;

x is selected from halogen, alkyl and aryl;

m is selected from titanium, zirconium and hafnium;

b. an alkyl aluminum auxiliary;

c. optionally borates.

2. The catalyst for olefin polymerization of naphthyloxy skeleton according to claim 1, wherein in formula I, R ₁ An aralkyl group selected from C6 to C24, and an optionally substituted or unsubstituted carbazolyl group of C12 to C24; r is R ₂ –R ₆ Are the same or different from each other and are each independently selected from hydrogen, C1-C10 alkyl;

E ₁ 、E ₂ a linear or non-linear alkyl group selected from C1 to C18;

x is selected from halogen, alkyl and aryl;

m is selected from titanium, zirconium and hafnium.

3. The catalyst for olefin polymerization of a naphthoxy skeleton according to claim 2, wherein the metal complex represented by formula I is selected from the group consisting of substances represented by the following structural expressions:

x is selected from halogen, alkyl and aryl; m is selected from titanium, zirconium and hafnium.

4. A catalyst for the polymerization of olefins having a naphthyloxy skeleton according to any of claims 1 to 3, wherein the alkylaluminum auxiliary is selected from the group consisting of C-containing ones ₁ -C ₈ Alkyl aluminoxane or modified aluminoxane.

5. The catalyst for olefin polymerization of a naphthyloxy skeleton according to claim 4, wherein the alkylaluminum auxiliary is selected from methylaluminoxane and tert-butyl modified methylaluminoxane.

6. The catalyst for polymerizing olefins having a naphthoxy skeleton according to claim 4, wherein the borate is one or more selected from the group consisting of trityl tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate-methyldioctadecyl ammonium salt, and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.

7. The catalyst for olefin polymerization of a naphthoxy skeleton according to claim 4, wherein the molar ratio of the alkyl aluminum auxiliary agent to the metal complex represented by formula I is 3 to 450 in terms of the molar ratio of metal Al to metal M;

the molar ratio of the borate to the metal complex shown in the formula I is 0-30, and the molar ratio of the element B to the metal M is calculated.

8. The catalyst for olefin polymerization of a naphthoxy skeleton according to claim 7, wherein the molar ratio of the alkyl aluminum auxiliary agent to the metal complex represented by formula I is 40 to 250 in terms of the molar ratio of metal Al to metal M;

the molar ratio of the borate to the metal complex shown in the formula I is 0-16, and the molar ratio of the element B to the metal M is calculated.

9. A process for the preparation of a polyolefin by copolymerizing an olefin/α -olefin, characterized in that the olefin/α -olefin is polymerized in the presence of the olefin polymerization catalyst according to any one of claims 1 to 8 to prepare a polyolefin.

10. The method for preparing polyolefin by copolymerizing olefin/alpha-olefin according to claim 9, wherein the polymerization temperature is 30 to 250 ℃; the polymerization pressure is 0.1-50 Mpa.

11. The method for preparing polyolefin by copolymerization of olefin/alpha-olefin according to claim 10, wherein the polymerization temperature is 80-220 ℃; the polymerization pressure is 1-10 MPa.

12. The process for producing a polyolefin by copolymerizing an olefin/α -olefin according to claim 11, wherein the amount of the olefin polymerization catalyst is 0.1 to 10. Mu. Mol/L based on the molar concentration of the metal M in the metal complex of the formula I in the reaction solvent.

13. A process for the preparation of an olefin polymerization catalyst having a naphthoxy skeleton according to any one of claims 1 to 8, which comprises a process for the preparation of a metal complex represented by formula I, specifically:

in the presence of a hydrogen extracting reagent, the ligand structure shown in the formula II and a metal salt MX ₄ Carrying out complexation reaction;

in formula II, R ₁ –R ₆ 、E ₁ 、E ₂ Definition of (d) and R in any one of claims 1 to 8 ₁ –R ₆ 、E ₁ 、E ₂ Is the same as defined in the following.

14. The method for preparing an olefin polymerization catalyst having a naphthyloxy skeleton according to claim 13, wherein the ligand represented by formula II is mixed with a metal salt MX ₄ The molar ratio of (2) is 1 (0.4-0.6); the mol ratio of the ligand shown in the formula II to the hydrogen drawing reagent is 1 (2-6).

15. The method for producing a naphthoxy skeleton olefin polymerization catalyst according to claim 13, wherein the metal salt MX is ₄ Wherein M is titanium, zirconium or hafnium, and X is halogen.

16. The method for producing a naphthoxy skeleton olefin polymerization catalyst according to claim 15, wherein the metal salt MX is ₄ Selected from titanium tetrachloride, zirconium tetrachloride, hafnium tetrachloride, titanium tetrabromide, zirconium tetrabromide, and hafnium tetrabromide.

17. The method for preparing an olefin polymerization catalyst with a naphthoxy skeleton according to claim 13, wherein the hydrogen-withdrawing reagent is one or more of alkyl lithium, phenyl lithium, sodium hydride and grignard reagent.

18. The method for producing a naphthoxy skeleton olefin polymerization catalyst according to claim 17, wherein the hydrogen-withdrawing reagent is n-hexyllithium.

19. The method for preparing an olefin polymerization catalyst having a naphthoxy skeleton according to claim 13, wherein the method for preparing the ligand represented by formula II is as follows:

wherein R is ₁ –R ₆ 、E ₁ 、E ₂ Definition of (d) and R in any one of claims 1 to 8 ₁ –R ₆ 、E ₁ 、E ₂ Is the same as defined in the specification; r is selected from hydrogen, boric acid group, hydroxyl or carboxyl;

1) Reacting a compound of formula III with a brominating reagent to produce a bromination product of formula IV;

2) Reacting a compound of formula IV and a compound of formula V in the presence of a palladium catalyst and a base to form a compound of formula VI;

3) The compounds of formula VI and VII are further reacted in the presence of a tin halide catalyst to form the compound of formula VIII.

20. The method for producing an olefin polymerization catalyst having a naphthoxy skeleton according to claim 19, wherein the reaction conditions in step 1) are: the reaction temperature is-20 to 25 ℃ and the reaction time is 1 to 8 hours.

21. The method for producing an olefin polymerization catalyst having a naphthoxy skeleton according to claim 19, wherein the reaction conditions in step 2) are: the reaction temperature is 25-150 ℃ and the reaction time is 1-36 h.

22. The method for producing an olefin polymerization catalyst having a naphthoxy skeleton according to claim 19, wherein the reaction conditions in step 3) are: the reaction temperature is-40 to 50 ℃ and the reaction time is 1 to 10 hours.

23. The method for preparing an olefin polymerization catalyst having a naphthoxy skeleton according to claim 19, wherein in the step 1), the compound of formula III is one or more selected from the group consisting of 3-methylnaphthalene-1-ol, 1, 8-dihydroxynaphthalene, and 1-hydroxymethyl-4-methylnaphthalene, and the brominating agent is liquid bromine;

in the step 2), the compound shown in the formula V is selected from one or more of 3, 5-di-tert-butylphenylboronic acid, 7H-dibenzocarbazole and 3, 6-dichloro carbazole, and the palladium catalyst is one or more of tetra (triphenylphosphine) palladium, 1' -bis (diphenylphosphino) ferrocene palladium (II) dichloride, palladium chloride, bis (triphenylphosphine) palladium dichloride, bis (tri-tert-butylphosphine) palladium, triphenylphosphine palladium acetate, bis (tricyclohexylphosphine) palladium (0), benzyl (chloro) bis (triphenylphosphine) palladium (II), tris (dibenzylidene-base acetone) dipalladium (0) and palladium acetate; the alkali is one or more of potassium carbonate, sodium carbonate, potassium phosphate, rubidium carbonate, cesium fluoride, sodium bicarbonate, sodium hydroxide, barium hydroxide and francium carbonate;

in the step 3), the compound of formula VII is selected from bis (1-methyl-2-hydroxyethyl) ether, diethylene glycol and 2- (2-hydroxy propoxy) -1-propanol, and the tin halide catalyst is one or more of tin tetrabromide, tin dibromide, tin diiodide, tin tetraiodide, tin dichloride and tin tetrachloride.

24. The process for preparing a naphthoxy skeleton olefin polymerization catalyst according to any one of claims 19 to 23, wherein in step 1), the molar ratio of the compound of formula III to the brominating agent is 1 (1-2);

in the step 2), the mol ratio of the compound shown in the formula IV to the compound shown in the formula V to the palladium catalyst to the alkali is 1 (1-1.5): 0.1-1): 0.2-3;

in the step 3), the mol ratio of the compound of the formula VI, the compound of the formula VII and the tin halide catalyst is 1 (1-1.5) to 0.1-2.