Catalyst for olefin polymerization and preparation method and application thereof

Abstract

The invention provides a catalyst for olefin polymerization as well as a preparation method and application of the catalyst. The catalyst comprises titanium, magnesium, halogen and a phosphonate internal electron donor, wherein the phosphonate internal electron donor has a structure as shown in a formula I: # imgabs0 #, the catalyst has high catalytic activity, and the obtained polymerization product has wide molecular weight distribution and good stereoregularity.

Description

Technical Field

[0001] The invention provides a catalyst for olefin polymerization and a preparation method and application thereof, belonging to the field of catalysts. Background Art

[0002] Polypropylene (PP) has a rapid growth in production and consumption in recent years due to its excellent comprehensive performance and easy processing. With the development of the PP industry, manufacturers are focusing on the quality management of general-purpose products while also working hard to develop new grades of special resins with high added value. Wide molecular weight distribution PP has the characteristics of excellent comprehensive physical properties and processing properties. It has been widely used in many fields such as biaxially oriented polypropylene (BOPP), random copolymer polypropylene (PPR), and high melt strength PP. New grades of special resins developed based on wide molecular weight distribution polypropylene are also emerging.

[0003] The internal electron donor component in Ziegler-Natta catalyst plays a key role in improving the catalyst performance.

[0004] In the prior art, succinate compounds are used as internal electron donors to obtain polymers with a relatively wide molecular weight distribution (CN1681853A, CN1398270A, CN1313869A, US0050014631).

[0005] CN1974612A discloses that a phosphate compound electron donor is used in a polypropylene catalyst. When the catalyst is used in propylene polymerization, a polypropylene homopolymer or copolymer product with a Mw / Mn of 7-9 can be obtained. The structural formula of the phosphate compound is:

[0006] The catalytic activity is relatively low during propylene polymerization, and the isotacticity of the resulting polymer is relatively low.

[0007] Similarly, CN101125898A discloses a solid catalyst component containing an organic phosphate compound, which can obtain a polymer with a Mw / Mn of 7-9.3 during propylene polymerization, and the isotacticity of the polymer is easy to control and has good processing performance. CN108264589A discloses a solid catalyst containing a bisphosphonate compound with a tetrahydroquinoline structure, which can obtain a high isotactic polypropylene with a wider molecular weight distribution in a reactor during propylene polymerization, but the molecular weight distribution is relatively narrow.

[0008] CN101787088A discloses a polymerization catalyst using a phosphorus-substituted sulfonyl compound as an internal electron donor, the catalyst has good polymerization catalytic activity, and the polymerization product has high isotacticity. The general formula of the internal electron donor is:

[0009] Where R1 , R 2 They are respectively the same or different chain alkyl or aryl groups, and the hydrogen atoms on the substituents may be substituted by any halogen atoms.

[0010] CN201019102020.9 provides a phenylphosphine-substituted sulfonyl compound as an internal electron donor; the polymer molecular weight distribution obtained by using the catalyst prepared by the internal electron donor is narrow. Summary of the invention

[0011] In order to solve the above problems, the purpose of the present invention is to provide a catalyst for olefin polymerization and its preparation method and application, the catalyst has high catalytic activity, and the obtained polymer product has a wide molecular weight distribution and good stereoregularity.

[0012] In order to achieve the above object, the present invention provides a catalyst for olefin polymerization, which comprises titanium, magnesium, halogen, and a phosphonate internal electron donor; wherein the phosphonate internal electron donor has a structure shown in Formula I:

[0013]

[0014] In Formula I, R 1 and R 2 The same or different, each independently selected from C 1 -C 20 Straight chain alkyl, C 1 -C 20 Branched alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 The aromatic group, C 7 -C 20 Alkyl, C 7 -C 20 Alkoxyaryl; R 3 Selected from hydrogen, C 1 -C 20 Straight chain alkyl, C 1 -C 20 Branched alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 The aromatic group, C 7 -C 20 Alkyl, C 7 -C 20 an alkoxyaryl group, a saturated condensed ring structure, or an unsaturated condensed ring structure.

[0015] According to a specific embodiment of the present invention, preferably, the catalyst comprises an alcoholate of a magnesium halide, a titanium compound, and the phosphonate internal electron donor.

[0016] According to a specific embodiment of the present invention, preferably, in Formula I, R 1 and R 2 Selected from C 3 -C 10 Alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 10 The aromatic group, C 7 -C 10 Alkyl, C 7 -C 10 Alkoxyaryl; R 3 Selected from C 3 -C 10 Straight chain alkyl, C 3 -C 10 Branched alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 10 The aromatic group, C 7 -C 10 Alkyl, C 7 -C 10 an alkoxyaryl group, a saturated condensed ring structure, or an unsaturated condensed ring structure.

[0017] According to a specific embodiment of the present invention, preferably, the phosphonate internal electron donor is selected from dimethyl (1-aminomethyl-2-oxopropyl)phosphonate, dimethyl [1-(1-aminoethyl)-2-oxopropyl]phosphonate, dimethyl [1-(1-aminopropyl)-2-oxopropyl]phosphonate, dimethyl [1-(1-amino-1-isopropylmethyl)-2-oxopropyl]phosphonate, dimethyl [1-(1-amino-1-tert-butylmethyl)-2-oxopropyl]phosphonate, dimethyl [1-(1-aminopentyl)-2-oxopropyl]phosphonate, dimethyl [1-(1-amino-n-hexyl)-2-oxopropyl]phosphonate, dimethyl [1-(1-amino-n-octyl)-2-oxopropyl]phosphonate, dimethyl [1-(1-amino-1- [1-(1-amino-1-p-tolylmethyl)-2-oxopropyl]phosphonate, dimethyl [1-(1-amino-1-o-tolylmethyl)-2-oxopropyl]phosphonate, dimethyl [1-(1-amino-1-p-ethylphenylmethyl)-2-oxopropyl]phosphonate, dimethyl [1-(1-amino-1-o-ethylphenylmethyl)-2-oxopropyl]phosphonate, dimethyl [1-(1-amino-1-p-methoxyphenylmethyl)-2-oxopropyl]phosphonate, dimethyl [1-(1-amino-1-o-methoxyphenylmethyl)-2-oxopropyl]phosphonate, dimethyl [1-(1-amino-1-naphthylmethyl)-2-oxopropyl]phosphonate, dimethyl [1-(1-amino-1-naphthylmethyl)-2-oxopropyl]phosphonate, dimethyl [1-(1-amino-1-p-methylphenylmethyl)-2-oxopropyl]phosphonate, dimethyl [1-(1-amino-1-naphthylmethyl)-2-oxopropyl]phosphonate, dimethyl [1-(1-amino-1-p-methylphenylmethyl)-2-oxopropyl]phosphonate, dimethyl [1-(1-amino-1-naphthylmethyl)-2-oxopropyl]phosphonate, dimethyl [1-(1-amino-1-p-methylphenylmethyl)-2-oxopropyl 1-(1-aminoethyl)-2-oxopropyl]phosphonate, diethyl [1-(1-aminopropyl)-2-oxopropyl]phosphonate, diethyl [1-(1-amino-1-isopropylmethyl)-2-oxopropyl]phosphonate, diethyl [1-(1-amino-1-tert-butylmethyl)-2-oxopropyl]phosphonate, diethyl [1-(1-aminopentyl)-2-oxopropyl]phosphonate, diethyl [1-(1-amino-n-hexyl)-2-oxopropyl]phosphonate, diethyl [1-(1-amino-n-octyl)-2-oxopropyl]phosphonate, diethyl [1-(1-amino-1-phenylmethyl)-2-oxopropyl]phosphonate, [1-(1-amino-1-p-tolylmethyl)-2-oxopropyl]phosphonate 1-(1-amino-1-o-tolylmethyl)-2-oxopropyl]phosphonate, diethyl [1-(1-amino-1-p-methoxyphenylmethyl)-2-oxopropyl]phosphonate, diethyl [1-(1-amino-1-o-methoxyphenylmethyl)-2-oxopropyl]phosphonate, diethyl [1-(1-amino-1-o-methoxyphenylmethyl)-2-oxopropyl]phosphonate, diethyl [1-(1-amino-1-naphthylmethyl)-2-oxopropyl]phosphonate, diisopropyl (1-aminomethyl-2-oxopropyl)phosphonate, diisopropyl [1-(1-aminoethyl)-2-oxopropyl]phosphonate, diisopropyl [1-(1-aminopropyl)-2-oxopropyl]phosphonate, diisopropyl [1-(1-amino-1-isopropylmethyl)-2-oxopropyl]phosphonate,[1-(1-aminopentyl)-2-oxopropyl]phosphonic acid diisopropyl ester, [1-(1-amino-1-phenylmethyl)-2-oxopropyl]phosphonic acid diisopropyl ester, [1-(1-amino-1-p-tolylmethyl)-2-oxopropyl]phosphonic acid diisopropyl ester, [1-(1-amino-1-o-methoxyphenylmethyl)-2-oxopropyl]phosphonic acid diisopropyl ester, [1-(1-amino-1-naphthylmethyl)-2-oxopropyl]phosphonic acid diisopropyl ester, [1-(1-aminoethyl)-2-oxopropyl]phosphonic acid diphenyl ester, [1-(1-amino-1-isopropylmethyl)-2-oxopropyl]phosphonic acid diphenyl ester, [1-(1-aminohexyl)-2-oxopropyl]phosphonic acid diphenyl ester, [1-(1 [1-(1-amino-1-p-tolylmethyl)-2-oxopropyl]phosphonic acid diphenyl ester, [1-(1-amino-1-p-methoxyphenylmethyl)-2-oxopropyl]phosphonic acid diphenyl ester, [1-(1-amino-1-naphthylmethyl)-2-oxopropyl]phosphonic acid diphenyl ester, (1-aminomethyl-2-oxopropyl)phosphonic acid dibenzyl ester, [1-(1-aminopropyl)-2-oxopropyl]phosphonic acid dibenzyl ester, [1-(1-aminopropyl)-2-oxopropyl]phosphonic acid dibenzyl ester, [1-(1-amino-1-isopropylmethyl)-2-oxopropyl]phosphonic acid dibenzyl ester, [1-(1-amino-1-tert-butylmethyl)-2-oxopropyl]phosphonic acid dibenzyl ester, [1-(1-amino-1-phenylmethyl)-2-oxopropyl]phosphonic acid dibenzyl ester, [1-(1-amino-1-tert-butylmethyl)-2-oxopropyl]phosphonic acid dibenzyl ester, [1-(1-amino-1-phenylmethyl)-2-oxopropyl]phosphonic acid dibenzyl ester )-2-oxopropyl]phosphonic acid dibenzyl ester, [1-(1-amino-1-p-methoxyphenylmethyl)-2-oxopropyl]phosphonic acid dibenzyl ester, [1-(1-amino-1-naphthylmethyl)-2-oxopropyl]phosphonic acid dibenzyl ester, [1-(1-aminoethyl)-2-oxopropyl]phosphonic acid di(4-isopropylphenyl) ester, [1-(1-amino-1-isopropylmethyl)-2-oxopropyl]phosphonic acid di(4-isopropylphenyl) ester, [1-(1-aminohexyl)-2-oxopropyl]phosphonic acid di(4-isopropylphenyl) ester, [1-(1-amino-1-phenylmethyl)-2-oxopropyl]phosphonic acid di(4-isopropylphenyl) ester, [1-(1-amino-1-p-tolylmethyl)-2 [1-(1-amino-1-p-methoxyphenylmethyl)-2-oxopropyl]phosphonic acid bis(4-isopropylphenyl) ester, [1-(1-amino-1-naphthylmethyl)-2-oxopropyl]phosphonic acid bis(4-isopropylphenyl) ester, [1-(1-amino-1-naphthylmethyl)-2-oxopropyl]phosphonic acid bis(4-isopropylphenyl) ester, [1-(1-aminoethyl)-2-oxopropyl]phosphonic acid bis(2-methoxyphenyl) ester, [1-(1-amino-1-isopropylmethyl)-2-oxopropyl]phosphonic acid bis(2-methoxyphenyl) ester, [1-(1-aminohexyl)-2-oxopropyl]phosphonic acid bis(2-methoxyphenyl) ester, [1-(1-amino-1-phenylmethyl)-2-oxopropyl]phosphonic acid bis(2-methoxyphenyl) ester,[1-(1-amino-1-p-tolylmethyl)-2-oxopropyl]phosphonic acid bis(2-methoxyphenyl) ester, [1-(1-amino-1-o-methoxyphenylmethyl)-2-oxopropyl]phosphonic acid bis(2-methoxyphenyl) ester, [1-(1-amino-1-naphthylmethyl)-2-oxopropyl]phosphonic acid bis(2-methoxyphenyl) ester, [1-(1-aminoethyl)-2-oxopropyl]phosphonic acid bis(2,4-diethoxyphenyl) ester, [1-(1-amino-1-isopropylmethyl)-2-oxopropyl]phosphonic acid bis(2,4-diethoxyphenyl) ester, [1-(1-aminohexyl)-2-oxopropyl]phosphonic acid bis(2,4-diethoxyphenyl) ester )-2-oxopropyl]phosphonic acid bis(2,4-diethoxyphenyl) ester, [1-(1-amino-1-phenylmethyl)-2-oxopropyl]phosphonic acid bis(2,4-diethoxyphenyl) ester, [1-(1-amino-1-p-tolylmethyl)-2-oxopropyl]phosphonic acid bis(2,4-diethoxyphenyl) ester, [1-(1-amino-1-o-methoxyphenylmethyl)-2-oxopropyl]phosphonic acid bis(2,4-diethoxyphenyl) ester, [1-(1-amino-1-naphthylmethyl)-2-oxopropyl]phosphonic acid bis(2,4-diethoxyphenyl) ester, or a combination of two or more thereof.

[0018] According to a specific embodiment of the present invention, preferably, in the alcoholate of the magnesium halide, the magnesium halide is selected from one or more of magnesium chloride, magnesium bromide, chloromethoxymagnesium, and chloroethoxymagnesium, and the alcohol is selected from one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, and isobutanol. The present invention does not particularly limit the alcoholate of the magnesium halide, and can be selected from the magnesium halide alcoholates conventionally used in the art.

[0019] According to a specific embodiment of the present invention, preferably, in the alcoholate of magnesium halide, the magnesium halide is magnesium chloride, and the alcohol is ethanol.

[0020] According to a specific embodiment of the present invention, preferably, the general formula of the titanium compound is Ti(OR') n X (4－n) , R' is selected from C 1 -C 20 Alkyl, C 6 -C 20 Aryl, C 7 -C 20 Aralkyl, X is halogen, and n is an integer of 0≤n≤4.

[0021] According to a specific embodiment of the present invention, preferably, the titanium compound is selected from one or a combination of two or more of tetraethoxytitanium, tetrabutoxytitanium, chlorotrialkoxytitanium, dichlorodialkoxytitanium, trichloroalkoxytitanium, titanium tetrachloride and titanium tetrabromide.

[0022] According to a specific embodiment of the present invention, preferably, the titanium compound is titanium tetrachloride.

[0023] According to a specific embodiment of the present invention, preferably, based on the mass of the catalyst as 100%, the composition of the catalyst comprises 6-20% of a phosphonate internal electron donor, more preferably 7-12% of a phosphonate internal electron donor, and the contents of titanium, magnesium and halogen are comparable to those of the prior art. The present invention does not particularly limit the contents of titanium, magnesium and halogen, and more preferably, based on the mass of the catalyst as 100%, the composition of the catalyst comprises 10-25% of magnesium, 1.5-10% of titanium, 50-60% of halogen and 6-20% of a phosphonate internal electron donor.

[0024] The polypropylene catalyst of the present invention can be prepared by existing technology, such as the preparation method of the catalyst disclosed in patent CN1453298A. The commonly used method is: mixing magnesium halide alcoholate and part of titanium halide, adding internal electron donor, heating treatment and filtering, adding remaining titanium halide, heating treatment, filtering, washing and drying to obtain the catalyst product.

[0025] The present invention also provides a method for preparing the above catalyst, which comprises the following steps:

[0026] (1) adding a magnesium halide alcoholate to a titanium compound at -50°C to 20°C, and reacting for 10 min to 6 h. In step (1), the molar ratio of magnesium to titanium is 1:5 to 1:100;

[0027] (2) raising the temperature to 0° C. to 100° C., adding a phosphonate internal electron donor represented by formula I, wherein the molar ratio of magnesium to the phosphonate internal electron donor is 2:1-20:1;

[0028] (3) heating to 100°C to 150°C and reacting for 0.5-6h;

[0029] (4) After filtering, add the same amount of titanium compound as in step (1), and react at 100° C. to 130° C. for 0.5-6 h to obtain the catalyst.

[0030] According to a specific embodiment of the present invention, preferably, the above preparation method comprises the following steps:

[0031] (1) adding a magnesium halide alcoholate to a titanium compound liquid at -30°C to 0°C, and reacting for 1-4 hours. In step (1), the molar ratio of magnesium to titanium is 1:20-1:60;

[0032] (2) raising the temperature to 30° C.-60° C., adding a phosphonate internal electron donor represented by formula I, wherein the molar ratio of magnesium to the phosphonate internal electron donor is 2:1-12:1;

[0033] (3) heating to 110°C to 130°C and reacting for 1-4 hours;

[0034] (4) After filtering, add the same amount of titanium compound liquid as in step (1), react at 110° C.-130° C. for 1-2 hours, and obtain the catalyst after filtering, washing and drying.

[0035] The catalyst of the present invention is used for propylene polymerization, and a certain amount of co-catalyst needs to be added. In order to obtain a better polymerization effect, the present invention also provides a catalyst system for olefin polymerization, which comprises the above catalyst, alkyl aluminum compound, and alkoxysilane compound.

[0036] According to a specific embodiment of the present invention, preferably, the general formula of the alkyl aluminum compound is AlR" m Y (3-m) , R" is selected from C 1 -C 20 Alkyl, C 6 -C 20 The aromatic group, C 7 -C 20 wherein Y is a halogen, and m is an integer of 0≤m≤3.

[0037] According to a specific embodiment of the present invention, preferably, the alkyl aluminum compound is selected from one or a combination of two or more of trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, diethyl aluminum monochloride, and diisobutyl aluminum monochloride.

[0038] According to a specific embodiment of the present invention, preferably, the alkyl aluminum compound is triethyl aluminum and / or triisobutyl aluminum.

[0039] According to a specific embodiment of the present invention, preferably, the alkoxysilane compound is selected from one or a combination of two or more of dimethoxydimethylsilane, diethoxydimethylsilane, dimethoxydiphenylsilane and methylcyclohexyldimethoxysilane.

[0040] According to a specific embodiment of the present invention, preferably, the alkoxysilane compound is methylcyclohexyldimethoxysilane.

[0041] According to a specific embodiment of the present invention, preferably, the molar ratio of titanium to aluminum in the catalyst system is 1:1-1:2000; the molar ratio of titanium to silicon is 1:1-1:50.

[0042] According to a specific embodiment of the present invention, preferably, the molar ratio of titanium to aluminum in the catalyst system is 1:1-1:500; the molar ratio of titanium to silicon is 1:1-1:20.

[0043] The present invention also provides application of the catalyst or the catalyst system in olefin polymerization.

[0044] According to a specific embodiment of the present invention, preferably, the olefin polymerization is propylene polymerization, such as bulk polymerization or slurry polymerization of propylene.

[0045] According to a specific embodiment of the present invention, preferably, the polymerization temperature is 0°C to 80°C, more preferably 20°C to 70°C.

[0046] The present invention has the following beneficial effects:

[0047] (1) The amino-substituted phosphonate compound used in the catalyst of the present invention has a C=O group, which changes the electron cloud density of the phosphonate compound, so that the catalyst can obtain a polymer with a wider molecular weight distribution.

[0048] (2) The amino-substituted phosphonate compound used in the catalyst of the present invention has a C=O group, which changes the electron cloud density of the phosphonate compound, so that the catalyst retains good activity and stereoregularity. DETAILED DESCRIPTION

[0049] In order to have a clearer understanding of the technical features, purposes and beneficial effects of the present invention, the technical solution of the present invention is now described in detail below, but it should not be construed as limiting the applicable scope of the present invention.

[0050] Test Method

[0051] (1) The Ti content in the catalyst was determined by spectrophotometry (722S model) in the following steps:

[0052] Under the protection of inert gas, weigh 0.2000g sample and dissolve it with 20mL (1:4) sulfuric acid; extract with 9mL heptane three times, shake for 5min each time to separate organic matter; place the organic phase in a 10mL volumetric flask and dilute with heptane (for determination of organic content); dilute the inorganic phase to a 50mL volumetric flask with water, shake well for use; take 2mL of the test solution in 25mL volumetric flasks, add 1mL 3% (m / v) hydrogen peroxide, dilute to scale with sulfuric acid (1:9), shake well, and place for 10min. Use blank as reference solution and 3cm colorimetric dish to determine the absorbance value at a wavelength of 410nm. Find the corresponding value from the titanium standard fitting line to calculate the content.

[0053] (2) The content of electron donor compounds was determined by gas chromatography (Techcomp GC7900): the organic phase was directly subjected to gas chromatography analysis using a heptane solution of the pure substance as a reference, and the content was calculated by the ratio of the peak area of ​​the analyte to that of the pure substance solution.

[0054] (3) The magnesium content in the catalyst is determined by the EDTA volumetric method. Triethanolamine and potassium sodium tartrate are used to mask impurities such as Ti, Al, and Fe. At pH = 10, acid chrome blue K-naphthol green B is used as a joint indicator and EDTA standard solution is used for complexometric titration. The experimental steps are as follows: 5 mL of the prepared test solution (for the determination of Ti, Mg, and Cl) is taken in duplicate, and 10 mL of 1:2 (v / v) triethanolamine aqueous solution, 10 mL of 10% (m / v) potassium sodium tartrate aqueous solution, 20 mL of pH = 10 buffer solution, 5-6 drops of indicator are added to a 250 mL conical flask, and shake well. Titrate with EDTA standard solution (C = 0.02 mol / L) until pure blue is the end point, and a blank test is performed at the same time. Calculate the magnesium content based on the volume of the EDTA standard solution used.

[0055] (4) The chlorine content in the catalyst is determined by potentiometric titration. In a weakly acidic ethanol aqueous solution, a standard silver nitrate solution is used as the titrant, and the titration endpoint is determined by means of the titration potential jump. The test steps are as follows: 10 mL of the prepared test solution for titanium measurement is placed in a 100 mL beaker, 20 mL of anhydrous ethanol and 20 mL of distilled water are added, the electromagnetic stirring bar is placed in the beaker, and placed on the tray of the potentiometer magnetic stirrer, the measuring electrode (silver electrode) and the reference electrode (calomel electrode) are inserted into the cup, and the stirrer is turned on. First, zero point calibration is performed, then positioning is performed, and titration is performed with a standard silver nitrate solution (C = 0.025 mol / L), and a blank test is performed at the same time. The chlorine content is calculated based on the volume of the standard silver nitrate solution used.

[0056] (5) Determination of Molecular Weight Distribution: High Temperature Gel Chromatography Analysis The relative molecular weight and distribution of the sample were determined on a Waters Alliance GPC 2000 gel permeation chromatograph produced by Waters Corporation of the United States. The mobile phase solvent was o-dichlorobenzene, the flow rate was 1.0 mL / min, and the measurement temperature was 135°C.

[0057] (6) The isotactic index of polymer is tested in accordance with GB / T 2412-1980.

[0058] Synthesis of Internal Electron Donor Compounds

[0059] Preparation Example 1

[0060] This preparation example provides [1-(1-amino-1-phenylmethyl)-2-oxopropyl]phosphonic acid diisopropyl ester, and its synthesis steps are as follows:

[0061] (1) Synthesis of diisopropyl (2-oxopropyl)phosphonate

[0062] Add 42g of anhydrous potassium carbonate, 60mL of petroleum ether, and 30.7mL of isopropanol to the reaction flask, stir and heat to reflux, then slowly drop 20mL of petroleum ether and 8.7mL of phosphorus trichloride into the reaction solution. After the addition is completed, continue to reflux for 1h, cool to room temperature and filter, wash the filter cake with petroleum ether, combine the filtrate, remove the solvent, and distill under reduced pressure to obtain a colorless liquid, which is diisopropyl phosphite. Bromoacetone reacts with diisopropyl phosphite to obtain the product (2-oxopropyl) diisopropyl phosphate. Diisopropyl phosphite 1 H NMR (CDCl 3 , 300MHz) analysis results: δ7.51-7.41 (m, 1H), 6.14-6.03 (m, 1H), 4.83-4.50 (m, 2H), 1.30 (d, J=2.4Hz, 12H).

[0063] The reaction of bromoacetone and diisopropyl phosphite was prepared according to the literature “M.-L.Ma, Z.-H.Peng, L.Chen, et al. Erratum: Synthesis of new MeO-BIPHEP-type chiral diphosphines by an improved way (Chinese Journal of Chemistry (2006) 24, 10, (1391)) [J]. 2006.”

[0064] (2) Synthesis of diisopropyl[1-(1-amino-1-phenylmethyl)-2-oxopropyl]phosphate

[0065] At 0°C, weigh α-aminosulfone (58.72 mg, 0.15 mmol) and (2-oxopropyl)phosphonic acid diisopropyl ester (22.22 mg, 0.1 mmol) and dissolve in toluene (1.5 mL), add TBAB (6.44 mg, 0.02 mmol) as a catalyst, and then add 0.25 mL of 25% sodium hydroxide aqueous solution, stir to react, monitor the reaction process by TLC until the phosphonate is completely consumed, add 20 mL of ethyl acetate to dilute after the reaction is completed, wash with water and saturated NaCl solution, collect the organic phase, dry over anhydrous sodium sulfate, concentrate and purify by column chromatography, mix the obtained compound with 6N hydrochloric acid, stir at 25°C for 2h, neutralize with saturated sodium carbonate aqueous solution, extract three times with dichloromethane, combine the organic phases and wash once with saturated brine. Dry, filter, and distill the filtrate under reduced pressure to obtain a colorless liquid, which is the product [1-(1-amino-1-phenylmethyl)-2-oxopropyl]phosphonic acid diisopropyl ester. 1 H NMR (CDCl 3, 300MHz) analysis results: δ7.08-7.21 (5H, ph-H); δ3.57 (2H, CH); δ3.2 (1H, CH); δ2.64-2.89 (2H, CH 2 ); δ2.6(1H,CH); δ2.09(3H,CH 3 );δ1,16(3H,-CH 3 ).

[0066] The internal electron donor compounds used in the following examples were synthesized according to the above method.

[0067] Example 1

[0068] This embodiment provides a catalyst, and the preparation method thereof is as follows:

[0069] Under anhydrous and oxygen-free conditions, 5.0 g of microspherical magnesium chloride alcoholate particles were added to 123 ml of titanium tetrachloride liquid at -20°C, reacted for 1 hour, and then gradually heated to 60°C; 0.0037 mol of [1-(1-aminoethyl)-2-oxopropyl]phosphonic acid diisopropyl ester was added, and the temperature was gradually raised to 120°C, reacted for 2 hours, washed 5 times at 60°C, and filtered with 30 ml of hexane at room temperature; 123 ml of titanium tetrachloride was added, reacted at 120°C for 1 hour and filtered. The catalyst was washed once with 100 ml of hexane and dried in vacuo to obtain the catalyst.

[0070] Preparation of spherical magnesium chloride alcoholate particles (self-made, preparation steps refer to CN1110281A, the same below): under anhydrous and oxygen-free conditions, add 24g of anhydrous magnesium chloride, 50mL of anhydrous ethanol, 390mL of white vaseline oil, 10mL of silicone oil and 2mL of Siban in a 1L high-pressure reactor, stir and heat to 130°C, and react at this temperature for 4 hours to completely dissolve the solid. Use nitrogen to pressurize the reactor to 1.0MPa, open the valve to discharge the material, and let the material in the reactor pass through a capillary with a diameter of 1.2mm and a length of 3.5m into 2.5L of anhydrous hexane cooled to -30°C in advance. The solid particles are washed 5 times with hexane and dried in vacuum at room temperature to obtain spherical magnesium chloride alcoholate particles with an average particle size of 50μm and a specific surface area of ​​150-230m 2 / g, the molar ratio of alcohol to magnesium chloride is 2.85:1, molecular formula: MgCl 2 2.85CH 3 CH 2 OH.

[0071] The obtained catalyst was used for bulk polymerization: 2 kg of propylene, triethylaluminum and methylcyclohexyldimethoxysilane were added to a 10-liter stainless steel reactor that had been vacuum dried and fully replaced with nitrogen and propylene gas, with the molar ratio of titanium to aluminum being 1:200 and the molar ratio of titanium to silicon being 1:20; 30 mg of the above catalyst and 0.3 g of hydrogen were added, the temperature was raised to 70°C, the reaction was carried out for 1 hour, the temperature was lowered to room temperature, the pressure was released, and a polymer was obtained.

[0072] The polymerization results are shown in Table 1.

[0073] Example 2

[0074] This embodiment provides a catalyst, and the preparation method thereof is as follows:

[0075] Under anhydrous and oxygen-free conditions, 5.0 g of microspherical magnesium chloride alcoholate particles were added to 74 ml of titanium tetrachloride liquid at -20°C, reacted for 1 hour, and then gradually heated to 60°C; 0.0045 mol of [1-(1-amino-1-o-methoxyphenylmethyl)-2-oxopropyl]phosphonic acid diisopropyl ester was added, and the temperature was gradually raised to 120°C, reacted for 2 hours, washed 5 times at 60°C, and filtered with 30 ml of hexane at room temperature; 74 ml of titanium tetrachloride was added, reacted at 120°C for 1 hour and filtered. The catalyst was washed once with 100 ml of hexane and dried in vacuo to obtain the catalyst.

[0076] The obtained catalyst was used for bulk polymerization: 2 kg of propylene, triethylaluminum and methylcyclohexyldimethoxysilane were added to a 10-liter stainless steel reactor that had been vacuum dried and fully replaced with nitrogen and propylene gas, with the molar ratio of titanium to aluminum being 1:150 and the molar ratio of titanium to silicon being 1:20; 30 mg of the above catalyst and 0.3 g of hydrogen were added, the temperature was raised to 70°C, the reaction was carried out for 1 hour, the temperature was lowered to room temperature, the pressure was released, and a polymer was obtained.

[0077] The polymerization results are shown in Table 1.

[0078] Example 3

[0079] This embodiment provides a catalyst, and the preparation method thereof is as follows:

[0080] Under anhydrous and oxygen-free conditions, 5.0 g of microspherical magnesium chloride alcoholate particles were added to 74 ml of titanium tetrachloride liquid at -20°C, reacted for 1 hour, and then gradually heated to 70°C; 0.0025 mol of [1-(1-amino-1-phenylmethyl)-2-oxopropyl]phosphonic acid diisopropyl ester was added, and the temperature was gradually raised to 110°C, reacted for 2 hours, washed 5 times at 60°C, and filtered with 30 ml of hexane at room temperature; 74 ml of titanium tetrachloride was added, reacted at 110°C for 1 hour and filtered. The catalyst was washed once with 100 ml of hexane and dried in vacuo to obtain the catalyst.

[0081] The obtained catalyst was used for bulk polymerization: 2 kg of propylene, triethylaluminum and methylcyclohexyldimethoxysilane were added to a 10-liter stainless steel reactor that had been vacuum dried and fully replaced with nitrogen and propylene gas, with the molar ratio of titanium to aluminum being 1:200 and the molar ratio of titanium to silicon being 1:25; 30 mg of the above catalyst and 0.2 g of hydrogen were added, the temperature was raised to 70°C, the reaction was carried out for 1 hour, the temperature was lowered to room temperature, the pressure was released, and a polymer was obtained.

[0082] The polymerization results are shown in Table 1.

[0083] Example 4

[0084] This embodiment provides a catalyst, and the preparation method thereof is as follows:

[0085] Under anhydrous and oxygen-free conditions, 5.0 g of microspherical magnesium chloride alcoholate particles were added to 147 ml of titanium tetrachloride liquid at -20°C, reacted for 1 hour, and then gradually heated to 40°C; 0.0037 mol of [1-(1-amino-1-isopropylmethyl)-2-oxopropyl] diphenyl phosphonate was added, and the temperature was gradually raised to 130°C, reacted for 2 hours, washed 5 times at 60°C, and filtered with 30 ml of hexane at room temperature; 74 ml of titanium tetrachloride was added, reacted at 130°C for 2 hours and filtered. The catalyst was washed once with 100 ml of hexane and dried in vacuo to obtain the catalyst.

[0086] The obtained catalyst was used for bulk polymerization: 2 kg of propylene, triethylaluminum and methylcyclohexyldimethoxysilane were added to a 10-liter stainless steel reactor that had been vacuum dried and fully replaced with nitrogen and propylene gas, with the molar ratio of titanium to aluminum being 1:200 and the molar ratio of titanium to silicon being 1:20; 30 mg of the above catalyst and 0.2 g of hydrogen were added, the temperature was raised to 70°C, the reaction was carried out for 1 hour, the temperature was lowered to room temperature, the pressure was released, and a polymer was obtained.

[0087] The polymerization results are shown in Table 1.

[0088] Example 5

[0089] This embodiment provides a catalyst, and the preparation method thereof is as follows:

[0090] Under anhydrous and oxygen-free conditions, 5.0 g of microspherical magnesium chloride alcoholate particles were added to 147 ml of titanium tetrachloride liquid at -20°C, reacted for 1 hour, and then gradually heated to 70°C; 0.0032 mol of [1-(1-amino-1-phenylmethyl)-2-oxopropyl] diphenyl phosphonate was added, and the temperature was gradually raised to 110°C, reacted for 3 hours, washed 5 times at 60°C, and filtered with 30 ml of hexane at room temperature; 147 ml of titanium tetrachloride was added, reacted at 110°C for 1 hour and filtered. The catalyst was washed once with 100 ml of hexane and dried in vacuo to obtain the catalyst.

[0091] The obtained catalyst was used for bulk polymerization: 2 kg of propylene, triethylaluminum and methylcyclohexyldimethoxysilane were added to a 10-liter stainless steel reactor that had been vacuum dried and fully replaced with nitrogen and propylene gas, with the molar ratio of titanium to aluminum being 1:300 and the molar ratio of titanium to silicon being 1:25; 30 mg of the above catalyst and 0.2 g of hydrogen were added, the temperature was raised to 70°C, the reaction was carried out for 1 hour, the temperature was lowered to room temperature, the pressure was released, and a polymer was obtained.

[0092] The polymerization results are shown in Table 1.

[0093] Example 6

[0094] This embodiment provides a catalyst, and the preparation method thereof is as follows:

[0095] Under anhydrous and oxygen-free conditions, 5.0 g of microspherical magnesium chloride alcoholate particles were added to 123 ml of titanium tetrachloride liquid at -20°C, reacted for 1 hour, and then gradually heated to 80°C; 0.0028 mol of [1-(1-amino-1-naphthylmethyl)-2-oxopropyl] diphenyl phosphonate was added, and the temperature was gradually raised to 120°C, reacted for 2 hours, washed 5 times at 60°C, and filtered with 30 ml of hexane at room temperature; 123 ml of titanium tetrachloride was added, reacted at 120°C for 1 hour and filtered. The catalyst was washed once with 100 ml of hexane and dried in vacuo to obtain the catalyst.

[0096] The obtained catalyst was used for bulk polymerization: 2 kg of propylene, triethylaluminum and methylcyclohexyldimethoxysilane were added to a 10-liter stainless steel reactor that had been vacuum dried and fully replaced with nitrogen and propylene gas, with the molar ratio of titanium to aluminum being 1:200 and the molar ratio of titanium to silicon being 1:10; 30 mg of the above catalyst and 0.3 g of hydrogen were added, the temperature was raised to 70°C, the reaction was carried out for 1 hour, the temperature was lowered to room temperature, the pressure was released, and a polymer was obtained.

[0097] The polymerization results are shown in Table 1.

[0098] Example 7

[0099] This embodiment provides a catalyst, and the preparation method thereof is as follows:

[0100] Under anhydrous and oxygen-free conditions, 5.0 g of microspherical magnesium chloride alcoholate particles were added to 98 ml of titanium tetrachloride liquid at -20°C, reacted for 1 hour, and then gradually heated to 60°C; 0.0037 mol of [1-(1-amino-1-isopropylmethyl)-2-oxopropyl]phosphonic acid di(2-methoxyphenyl) ester was added, and the temperature was gradually raised to 120°C, reacted for 2 hours, washed 5 times at 60°C, and filtered with 30 ml of hexane at room temperature; 98 ml of titanium tetrachloride was added, reacted at 120°C for 1 hour and filtered. The catalyst was washed once with 100 ml of hexane and dried in vacuo to obtain the catalyst.

[0101] The obtained catalyst was used for bulk polymerization: 2 kg of propylene, triethylaluminum and methylcyclohexyldimethoxysilane were added to a 10-liter stainless steel reactor that had been vacuum dried and fully replaced with nitrogen and propylene gas, with the molar ratio of titanium to aluminum being 1:200 and the molar ratio of titanium to silicon being 1:15; 30 mg of the above catalyst and 0.3 g of hydrogen were added, the temperature was raised to 70°C, the reaction was carried out for 1 hour, the temperature was lowered to room temperature, the pressure was released, and a polymer was obtained.

[0102] The polymerization results are shown in Table 1.

[0103] Example 8

[0104] This embodiment provides a catalyst, and the preparation method thereof is as follows:

[0105] Under anhydrous and oxygen-free conditions, 5.0 g of microspherical magnesium chloride alcoholate particles were added to 123 ml of titanium tetrachloride liquid at -20°C, reacted for 1 hour, and then gradually heated to 50°C; 0.0028 mol of [1-(1-amino-1-p-tolylmethyl)-2-oxopropyl]phosphonic acid di(2,4-diethoxyphenyl) ester was added, and the temperature was gradually raised to 110°C, reacted for 2 hours, washed 5 times at 60°C, and filtered with 30 ml of hexane at room temperature; 123 ml of titanium tetrachloride was added, reacted at 110°C for 2 hours and filtered. The catalyst was washed once with 100 ml of hexane and dried in vacuo to obtain the catalyst.

[0106] The obtained catalyst was used for bulk polymerization: 2 kg of propylene, triethylaluminum and methylcyclohexyldimethoxysilane were added to a 10-liter stainless steel reactor that had been vacuum dried and fully replaced with nitrogen and propylene gas, with the molar ratio of titanium to aluminum being 1:250 and the molar ratio of titanium to silicon being 1:20; 30 mg of the above catalyst and 0.3 g of hydrogen were added, the temperature was raised to 70°C, the reaction was carried out for 1 hour, the temperature was lowered to room temperature, the pressure was released, and a polymer was obtained.

[0107] The polymerization results are shown in Table 1.

[0108] Example 9

[0109] This embodiment provides a catalyst, and the preparation method thereof is as follows:

[0110] Under anhydrous and oxygen-free conditions, 5.0 g of microspherical magnesium chloride alcoholate particles were added to 98 ml of titanium tetrachloride liquid at -20°C, reacted for 1 hour, and then gradually heated to 60°C; 0.0022 mol of [1-(1-amino-1-tert-butylmethyl)-2-oxopropyl] dibenzyl phosphonate was added, and the temperature was gradually raised to 110°C, reacted for 2 hours, washed 5 times at 60°C, and filtered with 30 ml of hexane at room temperature; 98 ml of titanium tetrachloride was added, reacted at 110°C for 1 hour and filtered. The catalyst was washed once with 100 ml of hexane and dried in vacuo to obtain the catalyst.

[0111] The obtained catalyst was used for bulk polymerization: 2 kg of propylene, triethylaluminum and methylcyclohexyldimethoxysilane were added to a 10-liter stainless steel reactor that had been vacuum dried and fully replaced with nitrogen and propylene gas, with the molar ratio of titanium to aluminum being 1:200 and the molar ratio of titanium to silicon being 1:20; 30 mg of the above catalyst and 0.2 g of hydrogen were added, the temperature was raised to 70°C, the reaction was carried out for 1 hour, the temperature was lowered to room temperature, the pressure was released, and a polymer was obtained.

[0112] The polymerization results are shown in Table 1.

[0113] Comparative Example 1

[0114] This comparative example provides a catalyst, and its preparation method and propylene polymerization method are the same as those in Example 4, except that triphenyl phosphate (synthesis method reference CN1974612A) is used instead of [1-(1-amino-1-isopropylmethyl)-2-oxopropyl]phosphonic acid diphenyl ester during the catalyst preparation process.

[0115] The polymerization results are shown in Table 1.

[0116] Comparative Example 2

[0117] This comparative example provides a catalyst, and its preparation method and propylene polymerization method are the same as those in Example 7, except that a sulfonyl compound substituted with phenylphosphine (synthesis method reference CN101787088A) is used instead of [1-(1-amino-1-isopropylmethyl)-2-oxopropyl]phosphonic acid di(2-methoxyphenyl) ester during the catalyst preparation process.

[0118] The structure of the above-mentioned phenylphosphine-substituted sulfonyl compound is as follows:

[0119]

[0120] The polymerization results are shown in Table 1.

[0121] Comparative Example 3

[0122] This comparative example provides a catalyst, and its preparation method and propylene polymerization method are the same as Example 7, except that 2,3-diisopropylsuccinic acid diethyl ester is used instead of [1-(1-amino-1-isopropylmethyl)-2-oxopropyl]phosphonic acid di(2-methoxyphenyl) ester during the catalyst preparation process.

[0123] Comparative Example 4

[0124] This comparative example provides a catalyst, and its preparation method and propylene polymerization method are the same as those in Example 4, except that tetramethyl (6-methoxy-1,2,3,4-tetrahydroquinoline-2,4-disubstituted) bisphosphate (synthesis method reference CN108264589A) is used instead of [1-(1-amino-1-isopropylmethyl)-2-oxopropyl] diphenyl phosphonate during the catalyst preparation process.

[0125] The polymerization results are shown in Table 1.

[0126] Table 1 Catalyst propylene polymerization test results

[0127]

[0128]

[0129] The content percentages in Table 1 are calculated based on the mass of the obtained catalyst as 100%.

[0130] Example 10

[0131] The catalyst used in Example 7 was used to carry out propylene slurry polymerization: 3L hexane, 200g propylene, triethylaluminum and methylcyclohexyldimethoxysilane were added to a 5L stainless steel reactor that had been vacuum dried and fully replaced with nitrogen and propylene gas, with the molar ratio of titanium to aluminum being 1:200 and the molar ratio of titanium to silicon being 1:20; 30mg of the above catalyst and 0.2g of hydrogen were added, the temperature was raised to 70°C, the reaction was carried out for 1 hour, the temperature was lowered to room temperature, the pressure was released, the polymer was dried and weighed to calculate the catalyst activity.

[0132] The polymerization results are shown in Table 2.

[0133] Comparative Example 5

[0134] The catalyst provided in this comparative example is the same as that in comparative example 3, and the polymerization method is the same as that in example 10.

[0135] The polymerization results are shown in Table 2.

[0136] Table 2 Catalyst propylene slurry polymerization test results

[0137]

[0138]

[0139] As can be seen from Table 1, when the amino-substituted phosphonate compound is used as the catalyst of the internal electron donor for propylene polymerization, the activity is good, and the comprehensive performance of the obtained polypropylene is excellent, especially the molecular weight distribution, which can reach up to 13.5. At the same time, the polymer has good isotacticity, which is of great significance for the development of wide molecular weight distribution polypropylene with excellent performance.

Claims

1. A catalyst for olefin polymerization, comprising titanium, magnesium, halogen, and a phosphonate internal electron donor; in, The phosphonate internal electron donor has a structure shown in Formula I: In Formula I, R1 and R2 are the same or different and are independently selected from C1-C 20 Straight chain alkyl, C1-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkyl, C7-C 20 R3 is selected from hydrogen, C1-C 20 Straight chain alkyl, C1-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkyl, C7-C 20 an alkoxyaryl group, a saturated condensed ring structure, or an unsaturated condensed ring structure.

2. The catalyst according to claim 1, wherein The catalyst comprises an alcoholate of magnesium halide, a titanium compound and the phosphonate internal electron donor.

3. The catalyst according to claim 1 or 2, wherein In Formula I, R1 and R2 are selected from C3-C 10 Alkyl, C3-C 10 Cycloalkyl, C6-C 10 Aryl, C7-C 10 Alkyl, C7-C 10 R3 is selected from C3-C 10 Straight chain alkyl, C3-C 10 Branched alkyl, C3-C 10 Cycloalkyl, C6-C 10 Aryl, C7-C 10 Alkyl, C7-C 10 an alkoxyaryl group, a saturated condensed ring structure, or an unsaturated condensed ring structure.

4. The catalyst according to claim 1 or 2, wherein The phosphonate internal electron donor is selected from dimethyl (1-aminomethyl-2-oxopropyl)phosphonate, dimethyl [1-(1-aminoethyl)-2-oxopropyl]phosphonate, dimethyl [1-(1-aminopropyl)-2-oxopropyl]phosphonate, dimethyl [1-(1-amino-1-isopropylmethyl)-2-oxopropyl]phosphonate, dimethyl [1-(1-amino-1-tert-butylmethyl)-2-oxopropyl]phosphonate, dimethyl [1-(1-aminopentyl)-2-oxopropyl]phosphonate, dimethyl [1-(1-amino-n-hexyl)-2-oxopropyl]phosphonate, dimethyl [1-(1-amino-n-octyl)-2-oxopropyl]phosphonate, dimethyl [1-(1-amino-1-phenylmethyl)-2-oxopropyl]phosphonate, dimethyl phosphonate, dimethyl [1-(1-amino-1-p-tolylmethyl)-2-oxopropyl]phosphonate, dimethyl [1-(1-amino-1-o-tolylmethyl)-2-oxopropyl]phosphonate, dimethyl [1-(1-amino-1-p-ethylphenylmethyl)-2-oxopropyl]phosphonate, dimethyl [1-(1-amino-1-o-ethylphenylmethyl)-2-oxopropyl]phosphonate, dimethyl [1-(1-amino-1-p-methoxyphenylmethyl)-2-oxopropyl]phosphonate, dimethyl [1-(1-amino-1-o-methoxyphenylmethyl)-2-oxopropyl]phosphonate, dimethyl [1-(1-amino-1-naphthylmethyl)-2-oxopropyl]phosphonate, dimethyl [1-(1-amino-1-naphthylmethyl)-2-oxopropyl]phosphonate, dimethyl (1-aminomethyl-2-oxopropyl) diethyl phosphonate, diethyl [1-(1-aminoethyl)-2-oxopropyl]phosphonate, diethyl [1-(1-aminopropyl)-2-oxopropyl]phosphonate, diethyl [1-(1-amino-1-isopropylmethyl)-2-oxopropyl]phosphonate, diethyl [1-(1-amino-1-tert-butylmethyl)-2-oxopropyl]phosphonate, diethyl [1-(1-aminopentyl)-2-oxopropyl]phosphonate, diethyl [1-(1-amino-n-hexyl)-2-oxopropyl]phosphonate, diethyl [1-(1-amino-n-octyl)-2-oxopropyl]phosphonate, diethyl [1-(1-amino-1-phenylmethyl)-2-oxopropyl]phosphonate, [1-(1-amino-1-p-tolylmethyl)-2- [1-(1-amino-1-o-tolylmethyl)-2-oxopropyl]phosphonic acid diethyl ester, [1-(1-amino-1-p-methoxyphenylmethyl)-2-oxopropyl]phosphonic acid diethyl ester, [1-(1-amino-1-o-methoxyphenylmethyl)-2-oxopropyl]phosphonic acid diethyl ester, [1-(1-amino-1-naphthylmethyl)-2-oxopropyl]phosphonic acid diethyl ester, (1-aminomethyl-2-oxopropyl)phosphonic acid diisopropyl ester, [1-(1-aminoethyl)-2-oxopropyl]phosphonic acid diisopropyl ester, [1-(1-aminopropyl)-2-oxopropyl]phosphonic acid diisopropyl ester, [1-(1-amino-1-isopropylmethyl)-2-oxopropyl]phosphonic acid diisopropyl ester,[1-(1-aminopentyl)-2-oxopropyl]phosphonic acid diisopropyl ester, [1-(1-amino-1-phenylmethyl)-2-oxopropyl]phosphonic acid diisopropyl ester, [1-(1-amino-1-p-tolylmethyl)-2-oxopropyl]phosphonic acid diisopropyl ester, [1-(1-amino-1-o-methoxyphenylmethyl)-2-oxopropyl]phosphonic acid diisopropyl ester, [1-(1-amino-1-naphthylmethyl)-2-oxopropyl]phosphonic acid diisopropyl ester, [1-(1-aminoethyl)-2-oxopropyl]phosphonic acid diphenyl ester, [1-(1-amino-1-isopropylmethyl)-2-oxopropyl]phosphonic acid diphenyl ester, [1-(1-aminohexyl)-2-oxopropyl]phosphonic acid diphenyl ester, [1-(1 [1-(1-amino-1-p-tolylmethyl)-2-oxopropyl]phosphonic acid diphenyl ester, [1-(1-amino-1-p-methoxyphenylmethyl)-2-oxopropyl]phosphonic acid diphenyl ester, [1-(1-amino-1-naphthylmethyl)-2-oxopropyl]phosphonic acid diphenyl ester, (1-aminomethyl-2-oxopropyl)phosphonic acid dibenzyl ester, [1-(1-aminopropyl)-2-oxopropyl]phosphonic acid dibenzyl ester, [1-(1-aminopropyl)-2-oxopropyl]phosphonic acid dibenzyl ester, [1-(1-amino-1-isopropylmethyl)-2-oxopropyl]phosphonic acid dibenzyl ester, [1-(1-amino-1-tert-butylmethyl)-2-oxopropyl]phosphonic acid dibenzyl ester, [1-(1-amino-1-phenylmethyl)-2-oxopropyl]phosphonic acid dibenzyl ester, [1-(1-amino-1-tert-butylmethyl)-2-oxopropyl]phosphonic acid dibenzyl ester, [1-(1-amino-1-phenylmethyl)-2-oxopropyl]phosphonic acid dibenzyl ester )-2-oxopropyl]phosphonic acid dibenzyl ester, [1-(1-amino-1-p-methoxyphenylmethyl)-2-oxopropyl]phosphonic acid dibenzyl ester, [1-(1-amino-1-naphthylmethyl)-2-oxopropyl]phosphonic acid dibenzyl ester, [1-(1-aminoethyl)-2-oxopropyl]phosphonic acid di(4-isopropylphenyl) ester, [1-(1-amino-1-isopropylmethyl)-2-oxopropyl]phosphonic acid di(4-isopropylphenyl) ester, [1-(1-aminohexyl)-2-oxopropyl]phosphonic acid di(4-isopropylphenyl) ester, [1-(1-amino-1-phenylmethyl)-2-oxopropyl]phosphonic acid di(4-isopropylphenyl) ester, [1-(1-amino-1-p-tolylmethyl)-2 [1-(1-amino-1-p-methoxyphenylmethyl)-2-oxopropyl]phosphonic acid bis(4-isopropylphenyl) ester, [1-(1-amino-1-naphthylmethyl)-2-oxopropyl]phosphonic acid bis(4-isopropylphenyl) ester, [1-(1-amino-1-naphthylmethyl)-2-oxopropyl]phosphonic acid bis(4-isopropylphenyl) ester, [1-(1-aminoethyl)-2-oxopropyl]phosphonic acid bis(2-methoxyphenyl) ester, [1-(1-amino-1-isopropylmethyl)-2-oxopropyl]phosphonic acid bis(2-methoxyphenyl) ester, [1-(1-aminohexyl)-2-oxopropyl]phosphonic acid bis(2-methoxyphenyl) ester, [1-(1-amino-1-phenylmethyl)-2-oxopropyl]phosphonic acid bis(2-methoxyphenyl) ester,[1-(1-amino-1-p-tolylmethyl)-2-oxopropyl]phosphonic acid bis(2-methoxyphenyl) ester, [1-(1-amino-1-o-methoxyphenylmethyl)-2-oxopropyl]phosphonic acid bis(2-methoxyphenyl) ester, [1-(1-amino-1-naphthylmethyl)-2-oxopropyl]phosphonic acid bis(2-methoxyphenyl) ester, [1-(1-aminoethyl)-2-oxopropyl]phosphonic acid bis(2,4-diethoxyphenyl) ester, [1-(1-amino-1-isopropylmethyl)-2-oxopropyl]phosphonic acid bis(2,4-diethoxyphenyl) ester, [1-(1-aminohexyl)-2-oxopropyl]phosphonic acid bis(2,4-diethoxyphenyl) ester )-2-oxopropyl]phosphonic acid bis(2,4-diethoxyphenyl) ester, [1-(1-amino-1-phenylmethyl)-2-oxopropyl]phosphonic acid bis(2,4-diethoxyphenyl) ester, [1-(1-amino-1-p-tolylmethyl)-2-oxopropyl]phosphonic acid bis(2,4-diethoxyphenyl) ester, [1-(1-amino-1-o-methoxyphenylmethyl)-2-oxopropyl]phosphonic acid bis(2,4-diethoxyphenyl) ester, [1-(1-amino-1-naphthylmethyl)-2-oxopropyl]phosphonic acid bis(2,4-diethoxyphenyl) ester, or a combination of two or more thereof.

5. The catalyst according to claim 2, wherein In the alcoholate of magnesium halide, the magnesium halide is selected from one or a combination of two or more of magnesium chloride, magnesium bromide, chloromethoxymagnesium, and chloroethoxymagnesium, and the alcohol is selected from one or a combination of two or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, and isobutanol; Preferably, in the alcoholate of magnesium halide, the magnesium halide is magnesium chloride and the alcohol is ethanol.

6. The catalyst according to claim 2, wherein The general formula of the titanium compound is Ti(OR') n X (4－n) , R' is selected from C1-C 20 Alkyl, C6-C 20 Aryl, C7-C 20 Aralkyl, X is halogen, and n is an integer of 0≤n≤4.

7. The catalyst according to claim 6, wherein The titanium compound is selected from one or a combination of two or more of tetraethoxytitanium, tetrabutoxytitanium, chlorotrialkoxytitanium, dichlorodialkoxytitanium, trichloroalkoxytitanium, titanium tetrachloride, and titanium tetrabromide; Preferably, the titanium compound is titanium tetrachloride.

8. The catalyst according to claim 1 or 2, wherein Calculated based on 100% by mass of the catalyst, the composition of the catalyst comprises 6-20% of phosphonate internal electron donor, preferably 7-12% of phosphonate internal electron donor.

9. A method for preparing a catalyst according to any one of claims 1 to 8, comprising the following steps: (1) adding a magnesium halide alcoholate to a titanium compound at -50°C to 20°C, and reacting for 10 min to 6 h. In step (1), the molar ratio of magnesium to titanium is 1:5 to 1:100; (2) raising the temperature to 0° C. to 100° C., adding a phosphonate internal electron donor represented by formula I, wherein the molar ratio of magnesium to the phosphonate internal electron donor is 2:1-20:1; (3) heating to 100°C to 150°C and reacting for 0.5-6h; (4) After filtering, add the same amount of titanium compound as in step (1), and react at 100° C. to 130° C. for 0.5-6 h to obtain the catalyst.

10. The preparation method according to claim 9, wherein: The preparation method comprises the following steps: (1) adding a magnesium halide alcoholate to a titanium compound liquid at -30°C to 0°C, and reacting for 1-4 hours. In step (1), the molar ratio of magnesium to titanium is 1:20-1:60; (2) raising the temperature to 30° C.-60° C., adding a phosphonate internal electron donor represented by formula I, wherein the molar ratio of magnesium to the phosphonate internal electron donor is 2:1-12:1; (3) heating to 110°C to 130°C and reacting for 1-4 hours; (4) After filtering, add the same amount of titanium compound liquid as in step (1), react at 110° C.-130° C. for 1-2 hours, and obtain the catalyst after filtering, washing and drying.

11. A catalyst system for olefin polymerization, comprising the catalyst according to any one of claims 1 to 8, an alkyl aluminum compound, and an alkoxysilane compound.

12. The catalyst system according to claim 11, wherein The general formula of the alkyl aluminum compound is AlR" m Y (3-m) , R" is selected from C1-C 20 Alkyl, C6-C 20 Aryl, C7-C 20 wherein Y is a halogen, and m is an integer of 0≤m≤3.

13. The catalyst system according to claim 12, wherein The alkyl aluminum compound is selected from one or a combination of two or more of trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, diethyl aluminum monochloride, and diisobutyl aluminum monochloride; Preferably, the alkylaluminum compound is triethylaluminum and / or triisobutylaluminum.

14. The catalyst system according to claim 11, wherein The alkoxysilane compound is selected from one or a combination of two or more of dimethoxydimethylsilane, diethoxydimethylsilane, dimethoxydiphenylsilane, and methylcyclohexyldimethoxysilane; Preferably, the alkoxysilane compound is methylcyclohexyldimethoxysilane.

15. The catalyst system according to claim 11, wherein The molar ratio of titanium to aluminum in the catalyst system is 1:1-1:2000; the molar ratio of titanium to silicon is 1:1-1:

50.

16. The catalyst system according to claim 15, wherein The molar ratio of titanium to aluminum in the catalyst system is 1:1-1:500; the molar ratio of titanium to silicon is 1:1-1:

20.

17. Use of the catalyst according to any one of claims 1 to 8 or the catalyst system according to any one of claims 11 to 16 in olefin polymerization.

18. The use according to claim 17, wherein: The olefin polymerization is propylene polymerization, preferably bulk polymerization or slurry polymerization of propylene.

19. The use according to claim 18, wherein: The polymerization temperature is 0°C to 80°C.

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