Internal electron donor compound and preparation method and application thereof

Abstract

The invention discloses an internal electron donor compound which has a structure as shown in a formula I. A catalyst containing the internal electron donor compound can be used for preparing a catalyst with high polymerization reaction activity and excellent stereospecificity. Compared with diacetic acid-1, 8-naphthol ester prepared from naphthalene diphenol, the compound prepared from naphthalene dimethanol is more stable in structure, high in polymerization activity and higher in polymer isotacticity.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of organic synthesis, in particular to an internal electron donor compound and a preparation method and application thereof. BACKGROUND

[0002] Polypropylene (PP) as one of the general-purpose plastics which have an increasing impact, is widely used in industrial products, daily necessities, packaging films, coatings and other fields due to its excellent rigidity, high heat distortion temperature, easy molding processing, electrical insulation and excellent folding resistance. With the rapid development of the plastics industry, the demand for polypropylene is also rapidly increasing, and the development of propylene polymerization catalyst technology is the key to the development of the polypropylene industry. At present, there are four kinds of catalysts for producing polypropylene: the earliest and most widely used Ziegler-Natta (hereinafter referred to as Z-N) catalyst, metallocene catalyst, non-metallocene organic metal olefin polymerization catalyst, and alkyl-free metal compound catalyst. The fourth generation Ziegler-Natta catalyst system is still the main catalyst used in the polypropylene industry, which is generally composed of a main catalyst TiCl4 / internal electron donor / MgCl2, a cocatalyst and an external electron donor. The main role of the internal electron donor is to improve the stereoselectivity (isotacticity of the polymer) of the MgCl2 support catalyst by affecting the microcrystalline structure and morphology of the MgCl2 support, and it also has an important influence on controlling the Ti loading and Ti distribution of the support catalyst.

[0003] Many compounds such as mono- or poly-carboxylic acid esters, mono- or poly-ethers, acid anhydrides, ketones, etc. are used as internal electron donors to synthesize Ziegler-Natta catalysts. Patent documents US4522930, EP0045975, EP0086644, CN1306544, etc. respectively involve a class of malonic acid ester compounds, and the research results show that the activity and isotacticity of the diethyl malonate catalyst increase with the increase of the 2-position substituent. Patent documents EP0125911, CN1306544, etc. respectively report a class of glutaric acid ester compounds, and the results show that the catalyst activity and polypropylene isotacticity are related to the β-position substituent. Patent document CN1240729C involves a succinic acid ester internal electron donor; patent document CN100415778C reports a maleic acid ester compound, which can prepare transparent isotactic polypropylene; patent document EP0728724 involves a series of diether internal electron donors, which greatly improves the catalyst activity and polypropylene isotacticity; patent document US8404789 reports a sulfonamide compound as an internal electron donor. Patent documents CN104250321B, CN1328293C, CN03140565.7, CN112175119B disclose a class of benzoic acid ester electron donor compounds.

[0004] Currently, the fourth generation Z-N polypropylene catalyst most widely used in industrial production uses phthalate compounds (such as US6365685, US2001020073, etc.) as internal electron donors. However, phthalate compounds, as plasticizer substances, have a similar effect on female hormones in the human and animal bodies, interfere with the endocrine system, and affect human health. Therefore, the development of new internal electron donors that are not phthalate compounds is of great significance to the future polypropylene industry. SUMMARY

[0005] In view of this, the present application provides an internal electron donor compound and a preparation method and application thereof to overcome the problems of existing phthalate internal electron donors for olefin polymerization catalysts affecting human health and the like.

[0006] To achieve the above-mentioned purpose, the present application provides an internal electron donor compound having the structure shown in Formula I:

[0007]

[0008] wherein R1, R8 are each independently selected from C1-C12 straight-chain or branched alkyl, C3-C8 cycloalkyl, C6-C15 substituted or unsubstituted aryl, or C6-C15 aralkyl;

[0009] R2, R3, R4, R5, R6, R7 are each independently selected from H, halogen, C1-C12 straight-chain or branched alkyl, C3-C8 cycloalkyl, C6-C15 aryl or aralkyl, and any two adjacent groups among R2-R7 are optionally bonded to form a ring.

[0010] In an alternative embodiment, R1, R8 are each independently selected from C1-C8 straight-chain or branched alkyl, C5-C8 cycloalkyl, C6-C10 substituted or unsubstituted aryl, C6-C10 aralkyl;

[0011] R2, R3, R4, R5, R6, R7 are each independently selected from H, halogen, C1-C5 straight-chain or branched alkyl, C5-C8 cycloalkyl, or C6-C15 aryl or aralkyl.

[0012] In an alternative embodiment, R1, R8 are each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-heptane, isohexane, n-octane, isooctane, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, phenyl, p-tolyl, o-tolyl, or benzyl;

[0013] R2, R3, R4, R5, R6, R7are each independently selected from H, F, Cl, Br, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, n-pentyl, iso-pentyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, phenyl, or benzyl.

[0014] In an alternative embodiment, the internal electron donor compound is selected from naphthalene-1,8-di(bismethylene)dipropionate, naphthalene-1,8-di(bismethylene)diacetate, naphthalene-1,8-di(bismethylene)diformate, naphthalene-1,8-di(bismethylene)dibisopropionate, naphthalene-1,8-di(bismethylene)dibutyrate, naphthalene-1,8-di(bismethylene)diisobutyrate, naphthalene-1,8-di(bismethylene)dipentylate, naphthalene-1,8-di(bismethylene)dicyclopentylate, naphthalene-1,8-di(bismethylene)dihexylate, naphthalene-1,8-di(bismethylene)dicyclohexylate, naphthalene-1,8-di(bismethylene)diisooctylate, naphthalene-1,8-di(bismethylene)dibenzoate, naphthalene-1,8-di(bismethylene)di-phenylacetyl, naphthalene-1,8-di(bismethylene)di-p-toluylate, or naphthalene-1,8-di(bismethylene)di-o-toluylate.

[0015] The present application also provides a preparation method of the internal electron donor compound as described above, comprising the following steps:

[0016]

[0017] The 1,8-naphthalene dimethanol compound shown in formula II is subjected to esterification reaction with acyl chloride shown in formula III to obtain the internal electron donor compound shown in formula I;

[0018] wherein, R1, R8, R2, R3, R4, R5, R6, R7are defined as above, and X is halogen.

[0019] For or a mixture thereof.

[0020] The above reaction is a conventional esterification reaction of alcohol and acyl chloride to prepare ester. Specifically, 1,8-naphthalene dimethanol is used as the reaction substrate to react with corresponding acyl chloride and triethylamine, the feeding ratio is 1:1:1-1:20:50, preferably 1:1:1-1:5:10, DCM (dichloromethane) is used as the solvent, the reaction system is kept water-free, the reaction temperature is 10-50°C, preferably 20-30°C, and the reaction time is 18-20h, preferably 20-24h. After the reaction is completed, the product is obtained by washing, filtering and separating, and vacuum drying, and the yield is generally 70%-99%.

[0021] The application also provides an olefin polymerization catalyst solid component, comprising a magnesium-containing carrier, a titanium-containing compound supported on the magnesium-containing carrier, and an internal electron donor compound.

[0022] The internal electron donor compound is selected from the internal electron donor compounds described above.

[0023] In an alternative embodiment, the magnesium-containing carrier is a magnesium halide alcoholate, the general formula of which is Mg(OR') 2-m X m The titanium-containing compound has a general formula of Ti(OR''') 4-y X y ;

[0024] wherein R' is selected from C1-C20 alkyl, X is halogen, m is 0, 1 or 2, n is a decimal or integer of 0

[0025] In an alternative embodiment, X is selected from chlorine, bromine, or fluorine; R', R'', R''' are each independently selected from methyl, ethyl, propyl, isopropyl, butyl or isobutyl;

[0026] Preferably, the magnesium halide in the magnesium halide alcoholate is selected from magnesium chloride, magnesium bromide, chloromethoxymagnesium or chloroethoxymagnesium, and the alcoholate in the magnesium halide alcoholate is selected from methanol, ethanol, propanol, isopropanol, butanol or isobutanol;

[0027] The titanium-containing compound is selected from titanium tetraethoxide, titanium tetrabutoxide, chlorotrialkoxy titanium, dichlorodialkoxy titanium, trichloroalkoxy titanium, titanium tetrachloride or titanium tetrabromide.

[0028] The application also provides a preparation method of the above-mentioned olefin polymerization catalyst solid component, comprising the following steps:

[0029] S1: reacting the magnesium-containing carrier with the titanium-containing compound at -40-0 ℃ for 0.1-3 h, then increasing the temperature to 40-100 ℃, adding the internal electron donor compound and reacting for 0.5-3 h, and then separating to obtain a solid product;

[0030] S2: reacting the solid product with the titanium-containing compound at 80-140 ℃ for 0.1-3 h, then washing and drying to obtain the olefin polymerization catalyst solid component;

[0031] The total amount of the titanium-containing compound is calculated based on Ti, and the amount of the magnesium-containing carrier is calculated based on Mg, and the Ti / Mg molar ratio is 1-200.

[0032] In an alternative embodiment, the process further comprises the step of adding the solid product obtained in step S1 to a titanium-containing compound at a temperature of 80-140°C, and separating the solid product after 0.5-3 hours of reaction; and the step can be repeated 1-3 times.

[0033] In an alternative embodiment, the titanium-containing compound is selected from titanium tetrahalides.

[0034] In an alternative embodiment, the process for preparing the solid component of the olefin polymerization catalyst comprises the steps of:

[0035] S1: reacting the magnesium-containing support with a titanium-containing compound at a temperature of -40-0°C for 0.1-3 hours, and then raising the temperature to 40-100°C and adding an internal electron donor compound and reacting for 0.5-3 hours;

[0036] S2: adding a titanium-containing compound at a temperature of 80-140°C, and separating the solid product after 0.5-3 hours of reaction; and the step can be repeated 1-3 times.

[0037] S3: reacting the solid product with a titanium-containing compound at a temperature of 80-140°C for 0.1-3 hours, and then washing and drying to obtain the solid component of the olefin polymerization catalyst.

[0038] The present application also provides an olefin polymerization catalyst comprising the solid component of the olefin polymerization catalyst, a cocatalyst, and an external electron donor.

[0039] The solid component of the olefin polymerization catalyst is selected from the solid component of the olefin polymerization catalyst described above or the solid component of the olefin polymerization catalyst prepared by the process described above.

[0040] In an alternative embodiment, the cocatalyst is selected from alkyl aluminum compounds having the general formula AlR p X( 3-p ), wherein R is selected from C1-C20 alkyl, C6-C20 aralkyl, or C6-C20 aryl; X is halogen (F, Cl, Br, or I), and p is 0, 1, 2, or 3; and R is selected from methyl, ethyl, isopropyl, propyl, butyl, t-butyl, pentyl, isopentyl, hexyl, phenyl, benzyl, and the like;

[0041] The external electron donor is selected from siloxane compounds having the general formula 'R a Si(O”R) 4-aR is C1-C10 alkyl, C3-C10 cycloalkyl, or C6-C10 aryl; "R is C1-C4 alkyl; a is 0, 1, 2, or 3. Preferably, 'R is selected from methyl, ethyl, isopropyl, propyl, butyl, t-butyl, pentyl, isopentyl, hexyl, phenyl, cyclohexyl, cyclopentyl, and the like; "R is selected from methyl, ethyl, isopropyl, propyl, butyl, or t-butyl, and the like.

[0042] In an alternative embodiment, the co-catalyst is selected from trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, diethylaluminum chloride, diisobutylaluminum chloride, or ethylaluminum dichloride, and the like;

[0043] The external donor is selected from dimethoxydimethylsilane, diethoxydimethylsilane, methylcyclohexyldimethoxysilane, dimethoxydiphenylsilane, phenyltrimethoxysilane, phenyltriethoxysilane, or diphenyldimethoxysilane, and the like.

[0044] In an alternative embodiment, the molar ratio of titanium in the solid component of the olefin polymerization catalyst to aluminum in the co-catalyst is from 1:1 to 1:2000, preferably from 1:5 to 1:500;

[0045] The molar ratio of Si in the external donor to Ti in the solid component of the olefin polymerization catalyst is from 1:1 to 1:100, preferably from 1:1 to 1:50.

[0046] The present application also provides the use of the above-mentioned olefin polymerization catalyst in olefin polymerization. Various methods in the prior art of olefin polymerization can be used, including but not limited to bulk polymerization, slurry polymerization, gas phase polymerization, and the like. Taking propylene bulk polymerization as an example, the basic use process of the olefin polymerization catalyst is briefly described as follows: the polymerization reactor is sufficiently replaced with nitrogen and vacuum dried, propylene monomer is added, and the solid component of the olefin polymerization catalyst, the co-catalyst alkylaluminum, and the external donor alkoxysilane are added in a certain ratio. The polymerization temperature is from 20 to 90°C, preferably from 60 to 80°C. The polymerization reaction is carried out for 1 to 2 hours, the reactor is vented and sufficiently replaced with nitrogen, and the dry polymer is obtained.

[0047] Compared with the prior art, the present application has at least the following advantages:

[0048] The internal electron donor compound provided by the present application is a naphthalene-1,8-di(methylene)diester compound, the structure of which is more rigid, more planar, and a larger delocalized system can better control the performance of the electron donor. When used for olefin polymerization, especially propylene polymerization, it significantly improves the isotacticity of polypropylene and the catalytic activity of the catalyst, obtains a catalyst with high polymerization reactivity and excellent stereospecificity, and can achieve the same effect as phthalate internal electron donor compounds (replace phthalate) without interfering with the endocrine system and affecting human health. DETAILED DESCRIPTION

[0049] The present application will be described in detail below by examples. It is necessary to point out here that the following examples are only used to further illustrate the present application and cannot be understood as limiting the scope of protection of the present application, and those skilled in the art can make some non-essential improvements and adjustments to the present application according to the above content of the present application.

[0050] If the specific experimental steps or conditions are not specified in the examples, they can be carried out according to the conventional experimental steps described in the literature in the art or the operation or conditions. If the reagents or instruments used are not specified by the manufacturer, they are all conventional reagent products that can be obtained by purchase.

[0051] Example 1

[0052] The present embodiment provides an internal electron donor compound, the structural formula of which is as follows, and the preparation method specifically includes the following steps:

[0053] Naphthalene-1,8-di(methylene) dipropionic acid ester

[0054]

[0055] Under anhydrous and anaerobic conditions, 1,8-naphthalene dimethanol 0.96 g (5.11 mmol), about 2 mL (14.42 mmol) of triethylamine, and about 20 mL of anhydrous dichloromethane were added to a 50 mL flask. Stir at room temperature, slowly add 1.5 ml of propionyl chloride (17.12 mmol) dropwise into the flask, and during the dropping process, the solution gradually changes from white suspension to pink suspension. As the reaction proceeds, the solution becomes a yellow suspension. After 24 h of reaction, TLC (petroleum ether: ethyl acetate = 10:1) confirms that the reaction is complete, then 20 mL of water is added, stirred until the system is no longer exothermic, then NaOH solution is added to adjust the pH value to about 12, and then the layers are separated by standing. The obtained organic phase is washed with water twice, then dried with anhydrous sodium sulfate, and then filtered under suction to obtain a yellow filtrate. The volatile solvent is removed by a rotary evaporator to obtain a light yellow solid (i.e. naphthalene-1,8-di(methylene) dipropionic acid ester), with a yield of 93%, and a MP of 57-58℃.

[0056] 1 H NMR (400 MHz, CDC13) δ 7.93 (d, J = 8.0 Hz, 2H), 7.70 (d, J = 6.9 Hz, 2H), 7.50 (t, J = 7.6 Hz, 2H), 5.68 (s, 4H), 2.40 (q, J = 7.5 Hz, 4H), 1.29 - 1.05 (m, 6H).

[0057] 13 C NMR (101 MHz, CDC13) δ 173.96, 135.60, 131.80, 125.54, 66.36, 27.56, 9.06.

[0058] Example 2

[0059] This example provides an internal electron donor compound, the structural formula of which is as follows, and the preparation method specifically includes the following steps:

[0060] Naphthalene-1,8-di(methylene)dibenzoate

[0061]

[0062] Under anhydrous and anaerobic conditions, 1,8-naphthalene dimethanol 0.96 g (5.11 mmol) and triethylamine about 2 mL (14.42 mmol) were added into a 50 mL flask, and anhydrous dichloromethane about 20 mL was added. Stirring at room temperature, benzoyl chloride 1.5 ml (13.03 mmol) was slowly added dropwise into the flask, and the solution changed from white suspension to yellow suspension as the reaction proceeded. After 24 h of reaction, TLC (PE:EA = 10:1) confirmed that the reaction was complete, 20 ml of water was added, and after stirring until the system was no longer exothermic, NaOH solution was added to adjust the pH value to about 12, and then the layers were separated after standing. The obtained organic phase was washed with water twice, dried with anhydrous sodium sulfate, and then filtered under suction to obtain a yellow filtrate. The volatile solvent was removed by a rotary evaporator to obtain a yellow solid (i.e. naphthalene-1,8-di(methylene)dibenzoate), with a yield of 76%, and MP: 96-98°C.

[0063] 1 H NMR (400 MHz, CDC13) δ 7.93 (d, J = 8.0 Hz, 2H), 7.70 (d, J = 6.9 Hz, 2H), 7.50 (t, J = 7.6 Hz, 2H), 5.68 (s, 4H), 2.40 (q, J = 7.5 Hz, 4H), 1.29 - 1.05 (m, 6H).

[0064] 13C NMR (101 MHz, CDC13) δ 166.13, 135.72, 135.72, 133.13, 132.52, 131.49, 131.14, 130.08, 129.76, 128.45, 125.37, 67.25.

[0065] Example 3

[0066] The present example provides an internal electron donor compound, whose structural formula is as follows, and the preparation method specifically comprises the following steps:

[0067] Naphthalene-1,8-di(methylene)bis(4-methylbenzoate)

[0068]

[0069] Under anhydrous and anaerobic conditions, 1,8-naphthalene dimethanol 0.96 g (5.11 mmol) and triethylamine about 2 mL (14.42 mmol) were added into a 50 mL flask, and anhydrous dichloromethane about 20 mL was added. Stirring at room temperature, 1.5 ml of p-toluyl chloride (11.3 mmol) was added dropwise into the flask, and the solution changed from white suspension to light yellow suspension as the reaction proceeded. After 24 h of reaction, TLC (PE:EA=10:1 ) confirmed that the reaction was complete, 20 ml of water was added, and after stirring until the system was no longer exothermic, NaOH solution was added to adjust the pH value to about 12, and then the layers were separated after standing. The obtained organic phase was washed with water twice, dried with anhydrous sodium sulfate, and then filtered to obtain a yellow filtrate. The volatile solvent was removed by a rotary evaporator to obtain a white solid (naphthalene-1,8-di(methylene)bis(4-methylbenzoate)), with a yield of 61 %, and MP: 96-97 °C.

[0070] 1 H NMR (400 MHz, CDC13) δ 8.09 - 7.91 (m, 6H), 7.83 (d, J = 6.5 Hz, 2H), 7.62 - 7.47 (m, 2H), 7.23 (t, J = 9.3 Hz, 4H), 6.03 (s, 4H), 2.56 - 2.30 (m, 6H).

[0071] 13 C NMR (101 MHz, CDC13) δ 166.13, 135.72, 135.72, 133.13, 132.52, 131.49, 131.14, 130.08, 129.76, 128.45, 125.37, 67.25.

[0072] Example 4

[0073] The present embodiment provides an internal electron donor compound, the structural formula of which is as follows, and the preparation method specifically comprises the following steps:

[0074] Naphthalene-1,8-di(methylene)diacetate

[0075]

[0076] Under anhydrous and anaerobic conditions, 1,8-naphthalene dimethanol 0.96 g (5.11 mmol) and triethylamine about 2 mL (14.42 mmol) were added into a 50 mL flask, and about 20 mL of anhydrous dichloromethane was added. Stirring at room temperature, 1.5 ml of acetyl chloride (14.06 mmol) was slowly added dropwise into the flask, and the color of the solution changed from white to pink, and the solution changed from pink suspension to light yellow suspension as the reaction proceeded. After 24 h of reaction, TLC (PE:EA = 10:1) confirmed that the reaction was complete, 20 ml of water was added, and after stirring until the system was no longer exothermic, NaOH solution was added to adjust the pH value to about 12, and then the layers were separated after standing. The obtained organic phase was washed with water twice, dried over anhydrous sodium sulfate, and then filtered under suction to obtain a yellow filtrate. The volatile solvent was removed by a rotary evaporator to obtain a yellow solid (naphthalene-1,8-di(methylene)diacetate), with a yield of 98%, and a MP of 50-58°C.

[0077] 1 H NMR (400 MHz, DMSO) δ 8.03 (dd, J = 8.2, 1.2 Hz, 2H), 7.70 (dd, J = 7.1, 1.1 Hz, 2H), 7.63-7.42 (m, 2H), 5.56 (s, 4H), 2.08 (s, 6H).

[0078] 13 C NMR (101 MHz, CDCl3) δ 170.55, 135.61, 132.25, 131.26, 131.00, 125.27, 66.78, 21.18.

[0079] Example 5

[0080] The present embodiment provides an internal electron donor compound, the structural formula of which is as follows, and the preparation method specifically comprises the following steps:

[0081] Naphthalene-1,8-di(methylene)bis(2-methylbenzoate)

[0082]

[0083] Anhydrous and oxygen free conditions, in a 50 mL flask was added 1,8- naphthalene dimethanol 0.98 g (5.21 mmol) and triethylamine about 2 mL (14.42 mmol) and added anhydrous dichloromethane about 20 mL. With stirring at room temperature, 1.5 ml of o-tolyl benzoyl chloride (11.34 mmol) was added dropwise to the flask, as the reaction proceeded, the solution changed from a white suspension to a light yellow suspension. After 24 h of reaction, TLC (PE:EA = 10:1) confirmed the reaction was complete, added 20 ml of water, stirred until the system was no longer exothermic, added NaOH solution, adjusted the pH to about 12, allowed to separate into layers, the resulting organic phase was washed twice with water, dried over anhydrous sodium sulfate, suction filtered to obtain a light yellow filtrate, removed the volatile solvent with a rotary evaporator to obtain a light yellow solid, recrystallized with ethyl acetate to obtain a white solid (naphthalene-1,8-di(methylene) bis(2-methylbenzoate)), yield 66%, MP: 90-92 °C.

[0084] 1 H NMR (400 MHz, CDC13) δ 7.95 (dd, J = 7.9, 2.0 Hz, 4H), 7.84 (d, J = 7.1 Hz, 2H), 7.55 (t, J = 7.6 Hz, 2H), 7.39 (t, J = 7.4 Hz, 2H), 7.22 (dd, J = 6.3, 2.8 Hz, 4H), 6.01 (d, J = 2.0 Hz, 4H), 2.61 (d, J = 1.6 Hz, 6H).

[0085] 13 C NMR (101 MHz, CDC13): δ 166.97 (s), 135.74 (s), 132.43 (s), 132.13 (s), 131.76 (s), 131.55 (s), 131.34 (s), 130.70 (s), 129.42 (s), 125.80 (s), 125.37 (s), 67.10 (s), 21.82 (s).

[0086] Example 6

[0087] This example provides an internal electron donor compound, the structural formula is as follows, the preparation method specifically includes the following steps:

[0088] Naphthalene-1,8-di(methylene) dicyclohexyl carboxylate

[0089]

[0090] Anhydrous and anaerobic conditions, in a 50 mL flask was added 1,8- naphthalene dimethanol 0.96 g (5.11 mmol) and triethylamine about 2 mL (14.42 mmol), and added anhydrous dichloromethane about 20 mL. Stirring at room temperature, slowly added 2 ml of cyclohexyl formyl chloride (14.95 mmol) dropwise into the flask, as the reaction proceeds, the solution from white suspension to orange suspension. After 24 h of reaction, TLC (PE: EA = 10: 1) to confirm the reaction is complete, added 20 ml of water, stirring until the system is no longer exothermic after adding NaOH solution, adjust the pH value of about 12, static stratification, the resulting organic phase with water washed twice, dried with anhydrous sodium sulfate, suction filtration to obtain orange filtrate, remove the volatile solvent with a rotary evaporator can be obtained orange solid, washed with 10 ml of methanol, there is white solid precipitation, suction filtration after drying, to obtain white solid (naphthalene-1,8-di (methylene) dicyclohexyl formate), yield 46%, MP: 52-54 °C.

[0091] 1 H NMR (400 MHz, CDCl3) δ 7.94 (t, J = 1.6 Hz, 2H), 7.68 (d, J = 1.9 Hz, 2H), 7.48 (dd, J = 20.5, 3.1 Hz, 2H), 5.63 (s, 4H), 2.26 (m, 2H) 2.06 - 1.01 (m, 20H).

[0092] 13 C NMR (101 MHz, CDCl3): δ 175.54 (s), 135.72 (s), 132.20 (s), 131.49 (s), 131.28 (s), 131.14 (s), 125.24 (s), 66.49 (s), 43.09 (s), 28.95 (s), 25.76 (s), 25.42 (s).

[0093] Example 7

[0094] The present embodiment provides a kind of internal electron donor compound, its structural formula is as follows, preparation method specifically includes the following steps:

[0095] Naphthalene-1,8-di (methylene) bisphenyl acetic ester

[0096]

[0097] Anhydrous and anaerobic conditions, in a 50 mL flask was added 1,8- naphthalene dimethanol 0.97 g (5.21 mmol) and triethylamine about 2 mL (14.42 mmol), and added anhydrous dichloromethane about 20 mL. Stirring at room temperature, 1.5 ml of benzene acyl chloride (11.34 mmol) was added dropwise into the flask, as the reaction proceeds, the solution from white suspension to orange suspension and then into a yellow clear solution. After 24 h of reaction, TLC (PE: EA = 10:1) confirmed the reaction was complete, added 20 ml water, stirred until the system is no longer exothermic, then added NaOH solution, adjust the pH value to about 12, and then the layers were separated, the resulting organic phase was washed with water twice, dried with anhydrous sodium sulfate, and then filtered to obtain an orange filtrate, which was evaporated to remove the volatile solvent to obtain an orange solid, which was washed with 10 ml of methanol, and then filtered and dried to obtain a white solid (naphthalene-1,8-di(methylene) bisphenylacetic acid ester), yield 42%, MP: 60-64 °C.

[0098] 1 H NMR (400 MHz, CDCl3) δ 7.93 (dt, J = 8.2, 4.0 Hz, 2H), 7.65 (dd, J = 9.2, 8.4 Hz, 2H), 7.52 - 7.43 (m, 2H), 7.34 - 7.13 (m, 10H), 5.58 (s, 4H), 3.66 (s, 4H).

[0099] 13 C NMR (101 MHz, CDCl3): δ 170.94 (s), 135.57 (s), 133.74 (s), 132.22 (s), 131.22 (s), 130.90 (s), 129.33 (s), 128.56 (s), 127.12 (s), 125.23 (s), 67.06 (s), 41.47 (s).

[0100] Example 8

[0101] The present example provides an internal electron donor compound, the structural formula is as follows, the preparation method specifically includes the following steps:

[0102] 4-chloro-1,8-naphthalene dimethanol

[0103] LiAlH48.12 g (213.68 mmol) was weighed into a 1 L three-necked round bottom flask, anhydrous diethyl ether 200 mL, anhydrous toluene 120 mL were added, 4-chloro-1,8-naphthalene dicarboxylic anhydride 23.43 g (101.00 mmol) was added slowly with stirring, gas was generated, after refluxing at 72 °C for 10 h, the solution was cooled to room temperature, 75 mL water was added slowly to quench the excess LiAlH4, a large amount of bubbles was generated and white solid was produced, after no bubbles were generated, 1 mol / L HCl was added to adjust the pH value of the solution to be acidic, and the solution was extracted with ethyl acetate three times. The combined organic phase was dried over anhydrous MgSO4, filtered to obtain a yellow filtrate, the obtained filtrate was removed of the volatile solvent by a rotary evaporator to obtain a light yellow solid, and the light yellow solid was recrystallized with ethyl acetate to obtain white solid product 4-chloro-1,8-naphthalene dimethanol.

[0104] Naphthalene 4-chloro-1,8-di(methylene)diacetate

[0105]

[0106] Under anhydrous and anaerobic conditions, 4-chloro-1,8-naphthalene dimethanol 1.14 g (5.11 mmol) and triethylamine about 2 mL (14.42 mmol) were added to a 50 mL flask, and anhydrous dichloromethane about 20 mL was added. Stirring at room temperature, 1.5 mL of acetyl chloride (14.06 mmol) was added slowly into the flask, the color of the solution changed from white to pink, and the solution changed from pink suspension to light yellow suspension as the reaction proceeded. After 24 h of reaction, TLC (PE:EA = 10:1) confirmed that the reaction was complete, 20 mL of water was added, and after stirring for a period of time, NaOH solution was added to adjust the pH value to about 12, and the solution was allowed to stand and separate into layers. The obtained organic phase was washed with water twice, dried with anhydrous sodium sulfate, and filtered to obtain a yellow filtrate. The volatile solvent was removed by a rotary evaporator to obtain a yellow solid (naphthalene 4-chloro-1,8-di(methylene)diacetate) with a yield of 63%, and MP: 63-65 °C.

[0107] 1 H NMR (400 MHz, CDCl3) δ 8.12 (d, 1H) 7.43 (t, 1H), 7.45 (d, 1H), 7.09 (d, 1H), 6.92 (d, 1H), 5.46 (s, 4H), 2.12 (s, 6H).

[0108] 13C NMR (101 MHz, CDC13): δ 170.24 (s), 131.9 (s), 130.84 (s), 130.62 (s), 128.82 (s), 128.30 (s), 126.43 (s), 122.76 (s), 121.3 (s), 66.53 (s), 20.7 (s).

[0109] Comparative Example 1

[0110] This comparative example provides an internal electron donor compound having the following structural formula, and the method of preparation specifically includes the following steps:

[0111] 1,8-Naphthalenediol diacetate

[0112]

[0113] Under anhydrous and anaerobic conditions, 1,8-naphthalenediol 0.99 g (6.19 mmol) and triethylamine about 2 mL (14.42 mmol) were added to a 50 mL flask, and anhydrous dichloromethane about 20 mL was added. Stirring at room temperature, 1.5 ml of propionyl chloride (17.12 mmol) was added dropwise into the flask, and as the reaction proceeded, the solution changed from a white suspension to a light yellow suspension and then to a light yellow clear solution. After 24 h of reaction, TLC (PE:EA = 10:1) confirmed that the reaction was complete, 20 ml of water was added, and after stirring for a period of time, NaOH solution was added to adjust the pH value to about 12, and then it was left to separate the layers. The obtained organic phase was washed with water twice, dried with anhydrous sodium sulfate, and filtered under suction to obtain a yellow filtrate. The volatile solvent was removed by a rotary evaporator to obtain a yellow solid, which was washed with 10 ml of methanol, and a white solid was precipitated. After suction filtration and drying, a white solid (1,8-naphthalenediol diacetate) was obtained, with a yield of 77%, and MP: 154-156 °C.

[0114] 1 H NMR (400 MHz, CDC13) δ 7.93 (d, J = 8.0 Hz, 2H), 7.70 (d, J = 6.9 Hz, 2H), 7.50 (t, J = 7.6 Hz, 2H), 2.40 (q, J = 7.5 Hz, 4H), 1.29 - 1.05 (m, 6H).

[0115] 13 C NMR (101 MHz, CDC13) δ 173.96, 135.60, 131.80, 125.54, 66.36, 27.56, 9.06.

[0116] Comparative Example 2

[0117] The present comparative example provides an internal electron donor compound, dibutyl phthalate, having the following structural formula, and the method of preparation specifically includes the following steps:

[0118]

[0119] Sulfuric acid (98%, 94 mmol, 5 mL) was added to a mixture of phthalic acid (80 mmol), butanol (180 mmol) and acetonitrile (162 mmol) at room temperature and stirred well, maintaining the temperature between 80-85 °C for 16 hours, then the reaction system was cooled. The reaction system was added to a 20% sodium carbonate solution (100 mL) and extracted with dichloromethane (50 mL x 2) and then washed with water (100 mL), the combined organic phase was dried with sodium sulfate and the combined organic phase was concentrated under reduced pressure. The product was purified on silica gel using ethyl acetate: petroleum ether (1 :9), yield 75%.

[0120] 1 H NMR (400 MHz, CDC13) 7.72-7.69 (m, 2H, ArH), 7.54-7.50 (m, 2H, ArH), 4.30 (t, J = 6.7 Hz, 4H, OCH2), 1.75-1.68 (m, 4H, CH2), 1.48-1.39 (m, 4H, CH2), 0.95 (t, J = 7.4 Hz, 6H, CH3).

[0121] 13 C NMR (101 MHz, CDC13) 167.6, 132.2, 130.8, 128.7, 65.4, 30.5, 19.1, 13.6.

[0122] Comparative Example 3

[0123] The present comparative example provides an internal electron donor compound, dibutyl phthalate, having the following structural formula, and the method of preparation specifically includes the following steps:

[0124]

[0125] Naphthalene-1,8-dicarboxylic acid (5 g, 25.25 mmol) was dissolved in aqueous sodium carbonate solution (6 g, 56.6 mmol in 50 mL), the solution was heated to 40 °C, then dimethyl sulfate (14.1 mL, 150 mmol) was added to the solution, and stirred for another 2 hours at 40 °C, the resulting mixture was filtered at room temperature, the resulting product was washed with water, and dried to obtain. Yield 81%.

[0126] 1H NMR (400 MHz, CDC13): δ 8.00 (dd, 4H), 7.56 (t, 2H), 3.89 (s, 6H).

[0127] 13 C NMR (101 MHz, CDC13) δ 169, 134.23, 132.29, 130, 129.78, 125.16, 51.9.

[0128] For the convenience of comparison, the following magnesium-containing carriers are all spherical MgCl2·2.65C2H5OH carriers, and the titanium-containing compounds are all TiCl4. The cocatalysts are all triethylaluminum, and the external electron donors are all methylcyclohexyldimethoxysilane.

[0129] The internal electron donors prepared in the above examples and comparative examples were used to prepare the solid components of olefin polymerization catalysts in the following manner, and the propylene polymerization experiments were carried out. The specific experimental results are shown in Table 1.

[0130] Preparation of the solid components of olefin polymerization catalysts:

[0131] At 66°C, 300 rpm mechanical stirring, 150 mmol MgCl2and 15 mL silicon oil were dissolved in 500 mmol ethanol, and then 40 mL silicon oil was added to the obtained mixture. The temperature was increased to 110°C, and the mixture was stirred for 2 hours. The reaction mixture was transferred to another reactor containing 700 mL n-hexane, and was continuously stirred at 400 rpm at 17°C for 50 minutes. The solvent was removed, and the solid product was washed with hexane. The solid product was dried under nitrogen blowing, and the temperature was gradually increased from 20°C to 50°C at a temperature increasing rate of 2°C / min to complete the thermal dealcoholization. The product (spherical MgCl22.65C2H5OH) was collected and stored in a glove box atmosphere for later use.

[0132] 7.8 grams of spherical MgCl2·2.65C2H5OH carrier was slowly added to a reaction bottle containing 250 mL TiCl4, which was pre-cooled to -30°C. The temperature was increased to 80°C, 5 mmol of internal electron donor was added, and the temperature was maintained for 30 minutes. The temperature was increased to 130°C, and the reaction was carried out for 2 hours. Filtration was performed, and 250 mL TiCl4was added again for reaction at 130°C for 2 hours. The solid component of olefin polymerization catalyst was obtained after washing with n-hexane for 6 times and vacuum drying. The Ti content in the solid component was determined by inductively coupled plasma emission spectroscopy using an “I.C.P optical spectrometer ARL Accuris”. The specific results are shown in the following table, and the specific test method is as follows:

[0133] A mixture of 0.1-0.3 g of solid catalyst component and 3 g of lithium metaborate / lithium tetraborate (mass ratio of lithium metaborate to lithium tetraborate 1:1) was weighed on a "fluxy" platinum crucible to prepare the sample. The crucible was placed on a weak Bunsen burner flame to perform the combustion step, and then inserted into a special device "Claisse Fluxy" to complete the combustion after adding a few drops of KI solution. The residue was collected with 5% v / v HNO3 solution and analyzed for titanium by ICP at a wavelength of 368.52 nm.

[0134] Propylene polymerization:

[0135] The polymerization reaction was carried out in a 2L stainless steel autoclave.

[0136] First, the polymerization reactor was vented to 0 gauge pressure, and the reactor was sufficiently replaced with high-purity nitrogen and vacuumed under heating conditions for 1 hour. After the reactor was cooled to room temperature, 0.1 MPa of high-purity hydrogen and 300 g of propylene were introduced into the reactor, and the reactor was stirred at a speed of 200 rpm. The catalyst hopper was protected by nitrogen, and 10 mg of an olefin polymerization catalyst solid component, 2 mL of triethylaluminum (2.4 mol / L), and 2.5 mL of methylcyclohexyldimethoxysilane (0.18 mol / L) were sequentially added to the reactor. After 0.5 h of pre-complexing, 300 g of propylene was added to the reactor, and the temperature was raised to 70°C for 1 hour. At the end of the reaction, the stirring was stopped, the temperature was lowered, the pressure was released, and the solid propylene polymer was discharged. The isotacticity was measured by a chemical solvent method (see GB / T 2412-1980 for details), and the specific results are shown in the following table.

[0137] Table 1

[0138]

[0139] As can be seen from the data in the above table, the catalyst containing the internal electron donor compound provided by the present application can obtain a catalyst with high polymerization activity and excellent stereospecificity. Compared to diacetate-1,8-naphthol prepared from naphthalenediol and the compound prepared from naphthalene glycol, the structure of the compound of the present application is more stable, has high polymerization activity, and has higher polymer isotacticity.

[0140] Of course, the present application can have other various embodiments and modifications, and those skilled in the art can make various corresponding changes and modifications according to the present application without departing from the spirit and essence of the present application, but these corresponding changes and modifications should all belong to the protection scope of the claims of the present application.

Claims

1. An internal electron donor compound, characterized by, having the structure of Formula I: wherein R1, R8are each independently selected from C1-C12 linear or branched alkyl, C3-C8 cycloalkyl, C6-C15 substituted or unsubstituted aryl, or C6-C15 aralkyl; R2, R3, R4, R5, R6, R7are each independently selected from H, halogen, C1-C12 linear or branched alkyl, C3-C8 cycloalkyl, C6-C15 aryl or aralkyl, and any two adjacent groups of R2-R7 are optionally bonded to form a ring.

2. The internal electron donor compound according to claim 1, wherein R1, R8are each independently selected from C1-C8 linear or branched alkyl, C5-C8 cycloalkyl, C6-C10 substituted or unsubstituted aryl, C6-C10 aralkyl; R2, R3, R4, R5, R6, R7are each independently selected from H, halogen, C1-C5 linear or branched alkyl, C5-C8 cycloalkyl, or C6-C15 aryl or aralkyl.

3. The internal electron donor compound according to claim 1 or 2, wherein R1, R8are each independently selected from methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, n-pentyl, i-pentyl, n-hexyl, i-hexyl, n-heptane, i-heptane, n-octane, i-octane, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, phenyl, p-tolyl, o-tolyl, or benzyl; R2, R3, R4, R5, R6, R7are each independently selected from H, F, Cl, Br, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, n-pentyl, i-pentyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, phenyl, or benzyl.

4. The internal electron donor compound according to claim 1, wherein The internal electron donor compound is selected from naphthalene-1,8-di(bismethylene)dipropionate, naphthalene-1,8-di(bismethylene)diacetate, naphthalene-1,8-di(bismethylene)diformate, naphthalene-1,8-di(bismethylene)dipropionate, naphthalene-1,8-di(bismethylene) dibutyrate, naphthalene-1,8-di(bismethylene)diisobutyrate, naphthalene-1,8-di(bismethylene)dipentanoate, naphthalene-1,8-di(bismethylene)dicyclopentanoate, naphthalene-1,8-di(bismethylene)dihexanoate, naphthalene-1,8-di(bismethylene)dicyclohexanoate, naphthalene-1,8-di(bismethylene)diisooctanoate, naphthalene-1,8-di(bismethylene)dibenzoate, naphthalene-1,8-di(bismethylene)di-phenylacetic acid, naphthalene-1,8-di(bismethylene)di-p-toluic acid, or naphthalene-1,8-di(bismethylene)di-o-toluic acid.

5. A process for the preparation of the internal electron donor compound according to any one of claims 1 to 4, characterized in that, comprising the steps of: esterifying a 1,8-naphthalene dimethanol compound of Formula II with an acid chloride of Formula III to obtain the internal electron donor compound of Formula I; wherein R1, R8, R2, R3, R4, R5, R6, R7are as defined in any one of claims 1-3, and X is halogen.

6. An olefin polymerization catalyst solid component characterized in that, comprising a magnesium-containing support, a titanium-containing compound supported on the magnesium-containing support, and an internal electron donor compound; wherein the internal electron donor compound is selected from the internal electron donor compounds of any one of claims 1-4.

7. The solid component of an olefin polymerization catalyst according to claim 6, wherein the solid component is a solid component of a Ziegler-Natta catalyst. The magnesium-containing support is a magnesium halide alcoholate having the general formula Mg(OR') 2-m X m • n(R"OH), the titanium-containing compound having the general formula Ti(OR") 4-y X y ; wherein R' is selected from C1-C20 alkyl, X is halogen, m is 0, 1 or 2, n is a decimal number or integer of 0 8. The solid component of an olefin polymerization catalyst according to claim 7, wherein the solid component is a solid component of a Ziegler-Natta catalyst. X is selected from chlorine, bromine, or fluorine; R', R", R'" are each independently selected from methyl, ethyl, propyl, isopropyl, butyl or isobutyl; Preferably, the magnesium halide in the magnesium halide alcoholate is selected from magnesium chloride, magnesium bromide, chloromethoxymagnesium or chloroethoxymagnesium, and the alcoholate in the magnesium halide alcoholate is selected from methanol, ethanol, propanol, isopropanol, butanol or isobutanol; The titanium-containing compound is selected from titanium tetraethoxide, titanium tetrabutoxide, chlorotrialkoxy titanium, dichlorodialkoxy titanium, trichloroalkoxy titanium, titanium tetrachloride or titanium tetrabromide.

9. A process for the preparation of the solid component of the catalyst for the polymerization of olefins according to any one of claims 6 to 8, characterized in that, The process comprises the following steps: S1: reacting the magnesium-containing support with the titanium-containing compound at -40-0°C for 0.1-3h, then raising the temperature to 40-100°C, adding the internal electron donor compound and reacting for 0.5-3h, then separating to obtain the solid product; S2: reacting the solid product with the titanium-containing compound at 80-140°C for 0.1-3h, then washing and drying to obtain the solid component of the olefin polymerization catalyst; The total amount of the titanium-containing compound is calculated based on Ti, and the amount of the magnesium-containing support is calculated based on Mg, and the Ti / Mg molar ratio is 1-200.

10. The production method according to claim 9, wherein The process further comprises adding the solid product to the titanium-containing compound at 80-140°C, reacting for 0.5-3h, then separating to obtain a solid, and then performing the step of S2; The titanium-containing compound is selected from titanium tetrachloride.

11. An olefin polymerization catalyst characterized in that, The process comprises the following steps: The solid component of the olefin polymerization catalyst is selected from the solid component of the olefin polymerization catalyst according to any one of claims 6-8 or the solid component of the olefin polymerization catalyst according to the process of any one of claims 9 or 10.

12. The olefin polymerization catalyst of claim 11, wherein, The co-catalyst is selected from the group consisting of alkyl aluminum compounds having the general formula AlR p X, 3-p where R is selected from a C1-C20 alkyl group, a C6-C20 aralkyl group, or a C6-C20 aryl group; X is a halogen, and p is 0, 1, 2, or 3. The external electron donor is a siloxane compound having the general formula 'R a Si(O”R) 4-a , 'R is a C1-C10 alkyl group, a C3-C10 cycloalkyl group, or a C6-C10 aryl group; "R is a C1-C4 alkyl group; a is 0, 1, 2, or 3.

13. The olefin polymerization catalyst according to claim 11 or 12, characterized in that, The co-catalyst is selected from trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, diethylaluminum chloride, diisobutylaluminum chloride or ethylaluminum dichloride; The external electron donor is selected from dimethoxydimethylsilane, diethoxydimethylsilane, methylcyclohexyldimethoxysilane, dimethoxydiphenylsilane, phenyltrimethoxysilane, phenyltriethoxysilane or diphenyldimethoxysilane.

14. The olefin polymerization catalyst according to claim 11 or 12, characterized in that, The molar ratio of titanium in the solid component of the olefin polymerization catalyst to aluminum in the co-catalyst is 1:1-1:2000; The molar ratio of Si in the external electron donor to Ti in the solid component of the olefin polymerization catalyst is 1:1-1:100.

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