阅读说明：本技术 丙烯聚合催化剂、丙烯聚合催化剂体系及其制备与应用 (Propylene polymerization catalyst, propylene polymerization catalyst system, preparation and application thereof ) 是由 崔亮 义建军 雷珺宇 郝海军 王科峰 赵士胜 庄俊鹏 张圣辉 于 2020-05-09 设计创作，主要内容包括：本发明公开了一种丙烯聚合催化剂、丙烯聚合催化剂体系及其制备与应用。该丙烯聚合催化剂包括：活性态卤化镁,承载于其上的至少含有一个Ti-卤键的钛化合物,以及内给电子体化合物；所述内给电子体化合物选自具有式(1)结构的一种或两种以上的化合物；式中,R-(1)、R-(6)各自独立地选自C1-C12的直链或支链烷基、C3-C15的环烷基、或芳基,R′为H原子、C1-C5的直链或支链烷基、或苯基；R-(2)、R-(3)、R-(4)、R-(5)各自独立地选自H原子、卤素、C-(1)-C-(12)的直链或支链烷基、C-(3)-C-(8)的环烷基、C-(6)-C-(15)的芳基或芳烷基。本发明使用一种新型的内给电子体,能够得到具有聚合反应活性高,立体定向性优良的催化剂。(The invention discloses a propylene polymerization catalyst, a propylene polymerization catalyst system, and preparation and application thereof. The propylene polymerization catalyst comprises: the active magnesium halide, a titanium compound which is loaded on the active magnesium halide and at least contains one Ti-halogen bond, and an internal electron donor compound; the internal electron donor compound is selected from one or more than two compounds with a structure of a formula (1); in the formula, R 1 、R 6 Each independently selected from C1-C12 linear or branched alkyl, C3-C15 cycloalkyl, or aryl, R' is H atom, C1-C5 linear or branched alkyl, or phenyl; r 2 、R 3 、R 4 、R 5 Each independently selected from H atom, halogenElement, C 1 ‑C 12 Straight or branched alkyl of (2), C 3 ‑C 8 Cycloalkyl of, C 6 ‑C 15 Aryl or aralkyl groups of (a). The invention uses a novel internal electron donor to obtain the catalyst with high polymerization reaction activity and excellent stereospecificity.)

1. A propylene polymerization catalyst, wherein the propylene polymerization catalyst comprises: the electron donor compound comprises active magnesium halide, a titanium compound which is loaded on the active magnesium halide and at least contains one Ti-halogen bond, and an internal electron donor compound;

the internal electron donor compound is selected from one or more than two compounds with a structure of a formula (1);

in the formula, R₁、R₆Each independently selected from C1-C12 linear or branched alkyl, C3-C15 cycloalkyl, or aryl, R' is H atom, C1-C5 linear or branched alkyl, or phenyl;

R₂、R₃、R₄、R₅each independently selected from H atom, halogen, C₁-C₁₂Straight or branched alkyl of (2), C₃-C₈Cycloalkyl of, C₆-C₁₅Aryl or aralkyl groups of (a).

2. The propylene polymerization catalyst according to claim 1, wherein R' in formula (1) is a methyl group.

3. The propylene polymerization catalyst according to claim 2, wherein in formula (1), R is₆Selected from linear or branched alkyl of C1-C12, or phenyl.

4. The propylene polymerization catalyst according to claim 3, wherein R in the formula (1)₁Selected from linear or branched alkyl groups of C1-C12.

5. The propylene polymerization catalyst according to claim 4, wherein R in the formula (1)₂、R₃、R₄、R₅Are all H atoms.

6. The propylene polymerization catalyst according to claim 1, wherein the internal electron donor compound is one or more compounds selected from the group consisting of:

2- (N-methylbutylsulfonamido) benzoic acid butyl ester;

2- (N-methylphenylsulfonamido) benzoic acid methyl ester;

2- (N-methylbutylsulfonamido) benzoic acid methyl ester;

isopropyl 2- (N-methylphenylsulfonamido) benzoate;

propyl 2- (N-methylbutylsulfonamido) benzoate;

isobutyl 2- (N-methylethylsulfonamide) benzoate;

2- (N-methylmethanesulfonamido) benzoic acid methyl ester;

neopentyl 2- (N-methylbutylsulfonamido) benzoate;

cyclopentyl 2- (N-methylpropanesulfonamido) benzoate;

2- (N-methylpropanesulfonamido) cyclohexyl benzoate;

2- (N-methylcyclopropylsulfonamide) benzoic acid methyl ester;

2- (N-methylcyclopentylsulfonamide) benzoic acid methyl ester;

2- (N-methylpentylsulfonamido) benzoic acid methyl ester;

isopropyl 2- (N-methylcyclohexylsulfonamido) benzoate;

propyl 2- (N-methylheptylsulfonamido) benzoate;

isobutyl 2- (N-methyl-p-tolylsulfonamide) benzoate;

2- (N-methylbutylsulfonamido) benzoic acid phenyl ester;

isooctyl 2- (N-methylbutylsulfonamido) benzoate;

p-tolyl 2- (N-methylpropylsulfonamido) benzoate;

ethyl 2- (N-methylethylsulfonamide) benzoate;

ethyl 2- (N-methylpentylsulfonamido) benzoate;

isobutyl 2- (N-methylphenylsulfonamido) benzoate;

isobutyl 2- (N-methylbutylsulfonamido) benzoate;

neopentyl 2- (N-methyl-p-tolylsulfonamide) benzoate;

p-tolyl 2- (N-methylbutylsulfonamido) benzoate;

isooctyl 2- (N-methylethylsulfonamide) benzoate;

p-tolyl 2- (N-methylcyclohexylsulfonamido) benzoate;

propyl 2- (N-methyl- β -naphthylsulfonamide) benzoate;

2,3,4, 5-tetramethyl-6- (N-methylsulphonylamino) benzoic acid methyl ester;

4-bromo-6- (N-ethylsulfonylamino) benzoic acid methyl ester;

3-isopropyl-6- (N-butylsulfonamido) benzoic acid methyl ester;

2- (N-butylsulfonamido) benzoic acid butyl ester;

2- (N-phenylsulfonamido) benzoic acid methyl ester;

2- (N-butylsulfonamido) benzoic acid methyl ester;

isopropyl 2- (N-phenylsulfonamido) benzoate;

propyl 2- (N-butylsulfonamido) benzoate;

isobutyl 2- (N-ethylsulfonylamino) benzoate.

7. The propylene polymerization catalyst according to claim 1, wherein the precursor of the active magnesium halide is a magnesium halide alcoholate;

the magnesium halide alcoholate has the general formula of Mg (OR)¹)_2-mX_m·n(R²OH), in which formula R¹Selected from C1-C20 alkyl, X is halogen, m is 1 or 2, n is 0<n<Decimal or integer of 5, R²Selected from C1-C20 alkyl groups.

8. The propylene polymerization catalyst of claim 7, wherein the magnesium halide in the magnesium halide alcoholate comprises: one or more of magnesium chloride, magnesium bromide, chloromethoxymagnesium and chloroethoxymagnesium; the alcohols in the magnesium halide alcoholate include: one or more of methanol, ethanol, propanol, isopropanol, butanol and isobutanol.

9. The propylene polymerization catalyst according to claim 8, wherein the magnesium halide in the magnesium halide alcoholate is magnesium chloride and the alcohol is ethanol.

10. The propylene polymerization catalyst according to claim 1, wherein the titanium compound comprises: one or more of chlorotrialkoxy titanium, dichlorodialkoxy titanium, trichloroalkoxy titanium, titanium tetrachloride and titanium tetrabromide.

11. The propylene polymerization catalyst according to claim 10, wherein the titanium compound is titanium tetrachloride.

12. The propylene polymerization catalyst according to any one of claims 1 to 11, wherein the total mass of the propylene polymerization catalyst is 100%, wherein the mass content of the magnesium element is 10% to 25%, the mass content of the titanium element is 1% to 15%, the total mass content of the magnesium halide and the halogen in the titanium compound is 40% to 60%, and the mass content of the internal electron donor is 1% to 10%.

13. A process for preparing a propylene polymerization catalyst as claimed in any one of claims 1 to 12, wherein the process comprises the steps of:

s1, adding the precursor of the active magnesium halide into part of the titanium compound liquid, and cooling to a first preset temperature for reaction;

s2, gradually heating to a second preset temperature, and adding the internal electron donor compound to continue the reaction;

s3, adding the rest titanium compound under the third preset temperature condition, continuing to react, and filtering the reaction system after the reaction is finished to obtain solid residues;

s4, washing and drying the solid residue to obtain the propylene polymerization catalyst.

14. The preparation method of claim 13, wherein the first preset temperature in S1 is-40 ℃ to 0 ℃, and the reaction time is 0.1h to 3 h;

the second preset temperature in the S2 is 40-100 ℃, and the reaction time is 0.5-3 h;

the third preset temperature in S3 is 80-140 ℃, and the reaction time is 0.5-3 h;

the molar ratio of the magnesium element in the S2 to the internal electron donor compound is 1:1-20: 1.

15. A propylene polymerization catalyst system, wherein the propylene polymerization catalyst system comprises: a propylene polymerization catalyst as claimed in any one of claims 1 to 12, a cocatalyst and an external electron donor.

16. The propylene polymerization catalyst system of claim 15, wherein the cocatalyst is an alkylaluminum compound having the general formula AlR³ _pX_3-pIn the formula, R³Is C1-C20 alkyl; x is halogen, p is an integer of more than or equal to 1 and less than or equal to 3;

the external electron donor is a siloxane compound with the general formula R⁴ _qSi(OR⁵)_4-qIn the formula, R⁴Is C1-C10 alkyl, cycloalkyl or aryl; r⁵Is containing 1-4 carbonsAn alkyl group of atoms; q is an integer of 0-3.

17. The propylene polymerization catalyst system of claim 15 or 16, wherein the co-catalyst comprises one or a combination of two or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloride, diisobutylaluminum monochloride and ethylaluminum dichloride.

18. The propylene polymerization catalyst system of claim 15, wherein the external electron donor comprises one or a combination of two or more of methylcyclohexyldimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and diphenyldimethoxysilane.

19. The propylene polymerization catalyst system of any of claims 15-18, wherein the molar ratio of titanium in the propylene polymerization catalyst to aluminum in the cocatalyst is from 1:1 to 1: 2000;

the ratio of the external electron donor to the propylene polymerization catalyst is 1:1-1:100 according to the Si/Ti molar ratio.

20. Use of a propylene polymerization catalyst according to any one of claims 1-12 or a propylene polymerization catalyst system according to any one of claims 15-19 in propylene polymerization reactions.

Technical Field

The invention relates to the technical field of catalysts, and particularly relates to a propylene polymerization catalyst, a propylene polymerization catalyst system, and preparation and application thereof.

Background

The solid catalyst with Mg, Ti, halogen and electron donor as basic components may be used in CH₂The polymerization of ═ CHR olefins, particularly α -olefins having 3 or more carbon atoms, can give polymers in higher yields and with higher stereoregularity. The internal electron donor compound is used as an important component of the Ziegler-Natta catalyst, plays a crucial role in improving the performance of the catalyst, is one of key factors influencing the performance of the catalyst, can improve the activity of the catalyst, and can improve the orientation capability of the catalyst, so that a polymerization product has high stereoregularity. Therefore, the development of electron donor compounds has led to the continuous renewal of polyolefin catalysts.

Many compounds can be used as internal electron donors of Ziegler-Natta catalysts: polycarboxylic acids, mono-or polycarboxylic acid esters, anhydrides, ketones, monoethers or polyethers and derivatives thereof, among which the aromatic dicarboxylic acid esters are more commonly used, such as di-n-butyl phthalate or diisobutyl phthalate (US6365685B1, US20010020073a 1). WO2005097841A1 provides a catalyst component in which an electron donor is used which is a ketoester derivative of a particular formula; one internal electron donor to which WO2005047351a1 relates is a thiophene dicarboxylate having a particular chemical formula; WO2004106388A2 relates to internal electron donors selected from the group consisting essentially of ethers, esters and alkoxysilanes, in particular C1-C20 cyclic ethers, alkyl esters and aliphatic carboxyls; WO03002617A1 relates to monofunctional electron donors (MD) selected from esters, ethers, amides or ketones; US6433119B1 relates to the use of an internal electron donor in a supported catalyst component comprising an acetate, an anhydride, a ketone, an aldehyde and mono-and di-functional organic acid esters; US20030207754a1 and US20030199388a1 relate to the internal electron donor being a propylene glycol; the internal electron donor referred to in WO2004005359A1, US6818583B1, US20020183575A1 and US20050032633A1 patents is a succinate ester, which can improve the activity of the catalyst and the molecular weight distribution of the obtained polypropylene is obviously widened. Research results of WO03076480A1, WO03022894A1, US6395670B1, US20050154157A1, EP728769A1 and the like show that a substituent with larger volume and higher symmetry on a carbon atom at the 2-position in a1, 3-diether electron donor compound is beneficial to improving catalytic activity and polymer isotacticity, and the catalyst has sensitive hydrogen regulation performance. Compounds such as glycol esters, cyclic esters, polyether esters, and phosphoric esters have been reported to be used as internal electron donors in CN1453298A, CN1690039A, CN101125898A, CN105985469A, and CN 104628911A.

Although the catalyst taking phthalate diester as an internal electron donor is applied, the male fertility can be influenced by the residue of the phthalate diester in a polypropylene product in the using process of the catalyst, and corresponding regulations are successively formulated in various countries to limit the use of plastic products with excessive phthalate content. Therefore, in the development process of olefin polymerization catalysts, various research units continuously develop and explore internal electron donor compounds with novel structures and apply the internal electron donor compounds to olefin polymerization catalysts with the basic requirement of avoiding the use of phthalic diester in the preparation process and the purpose of improving the comprehensive performance of the catalysts.

Disclosure of Invention

The invention aims to provide a propylene polymerization catalyst, a propylene polymerization catalyst system, and preparation and application thereof. The propylene polymerization catalyst has high polymerization activity and good stereospecificity.

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

the first aspect of the present invention provides a propylene polymerization catalyst comprising: the electron donor compound comprises active magnesium halide, a titanium compound which is loaded on the active magnesium halide and at least contains one Ti-halogen bond, and an internal electron donor compound;

the internal electron donor compound is selected from one or more than two compounds with a structure of a formula (1);

in the formula, R₁、R₆Each independently selected from C1-C12 linear or branched alkyl, C3-C15 cycloalkyl, or aryl, R' is H atom, C1-C5 linear or branched alkyl, or phenyl;

R₂、R₃、R₄、R₅each independently selected from H atom, halogen, C₁-C₁₂Straight or branched alkyl of (2), C₃-C₈Cycloalkyl of, C₆-C₁₅Aryl or aralkyl groups of (a).

In one embodiment of the present invention, in formula (1), the R' is methyl.

In one embodiment of the present invention, in formula (1), R is₆Selected from linear or branched alkyl of C1-C12, or phenyl.

In one embodiment of the present invention, in formula (1), the R is₁Selected from linear or branched alkyl groups of C1-C12.

In one aspect of the inventionIn embodiments, of formula (1), the R₂、R₃、R₄、R₅Are all H atoms.

In one embodiment of the present invention, the internal electron donor compound is any one or two or more compounds selected from the group consisting of:

2- (N-methylbutylsulfonamido) benzoic acid butyl ester:

methyl 2- (N-methylphenylsulfonamido) benzoate:

methyl 2- (N-methylbutylsulfonamido) benzoate:

isopropyl 2- (N-methylphenylsulfonamido) benzoate:

propyl 2- (N-methylbutylsulfonamido) benzoate:

isobutyl 2- (N-methylethylsulfonamide) benzoate:

methyl 2- (N-methylmethanesulfonamido) benzoate:

neopentyl 2- (N-methylbutylsulfonamido) benzoate:

cyclopentyl 2- (N-methylpropanesulfonamido) benzoate:

cyclohexyl 2- (N-methylpropylsulfonamido) benzoate:

methyl 2- (N-methylcyclopropylsulfonamide) benzoate:

methyl 2- (N-methylcyclopentylsulfonamide) benzoate:

methyl 2- (N-methylpentylsulfonamido) benzoate:

isopropyl 2- (N-methylcyclohexylsulfonamido) benzoate:

propyl 2- (N-methylheptylsulfonamido) benzoate:

isobutyl 2- (N-methyl-p-tolylsulfonamide) benzoate:

2- (N-methylbutylsulfonamido) benzoic acid phenyl ester:

isooctyl 2- (N-methylbutylsulfonamido) benzoate;

p-tolyl 2- (N-methylpropylsulfonamido) benzoate;

ethyl 2- (N-methylethylsulfonamide) benzoate;

ethyl 2- (N-methylpentylsulfonamido) benzoate;

isobutyl 2- (N-methylphenylsulfonamido) benzoate;

isobutyl 2- (N-methylbutylsulfonamido) benzoate;

neopentyl 2- (N-methyl-p-tolylsulfonamide) benzoate;

p-tolyl 2- (N-methylbutylsulfonamido) benzoate;

isooctyl 2- (N-methylethylsulfonamide) benzoate;

p-tolyl 2- (N-methylcyclohexylsulfonamido) benzoate;

propyl 2- (N-methyl- β -naphthylsulfonamide) benzoate;

2,3,4, 5-tetramethyl-6- (N-methylsulphonylamino) benzoic acid methyl ester;

4-bromo-6- (N-ethylsulfonylamino) benzoic acid methyl ester;

3-isopropyl-6- (N-butylsulfonamido) benzoic acid methyl ester;

2- (N-butylsulfonamido) benzoic acid butyl ester;

2- (N-phenylsulfonamido) benzoic acid methyl ester;

2- (N-butylsulfonamido) benzoic acid methyl ester;

isopropyl 2- (N-phenylsulfonamido) benzoate;

propyl 2- (N-butylsulfonamido) benzoate;

isobutyl 2- (N-ethylsulfonylamino) benzoate.

In one embodiment of the present invention, the internal electron donor compound is selected from one of the following compounds:

2- (N-methylbutylsulfonamido) benzoic acid butyl ester:

methyl 2- (N-methylphenylsulfonamido) benzoate:

methyl 2- (N-methylbutylsulfonamido) benzoate:

isopropyl 2- (N-methylphenylsulfonamido) benzoate:

propyl 2- (N-methylbutylsulfonamido) benzoate:

isobutyl 2- (N-methylethylsulfonamide) benzoate:

in one embodiment of the invention, the precursor of the active magnesium halide is a magnesium halide alcoholate;

the magnesium halide alcoholate has the general formula of Mg (OR)¹)_2-mX_m·n(R²OH), in which formula R¹Selected from C1-C20 alkyl, X is halogen, m is 1 or 2, n is 0<n<Decimal or integer of 5, R²Selected from C1-C20 alkyl groups.

In one embodiment of the present invention, the magnesium halide in the magnesium halide alcoholate comprises: one or more of magnesium chloride, magnesium bromide, chloromethoxymagnesium and chloroethoxymagnesium; the alcohols in the magnesium halide alcoholate include: one or more of methanol, ethanol, propanol, isopropanol, butanol and isobutanol.

In one embodiment of the invention, the magnesium halide in the magnesium halide alcoholate is magnesium chloride and the alcohol is ethanol.

In one embodiment of the present invention, the titanium compound includes: one or more of chlorotrialkoxy titanium, dichlorodialkoxy titanium, trichloroalkoxy titanium, titanium tetrachloride and titanium tetrabromide.

In one embodiment of the invention, the titanium compound is titanium tetrachloride.

In one embodiment of the present invention, the propylene polymerization catalyst contains 10 to 25% by mass of magnesium element, 1 to 15% by mass of titanium element, 40 to 60% by mass of magnesium halide and halogen in titanium compound, and 1 to 10% by mass of internal electron donor, based on 100% by mass of the total propylene polymerization catalyst.

The second aspect of the present invention provides a method for preparing the above propylene polymerization catalyst, comprising the steps of:

s1, adding the precursor of the active magnesium halide into part of the titanium compound liquid, and cooling to a first preset temperature for reaction;

s2, gradually heating to a second preset temperature, and adding the internal electron donor compound to continue the reaction;

s3, adding the rest titanium compound under the third preset temperature condition, continuing to react, and filtering the reaction system after the reaction is finished to obtain solid residues;

s4, washing and drying the solid residue to obtain the propylene polymerization catalyst.

In one embodiment of the present invention, the first preset temperature in S1 is-40 ℃ to 0 ℃, and the reaction time is 0.1h to 3 h;

the second preset temperature in the S2 is 40-100 ℃, and the reaction time is 0.5-3 h;

the third preset temperature in S3 is 80-140 ℃, and the reaction time is 0.5-3 h;

the molar ratio of the magnesium element in the S2 to the internal electron donor compound is 1:1-20: 1; preferably, the molar ratio of the magnesium element to the internal electron donor compound is 2:1 to 10: 1.

Wherein, the internal electron donor compound is prepared by the following method:

reacting a 2-aminobenzoate compound of formula (2) as a raw material with a base in an organic solvent at a temperature range of-78 ℃ to 50 ℃ in a molar ratio of 1:1-1:2 for 1 to 10 hours, reacting with R 'X for 1 to 150 hours without separation, wherein the feeding molar ratio of the 2-aminobenzoate compound of the formula (2) to the R' X is 1:1-1: 50;

in the formula (2), R₁、R₆Each independently selected from C1-C12 linear or branched alkyl, C3-C15 cycloalkyl, or aryl, R' is H atom, C1-C5 linear or branched alkyl, or phenyl; r₂、R₃、R₄、R₅Each independently selected from H atom, halogen, C₁-C₁₂Straight or branched alkyl of (2), C₃-C₈Cycloalkyl of, C₆-C₁₅Aryl or aralkyl of (a); in R 'X, R' is methyl; x ═ Br, I or O₃SC₆H₅。

Regarding the preparation of the internal electron donor compound, in one embodiment of the present invention, the base is selected from one of NaH and lithium diisopropylamide.

Regarding the preparation of the internal electron donor compound, in one embodiment of the present invention, the organic solvent is one selected from the group consisting of N, N-dimethylformamide, and tetrahydrofuran.

Regarding the preparation of the internal electron donor compound, in one embodiment of the present invention, the preparation method comprises:

reacting 2-aminobenzoate compound of a formula (2) serving as a reaction substrate with NaH and methyl iodide at a feeding molar ratio of 1:1: 1-1: 20: 50; DMF and THF are used as solvent, and an anhydrous and oxygen-free reaction system is maintained, the reaction temperature is-78-50 ℃, and the reaction time is 1-150 h. After the reaction is finished, the solid or oily liquid is obtained by vacuum drying after the operations of neutralization, extraction, washing, rotary evaporation, column chromatographic separation and the like, namely the corresponding methylated product (namely the internal electron donor compound of the invention) with the yield of about 70 percent.

Regarding the preparation of the internal electron donor compound, in one embodiment of the present invention, the feeding molar ratio of the 2-aminobenzoate compound of formula (2), NaH and methyl iodide is 1:1:1 to 1:5: 10.

Regarding the preparation of the internal electron donor compound, in one embodiment of the present invention, the reaction temperature is selected from 0 to 30 ℃.

Regarding the preparation of the internal electron donor compound, in one embodiment of the present invention, the reaction time is 12h to 100 h.

The present invention provides a general synthesis of a 2-aminobenzoate compound of formula (2):

dissolving a 2-aminobenzoate compound of a formula (3) in tetrahydrofuran or Dimethylformamide (DMF), adding 1-5 times of triethylamine serving as an acid-binding agent, and adding alkylsulfonyl chloride at-30-50 ℃; the preferred reaction temperature is from 0 to 10 degrees. After the addition is finished, the reaction lasts for 2 to 120 hours; the preferable reaction time is 30 to 40 hours. Adding water for hydrolysis, extracting with ethyl acetate, concentrating, and purifying by column chromatography. The yield obtained by the synthesis process is between 30 and 95 percent.

In one embodiment of the present invention, the 2-aminobenzoate compound of formula (3) is obtained by esterification of 2-aminobenzoic acid with alcohol; the general synthesis procedure is as follows:

dissolving 2-aminobenzoic acid in HOR₁In alcohol; HOR₁Large excess as solvent, 2-aminobenzoic acid and HOR₁The proportion of the compound is from 1:5 to 10000, and 2-aminobenzoic acid is preferably dissolved at room temperature; at a concentration of 0.01 to 1 molar times of concentrated H₂SO₄The preferred amount of addition is 0.2 times for the catalyst. The reaction temperature is in the range of room temperature to 150 deg.C, preferably 100 deg.C. The reaction time is 5-60 h, and the preferable reaction time is 36 h. After hydrolysis, the mixture was concentrated with dichloromethane and purified by column chromatography. The yield is 30-95%.

Wherein, HOR₁R in (1)₁As in formula (1) R₁The definition of (1).

In a third aspect, the present invention provides a propylene polymerization catalyst system comprising: the propylene polymerization catalyst, the cocatalyst and the external electron donor.

In one embodiment of the invention, the cocatalyst is an alkylaluminum compound having the general formula AlR³ _pX_3-pIn the formula, R³Is C1-C20 alkyl; x is halogen, p is an integer of more than or equal to 1 and less than or equal to 3;

the external electron donor is a siloxane compound with the general formula R⁴ _qSi(OR⁵)_4-qIn the formula, R⁴Is C1-C10 alkyl, cycloalkyl or aryl; r⁵Is an alkyl group having 1 to 4 carbon atoms; q is an integer of 0-3.

In one embodiment of the invention, the cocatalyst comprises trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloride, diisobutylaluminum monochloride or ethylaluminum dichloride.

In one embodiment of the present invention, the external electron donor comprises phenyltrimethoxysilane, phenyltriethoxysilane, or diphenyldimethoxysilane.

In one embodiment of the present invention, the molar ratio of titanium in the propylene polymerization catalyst to aluminum in the cocatalyst is from 1:1 to 1: 2000; preferably 1:5 to 1: 500;

the ratio of the external electron donor to the propylene polymerization catalyst is 1:1-1:100 according to the Si/Ti molar ratio; preferably 1:1 to 1: 50.

The fourth aspect of the present invention provides the use of the above propylene polymerization catalyst or the above propylene polymerization catalyst system in propylene polymerization.

In the above applications, various methods known in the art for olefin polymerization may be used, including but not limited to bulk polymerization, slurry polymerization, and gas phase polymerization. The basic process of using the catalyst is briefly described here by taking bulk polymerization of propylene as an example: the polymerization reaction kettle is fully replaced by nitrogen, and is subjected to vacuum drying treatment, a propylene monomer is added, the propylene polymerization catalyst, the cocatalyst and the external electron donor are added according to a certain proportion, the polymerization temperature is 20-90 ℃, preferably 60-80 ℃, the polymerization reaction lasts for 1-2 hours, and the polymerization reaction kettle is vented and fully replaced by nitrogen to obtain a dry polymer.

The invention has the beneficial effects that:

the propylene polymerization catalyst of the invention uses a novel internal electron donor, and can obtain a catalyst with high polymerization reaction activity and excellent stereospecificity.

Drawings

FIG. 1 shows a schematic representation of butyl 2- (N-methylbutylsulfonamido) benzoate obtained in example 1¹And (4) H spectrum.

FIG. 2 shows a schematic representation of butyl 2- (N-methylbutylsulfonamido) benzoate obtained in example 1¹³And (4) C spectrum.

FIG. 3 shows a schematic representation of methyl 2- (N-methylphenylsulfonamido) benzoate obtained in example 2¹And (4) H spectrum.

FIG. 4 shows a schematic representation of methyl 2- (N-methylphenylsulfonamido) benzoate obtained in example 2¹³And (4) C spectrum.

FIG. 5 is a drawing showing the preparation of methyl 2- (N-methylbutylsulfonamido) benzoate obtained in example 3¹And (4) H spectrum.

FIG. 6 is a drawing showing a preparation process of methyl 2- (N-methylbutylsulfonamido) benzoate obtained in example 3¹³And (4) C spectrum.

FIG. 7 shows a schematic representation of isopropyl 2- (N-methylphenylsulfonamido) benzoate obtained in example 4¹And (4) H spectrum.

FIG. 8 shows a schematic representation of isopropyl 2- (N-methylphenylsulfonamido) benzoate obtained in example 4¹³And (4) C spectrum.

FIG. 9 is a drawing showing propyl 2- (N-methylbutylsulfonamido) benzoate obtained in example 5¹And (4) H spectrum.

FIG. 10 is a drawing showing propyl 2- (N-methylbutylsulfonamido) benzoate obtained in example 5¹³And (4) C spectrum.

FIG. 11 shows the preparation of isobutyl 2- (N-methylethylsulfonamide) benzoate obtained in example 6¹And (4) H spectrum.

FIG. 12 shows a scheme for producing isobutyl 2- (N-methylethylsulfonamide) benzoate obtained in example 6¹³And (4) C spectrum.

Detailed Description

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

The test method comprises the following steps:

1. the structure of the synthesized electron donor compound is determined by a nuclear magnetic resonance method.

2. The isotacticity of the polymerization product was determined by boiling n-heptane extraction. According to the national standard GB/T2412-2008.

3. The catalyst activity is calculated as the mass ratio of the polymer formed by the reaction to the catalyst charged.

Synthesis of compounds

Example 1:

this example provides a butyl 2- (N-methylbutylsulfonamido) benzoate having the following structure:

the preparation method of the 2- (N-methylbutylsulfonamido) butyl benzoate comprises the following three steps:

the first step is as follows: in a 1000mL flask was added 30.0g of 2-aminobenzoic acid, 800mL of n-butanol, 50mL of concentrated H₂SO₄(ii) a After reacting for about 36h with continuous heating under heating and stirring in an oil bath at 100 deg.C, the reaction solution was transferred to a 2000mL flask, n-butanol and water were removed, the orange-yellow residue was dissolved in 600mL water, transferred to a 2000mL NaHCO beaker, and an appropriate amount of NaHCO was added₃Neutralizing excess H₂SO₄Until no bubble is generated (PH is less than or equal to 7); then, about 300mL of methylene chloride was added thereto for extraction, the organic phase was separated, and the solvent was removed to obtain a crude product.

Column chromatography purification afforded 16.62g of butyl 2-aminobenzoate as an oil in 39% yield.

The second step is that: in a 250mL flask was added 12.00g of butyl 2-aminobenzoate, 50mL of tetrahydrofuran and 11mL of triethylamine; then, 12g of butylsulfonyl chloride dissolved in 70mL of ethyl acetate is dropwise added into the flask, and after the dropwise addition is finished, stirring is carried out for about 42 hours; thereafter, the reaction solution was transferred to a 1000mL separatory funnel, about 300mL of water was added to the reaction solution, extraction was performed with ethyl acetate, and the crude product obtained after removal of the solvent was purified by column chromatography to obtain 14g of butyl 2-butanesulfonamide benzoate with a yield of 70%.

The third step: dissolving 1.52g NaH in 30mL of DMF, adding 13g of butyl 2-butanesulfonamide benzoate dissolved in 60mL of DMF to a Schlenk bottle, and stirring for about 2H₂After releasing, dropwise adding 18g of iodomethane dissolved in 150mL of THF into the reaction solution, stirring at room temperature for 36 hours, and slowly dropwise adding a proper amount of concentrated hydrochloric acid into the reaction solution to neutralize redundant NaH until the pH of the reaction solution is less than or equal to 7; then transferring the reaction solution to a 1000mL separating funnel, and adding about 200mL of hydrolysis solution; extraction was performed with methyl t-butyl ether, and the crude product obtained by concentrating the extracted organic phase was purified by column chromatography to obtain 10g of butyl 2- (N-methylbutylsulfonamido) benzoate as a yellow oil in a yield of 71%.

The nuclear magnetic hydrogen spectrum and carbon spectrum of butyl 2- (N-methylbutylsulfonamido) benzoate are shown in FIG. 1 and FIG. 2.

¹H NMR(400MHz,CDCl₃,25℃,TMS):δ(ppm)7.88(d,1H,J＝8.0Hz),7.54(t,1H,J＝8.8Hz),7.42(q,2H,J＝9.6Hz),4.33(t,2H,J＝6.8Hz),3.35(d,3H,J＝2.8Hz),3.07(t,2H,J＝8.0Hz),1.86-1.73(m,4H),1.53-1.39(m,4H),1.01-0.91(m,6H).

¹³C NMR(400MHz,CDCl₃,25℃,TMS):δ(ppm)166.22,140.37,132.58,131.20,130.64,130.61,128.16,65.32,51.61,39.37,30.60,25.27,21.69,19.22,13.59.

Example 2:

methyl 2- (N-methylphenylsulfonamido) benzoate:

the reaction procedure was the same as in example 1. The difference is that in the first step of reaction, the raw material n-butanol is replaced by methanol, and methyl 2-aminobenzoate is synthesized first; then, butylsulfonyl chloride was replaced with phenylsulfonyl chloride according to the second step in example 1 to give methyl 2-phenylsulfonamidobenzoate, and butyl 2-butylsulfonamidobenzoate was replaced with methyl 2-phenylsulfonamidobenzoate according to the third step in example 1 to give methyl 2- (N-methylphenylsulfonamido) benzoate as white solid particles with a melting point of 97 ℃ in a yield of 59%.

The nuclear magnetic hydrogen spectrum and carbon spectrum of the methyl 2- (N-methyl phenyl sulfonamide) benzoate are shown in figure 3 and figure 4.

¹H NMR(400MHz,CDCl₃,25℃,TMS):δ(ppm)7.88-7.86(dd,1H,J₁＝8.0Hz,J₂＝2.8Hz),7.67(d,2H,J＝8.0Hz),7.60(t,1H,J＝8.0Hz),7.52-7.39(m,4H),6.96-6.94(dd,1H,J₁＝8.0Hz,J₂＝2.0Hz),3.85(s,3H),3.13(s,3H).

¹³C NMR(400MHz,CDCl₃,25℃,TMS):δ(ppm)166.72,140.04,138.75,132.53,132.23,132.14,131.14,128.98,128.82,128.18,127.54,52.35,38.98.

Example 3:

methyl 2- (N-methylbutylsulfonamido) benzoate:

the reaction procedure was the same as in example 1. The difference is that the raw material n-butanol in the first step of reaction is replaced by methanol; firstly, synthesizing 2-methyl aminobenzoate; then, according to the second step in example 1, methyl 2-butanesulfonamide benzoate was obtained, and according to the third step in example 1, butyl 2-butanesulfonamide benzoate was replaced with methyl 2-butanesulfonamide benzoate, and methyl 2- (N-methylbutylsulfonamido) benzoate was obtained as a reddish brown powdery product with a melting point of 42 ℃ in a yield of 53%.

The nuclear magnetic spectrum and carbon spectrum of methyl 2- (N-methylbutylsulfonamido) benzoate are shown in FIG. 5 and FIG. 6.

¹H NMR(400MHz,CDCl₃,25℃,TMS):δ(ppm)7.90-7.87(dq,1H,J₁＝1.6Hz,J₂＝7.6Hz),7.56(t,1H,J＝8.4Hz),7.41(q,2H,J＝8.4Hz),3.93(t,3H,J＝1.6Hz),3.34(t,3H,J＝1.2Hz),3.07(t,2H,J＝8.0Hz),1.86-1.78(m,2H),1.44(q,2H,J＝7.6Hz),0.94(t,3H,J＝7.6Hz).

¹³C NMR(400MHz,CDCl₃,25℃,TMS):δ(ppm)166.57,140.46,132.74,131.24,131.02,130.60,128.16,52.39,51.65,39.36,25.27,21.69,13.59.

Example 4:

isopropyl 2- (N-methylphenylsulfonamido) benzoate:

the reaction procedure was the same as in example 1. The difference is that in the first step of reaction, raw material n-butyl alcohol is replaced by isopropanol, and 2-isopropyl aminobenzoate is synthesized firstly; then, butylsulfonyl chloride was replaced with phenylsulfonyl chloride in the second step of example 1 to give isopropyl 2-phenylsulfonamidobenzoate, and butyl 2-butylsulfamoylbenzoate was replaced with isopropyl 2-phenylsulfonamidobenzoate in the third step of example 1 to give isopropyl 2- (N-methylphenylsulfonamido) benzoate as white needle-shaped flocculent crystals with a melting point of 118 ℃ in a yield of 68%.

The nuclear magnetic spectrum and carbon spectrum of isopropyl 2- (N-methylphenyl sulfonamido) benzoate are shown in FIG. 7 and FIG. 8.

¹H NMR(400MHz,CDCl₃,25℃,TMS):δ(ppm)7.87-7.85(m,1H),7.67(d,2H,J＝8.4Hz),7.60(t,1H,J＝7.2Hz),7.49(t,2H,J＝8.0Hz),7.42-7.35(m,2H),6.80-6.78(m,1H),5.30-5.21(m,1H),3.31(s,3H),1.42(d,6H,J＝6.4Hz).

¹³C NMR(400MHz,CDCl₃,25℃,TMS):δ(ppm)165.98,139.82,138.70,133.52,132.53,131.80,130.99,128.82,128.38,128.20,127.53,69.12,38.98,21.82.

Example 5:

propyl 2- (N-methylbutylsulfonamido) benzoate:

the reaction procedure was the same as in example 1. The difference is that in the first step of reaction, the raw material n-butyl alcohol is replaced by n-propyl alcohol, and then 2-propyl aminobenzoate is synthesized; then, according to the second step in example 1, propyl 2-butanesulfonamide benzoate was obtained, and according to the third step in example 1, butyl 2-butanesulfonamide benzoate was replaced with propyl 2-butanesulfonamide benzoate, and propyl 2- (N-methylbutylsulfonamido) benzoate was obtained as a golden yellow oily liquid product in a yield of 73%.

The nuclear magnetic hydrogen spectrum and carbon spectrum of propyl 2- (N-methylbutylsulfonamido) benzoate are shown in FIG. 9 and FIG. 10.

¹H NMR(400MHz,CDCl₃,25℃,TMS):δ(ppm)7.89(t,1H,J＝4.0Hz),7.55(q,1H,J＝5.6Hz),7.46-7.40(m,2H),4.32-4.27(m,2H),3.36(s,3H),3.09-3.05(m,2H),1.87-1.79(m,4H),1.50-1.43(m,2H),1.06-0.93(dt,6H,J₁＝7.6Hz,J₂＝40Hz).

¹³C NMR(400MHz,CDCl₃,25℃,TMS):δ(ppm)166.23,140.36,132.58,131.22,131.20,130.58,128.16,67.06,51.58,39.38,25.27,21.95,13.59,10.49。

Example 6:

isobutyl 2- (N-methylethylsulfonamide) benzoate:

the reaction procedure was the same as in example 1. The difference is that the raw material n-butyl alcohol is replaced by isobutyl, and isobutyl 2-aminobenzoate is synthesized firstly; then, the second step of example 1 was followed to replace butylsulfonyl chloride with ethylsulfonyl chloride to give isobutyl 2-ethylsulfonylaminobenzoate, and the third step of example 1 was followed to replace butyl 2-butylsulfonylaminobenzoate with isobutyl 2-ethylsulfonylaminobenzoate to give isobutyl 2- (N-methylethylsulfonylamino) benzoate as an off-white powder product having a melting point of 78 ℃ and a yield of 53%.

The nuclear magnetic spectrum and carbon spectrum of isobutyl 2- (N-methylethylsulfonamide) benzoate are shown in FIGS. 11 and 12.

¹H NMR(400MHz,CDCl₃,25℃,TMS):δ(ppm)7.90(d,1H,J＝7.6Hz),7.56(t,1H,J＝7.6Hz),7.48-7.40(m,2H),7.29(s,1H),4.12(d,2H,J＝6.8Hz),3.36(d,3H,J＝0.8Hz),3.11(q,2H,J＝7.2Hz),2.16-2.06(m,1H),1.39(t,3H,J＝7.2Hz),1.04-1.02(dd,6H,J₁＝1.2Hz,J₂＝6.8Hz).

¹³C NMR(400MHz,CDCl₃,25℃,TMS):δ(ppm)166.12,140.45,132.62,131.15,130.79,130.77,128.18,71.56,46.30,39.53,27.75,19.23,8.01。

Secondly, preparing and evaluating a catalyst:

example 7

This example provides a propylene polymerization catalyst, which is prepared by the following steps:

mixing spherical MgCl₂·2.65C₂H₅7.8g of OH support are slowly added to a solution containing 250mL of TiCl₄Precooling the mixture into a reaction bottle at the temperature of minus 30 ℃, gradually heating the reaction bottle to the temperature of 80 ℃, adding 5mmol of internal electron donor methyl 2- (N-methylphenyl sulfonylamino) benzoate, keeping the temperature for 30 minutes, heating the reaction bottle to the temperature of 130 ℃, reacting the reaction bottle for 2 hours, filtering the reaction bottle, and adding 250mL of TiCl₄Reacting at 130 deg.C for 2 hr, washing with n-hexane for 6 times, and vacuum drying to obtain catalyst 3.6g with titanium content of 2.2%.

The above propylene polymerization catalyst was used in propylene polymerization experiments:

the polymerization reaction was carried out in a 2L stainless steel autoclave.

Firstly, emptying the pressure of a polymerization kettle until the gauge pressure is 0, fully replacing the reaction kettle by high-purity nitrogen, and vacuumizing for 1 hour under the heating condition; after the reaction kettle is cooled to room temperature, introducing 0.1MPa high-purity hydrogen and 300g propylene into the reaction kettle, and stirring at a low speed; under the protection of nitrogen, a catalyst feeding hopper sequentially adds 10mg of the catalyst of the embodiment, 2mL of triethylaluminum (2.4mol/L) and 2.5mL of methylcyclohexyldimethoxysilane (0.18mol/L), the materials are added into a reaction kettle after short-time pre-complexation, then 300g of propylene is added, the temperature is raised to 70 ℃ for reaction for 1 hour, the stirring is stopped when the reaction is finished, the temperature is reduced, the pressure is released, and the solid propylene polymer is obtained after discharging.

The polymerization activity of one hour of polymerization using this catalyst was 38.3kg PP/g cat and the isotacticity of the resulting polypropylene was 98.2%.

Example 8

This example provides a propylene polymerization catalyst, which is prepared according to the same procedure as in example 7 except that propyl 2- (N-methylbutylsulfonamido) benzoate was used as the electron donor, to obtain 0.87g of a solid catalyst having a titanium content of 2.85%.

The above propylene polymerization catalyst was used in propylene polymerization experiments:

the procedure is as in example 7.

The polymerization activity of one hour of polymerization using this catalyst was 36.3kg PP/g cat and the isotacticity of the resulting polypropylene was 97.9%.

Example 9

This example provides a propylene polymerization catalyst, which is prepared according to the same procedure as in example 7, except that isopropyl 2- (N-methylphenyl sulfonamido) benzoate is used as the electron donor, thereby obtaining 0.78 g of a solid catalyst, wherein the titanium content is 3.2%. The polymerization activity of one hour of polymerization using this catalyst was 35.0kg PP/g cat and the isotacticity of the resulting polypropylene was 97.3%.

Example 10

This example provides a propylene polymerization catalyst, which is prepared according to the same procedure as in example 7, except that butyl 2- (N-methylbutylsulfonamido) benzoate is used as the electron donor, and 0.78 g of the solid catalyst is obtained, wherein the titanium content is 3.2%.

The above propylene polymerization catalyst was used in propylene polymerization experiments:

the procedure is as in example 7.

The polymerization activity of one hour of polymerization using this catalyst was 35.0kg PP/g cat and the isotacticity of the resulting polypropylene was 97.3%.

Example 11

This example provides a propylene polymerization catalyst, which is prepared according to the same procedure as in example 7, except that the electron donor is methyl 2- (N-methylbutylsulfonamido) benzoate, thus obtaining 3.6g of the catalyst, and the titanium content is 2.2%.

The above propylene polymerization catalyst was used in propylene polymerization experiments:

the procedure is as in example 7.

The polymerization activity of one hour of polymerization using this catalyst was 37.6kg PP/g cat and the isotacticity of the resulting polypropylene was 96.0%.

Example 12

This example provides a propylene polymerization catalyst, which is prepared according to the same procedure as in example 7, except that the electron donor is isobutyl 2- (N-methylethylsulfonamide) benzoate, thus obtaining 3.2g of a spherical catalyst, and the titanium content is 2.8%.

The above propylene polymerization catalyst was used in propylene polymerization experiments:

the procedure is as in example 7.

The polymerization activity of one hour of polymerization using this catalyst was 38.2kg PP/g cat and the isotacticity of the resulting polypropylene was 96.8%.

Example 13

This example provides a propylene polymerization catalyst, which is prepared according to the same procedure as in example 7, except that the electron donor is isopropyl 2- (N-methylcyclohexylsulfonamido) benzoate, and the spherical catalyst was 3.0g, and the titanium content was 3.0%.

The above propylene polymerization catalyst was used in propylene polymerization experiments:

the procedure is as in example 7.

The polymerization activity of one hour of polymerization using this catalyst was 38.9kg PP/g cat and the isotacticity of the resulting polypropylene was 95.8%.

Example 14

This example provides a propylene polymerization catalyst, which is prepared according to the same procedure as in example 7, except that the electron donor is ethyl 2- (N-methylethylsulfonamide) benzoate, and thus spherical catalyst (3.4 g) was obtained, and the titanium content was 2.9%.

The above propylene polymerization catalyst was used in propylene polymerization experiments:

the procedure is as in example 7.

The polymerization activity of one hour of polymerization using this catalyst was 35.3kg PP/g cat and the isotacticity of the resulting polypropylene was 96.5%.

The data show that the compound of the invention is used as an electron donor of a polypropylene catalyst, the activity ratio of the catalyst is higher, and the stereospecificity is better.

It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.