阅读说明：本技术 一种用于制备烯烃聚合物的固体催化剂及固体催化剂体系 (Solid catalyst for preparing olefin polymer and solid catalyst system ) 是由 林洁 张晓帆 黄庭 付梅艳 孙竹芳 夏先知 周俊领 张军辉 赵惠 郭子芳 严立安 于 2020-06-05 设计创作，主要内容包括：本发明提供一种用于制备烯烃聚合物的固体催化剂,其包括下述组分或下述组分的反应产物：镁元素、钛元素、卤素以及第一内给电子体和第二内给电子体,所述第一内给电子体包含式(I)所示的柱芳烃化合物,所述第二内给电子体选自醇酯化合物、芳香族羧酸酯类化合物、二醚化合物和琥珀酸酯类化合物中的一种或多种。通过在固体催化剂组分中引入式(I)所示的柱芳烃化合物或其衍生物做内给电子体,可以提高催化剂的立构定向性,提高聚合产物的分子量。(The invention provides a solid catalyst for preparing olefin polymers, which comprises the following components or the reaction product of the following components: the preparation method comprises the following steps of (1) preparing a magnesium element, a titanium element, halogen, a first internal electron donor and a second internal electron donor, wherein the first internal electron donor comprises a columnar aromatic hydrocarbon compound shown in a formula (I), and the second internal electron donor is selected from one or more of an alcohol ester compound, an aromatic carboxylic acid ester compound, a diether compound and a succinate compound. By introducing the columnar aromatic hydrocarbon compound shown in the formula (I) or the derivative thereof as an internal electron donor into the solid catalyst component, the stereospecificity of the catalyst can be improved, and the molecular weight of a polymerization product can be improved.)

1. A solid catalyst for the preparation of an olefin polymer comprising the following components or the reaction product of the following components: magnesium element, titanium element, halogen, a first internal electron donor and a second internal electron donor,

wherein the first internal electron donor comprises a columnar aromatic hydrocarbon compound shown as a formula (I),

in the formula (I), the compound is shown in the specification,

is a basic unit, wherein M₁、M₂、M₃、M₄、R₁And R₂The same or different, each independently selected from hydrogen, hydroxy, cyano, nitro, amino, -CHO, -R₃CHO、-C(O)R₄、-C(O)OH、-R₃C(O)OH、-C(O)OR₄、-R₃C(O)OR₄、-OR₄、-R₃OR₄Halogen atom, C with or without substituents₁-C₁₀Alkyl and C with or without substituents₁-C₁₀Alkoxy, wherein R₃Is C with or without substituents₁-C₆Alkylene radical, R₄Is C with or without substituents₁-C₆Alkyl, the substituents being selected from the group consisting of hydroxy, amino, -CHO, -C (O) OH, halogen, C₁-C₆Alkyl radical, C₁-C₆Alkoxy and heteroatoms;

n represents the number of basic units and is an integer of 3-20;

when the adjacent groups within or between adjacent base units are-C (O) R₄、-C(O)OR₄、-R₃C(O)OR₄、-OR₄、-R₃OR₄C with or without substituents₁-C₁₀Hydrocarbyl and C with or without substituents₁-C₁₀Hydrocarbyloxy, two adjacent groups are optionally linked to each other to form a cyclic structure selected from the group consisting of a saturated or unsaturated monocyclic ring, a saturated or unsaturated polycyclic ring, and combinations thereof,

the second internal electron donor is selected from one or more of alcohol ester compounds, aromatic carboxylic acid ester compounds, diether compounds and succinate compounds.

2. The solid catalyst according to claim 1, wherein in the formula (I), M is₁、M₂、M₃And M₄The same or different, and the same or different,each independently selected from hydrogen, hydroxy, amino, -CHO, fluoro, chloro, bromo, iodo, C₁-C₁₀Alkyl, halogen atom substituted C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy and halogen substituted C₁-C₁₀An alkoxy group; r₁And R₂The same or different, each independently selected from hydrogen, C with or without substituent₁-C₁₀Alkyl and C with or without substituents₁-C₁₀An alkoxy group; n is an integer of 4 to 10;

preferably, in formula (I), M₁、M₂、M₃And M₄The same or different, each independently selected from hydrogen, hydroxy, amino, -CHO, fluoro, chloro, bromo, iodo, C₁-C₆Alkoxy and halogen substituted C₁-C₆An alkoxy group; r₁And R₂The same or different, each independently selected from hydrogen, C with or without substituent₁-C₆Alkyl and C with or without substituents₁-C₆An alkoxy group; n is an integer of 4 to 7;

more preferably, in formula (I), M₁And M₂Are the same or different and are each independently selected from C₁-C₆An alkoxy group.

3. The solid catalyst according to claim 1 or 2, characterized in that the column aromatic compound of formula (I) is selected from one or more of the following compounds:

compound a 1: m₁＝M₂＝OCH₃；M₃＝M₄＝H；R₁＝R₂＝H；n＝5；

Compound a 2: m₁＝M₂＝OCH₃；M₃＝M₄＝H；R₁＝R₂＝H；n＝6；

Compound a 3: m₁＝M₂＝OCH₃；M₃＝M₄＝H；R₁＝R₂＝H；n＝7；

Compound B1: m₁＝M₂＝OCH₂CH₃；M₃＝M₄＝H；R₁＝R₂＝H；n＝5；

Compound B2: m₁＝M₂＝OCH₂CH₃；M₃＝M₄＝H；R₁＝R₂＝H；n＝6；

Compound B3: m₁＝M₂＝OCH₂CH₃；M₃＝M₄＝H；R₁＝R₂＝H；n＝7；

Compound C1: m₁＝M₂＝OCH₂CH₂CH₃；M₃＝M₄＝H；R₁＝R₂＝H；n＝5；

Compound C2: m₁＝M₂＝OCH₂CH₂CH₃；M₃＝M₄＝H；R₁＝R₂＝H；n＝6；

Compound C3: m₁＝M₂＝OCH₂CH₂CH₃；M₃＝M₄＝H；R₁＝R₂＝H；n＝7；

Compound D1: m₁＝M₂＝OCH(CH₃)₂；M₃＝M₄＝H；R₁＝R₂＝H；n＝5；

Compound D2: m₁＝M₂＝OCH(CH₃)₂；M₃＝M₄＝H；R₁＝R₂＝H；n＝6；

Compound D3: m₁＝M₂＝OCH(CH₃)₂；M₃＝M₄＝H；R₁＝R₂＝H；n＝7；

Compound E1: m₁＝OCH₃；M₂＝OCH₂CH₂CH₃；M₃＝M₄＝H；R₁＝R₂＝H；n＝5；

Compound E2: m₁＝OCH₃；M₂＝OCH₂CH₂CH₃；M₃＝M₄＝H；R₁＝R₂＝H；n＝6；

Compound E3: m₁＝OCH₃；M₂＝OCH₂CH₂CH₃；M₃＝M₄＝H；R₁＝R₂＝H；n＝7；

Compound F1: m₁＝OCH₃；M₂＝CHO；M₃＝M₄＝H；R₁＝R₂＝H；n＝5；

Compound F2: m₁＝OCH₃；M₂＝CHO；M₃＝M₄＝H；R₁＝R₂＝H；n＝6；

Compound F3: m₁＝OCH₃；M₂＝CHO；M₃＝M₄＝H；R₁＝R₂＝H；n＝7；

Compound G1: m₁＝OCH₃；M₂＝OCH₂CH₂Cl；M₃＝M₄＝H；R₁＝R₂＝H；n＝5；

Compound G2: m₁＝OCH₃；M₂＝OCH₂CH₂Cl；M₃＝M₄＝H；R₁＝R₂＝H；n＝6；

Compound G3: m₁＝OCH₃；M₂＝OCH₂CH₂Cl；M₃＝M₄＝H；R₁＝R₂＝H；n＝7；

Compound H1: m₁＝OCH₃；M₂＝I；M₃＝M₄＝H；R₁＝R₂＝H；n＝5；

Compound H2: m₁＝OCH₃；M₂＝I；M₃＝M₄＝H；R₁＝R₂＝H；n＝6；

Compound H3: m₁＝OCH₃；M₂＝I；M₃＝M₄＝H；R₁＝R₂＝H；n＝7；

Compound I1: m₁＝M₃＝OCH₃；M₂＝M₄＝H；R₁＝R₂＝H；n＝5；

Compound I2: m₁＝M₃＝OCH₃；M₂＝M₄＝H；R₁＝R₂＝H；n＝6；

Compound I3: m₁＝M₃＝OCH₃；M₂＝M₄＝H；R₁＝R₂＝H；n＝7；

Compound J1: m₁＝M₂＝OCH₃；M₃＝M₄＝OCH₂CH₂CH₃；R₁＝R₂＝H；n＝5；

Compound J2: m₁＝M₂＝OCH₃；M₃＝M₄＝OCH₂CH₂CH₃；R₁＝R₂＝H；n＝6；

Compound J3: m₁＝M₂＝OCH₃；M₃＝M₄＝OCH₂CH₂CH₃；R₁＝R₂＝H；n＝7；

Compound K1: m₁＝M₂＝OCH₃；M₃＝M₄＝H；R₁＝R₂＝CH₃；n＝5；

Compound K2: m₁＝M₂＝OCH₃；M₃＝M₄＝H；R₁＝R₂＝CH₃；n＝6；

Compound K3: m₁＝M₂＝OCH₃；M₃＝M₄＝H；R₁＝R₂＝CH₃；n＝7；

Compound L1: m₁＝OH；M₃＝H；M₂＝M₄＝Br；R₁＝R₂＝H；n＝5；

Compound L2: m₁＝OH；M₃＝H；M₂＝M₄＝Br；R₁＝R₂＝H；n＝6；

Compound L3: m₁＝OH；M₃＝H；M₂＝M₄＝Br；R₁＝R₂＝H；n＝7；

Compound M1: m₁＝M₂＝CHO；M₃＝M₄＝H；R₁＝R₂＝H；n＝5；

Compound M2: m₁＝M₂＝CHO；M₃＝M₄＝H；R₁＝R₂＝H；n＝6；

Compound M3: m₁＝M₂＝CHO；M₃＝M₄＝H；R₁＝R₂＝H；n＝7；

Compound N1: m₁＝OCH₃；M₂＝M₃＝M₄＝H；R₁＝R₂＝H；n＝5；

Compound N2: m₁＝OCH₃；M₂＝M₃＝M₄＝H；R₁＝R₂＝H；n＝6；

Compound N3: m₁＝OCH₃；M₂＝M₃＝M₄＝H；R₁＝R₂＝H；n＝7；

Compound O1: m₁＝OH；M₂＝M₃＝M₄＝H；R₁＝R₂＝H；n＝5；

Compound O2: m₁＝OH；M₂＝M₃＝M₄＝H；R₁＝R₂＝H；n＝6；

Compound O3: m₁＝OH；M₂＝M₃＝M₄＝H；R₁＝R₂＝H；n＝7；

Compound P1: m₁＝OCH₃；M₂＝OH；M₃＝M₄＝H；R₁＝R₂＝H；n＝5；

Compound P2: m₁＝OCH₃；M₂＝OH；M₃＝M₄＝H；R₁＝R₂＝H；n＝6；

Compound P3: m₁＝OCH₃；M₂＝OH；M₃＝M₄＝H；R₁＝R₂＝H；n＝7；

Compound Q1: m₁＝OCH₃；M₂＝CH₃COO；M₃＝M₄＝H；R₁＝R₂＝H；n＝5；

Compound Q2: m₁＝OCH₃；M₂＝CH₃COO；M₃＝M₄＝H；R₁＝R₂＝H；n＝6；

Compound Q3: m₁＝OCH₃；M₂＝CH₃COO；M₃＝M₄＝H；R₁＝R₂＝H；n＝7；

Compound R1: m₁＝OCH₃；M₂＝Ph；M₃＝M₄＝H；R₁＝R₂＝H；n＝5；

Compound R2: m₁＝OCH₃；M₂＝Ph；M₃＝M₄＝H；R₁＝R₂＝H；n＝6；

Compound R3: m₁＝OCH₃；M₂＝Ph；M₃＝M₄＝H；R₁＝R₂＝H；n＝7。

4. The solid catalyst according to any one of claims 1 to 3, wherein the alcohol ester compound is selected from the group consisting of glycol ester compounds represented by the formula (II),

in the formula (II), R¹And R²Identical or different, each independently selected from C with or without substituents₁-C₂₀Alkyl, C with or without substituents₂-C₂₀Alkenyl, C with or without substituents₂-C₂₀Alkynyl, C with or without substituents₃-C₂₀Cycloalkyl, C with or without substituents₆-C₂₀Aryl, C with or without substituents₇-C₂₀Alkylaryl, C with or without substituents₇-C₂₀Aralkyl and C with or without substituents₁₀-C₂₀The condensed ring aromatic groups are preferably each independently selected from C having or not having a substituent₁-C₁₀Alkyl, C with or without substituents₂-C₁₀Alkenyl, C with or without substituents₃-C₁₀Cycloalkyl, C with or without substituents₆-C₁₀Aryl, C with or without substituents₇-C₁₀Alkylaryl, C with or without substituents₇-C₁₀Aralkyl and C with or without substituents₁₀-C₁₅A condensed ring aryl group, the substituent is selected from hydroxyl, halogen atom, cyano, nitro, amino, mono-C₁-C₆Alkylamino radical, bis-C₁-C₆One or more of alkylamino, aldehyde, carboxyl and heteroatom; m is a divalent linking group, preferably selected from C with or without substituents₁-C₂₀Alkylene, C with or without substituents₃-C₂₀Cycloalkylene and C with or without substituents₆-C₂₀Arylene group, the substituents being selected from nitrogen, oxygen, sulfur, silicon, phosphorus, halogen atoms and C₁-C₂₀Alkyl when the substituent is multiple C₁-C₂₀When alkyl, the substituents are optionally bonded to one or more rings;

preferably, the alcohol ester compound is selected from the group consisting of glycol ester compounds represented by formula (III),

r 'in the formula (III)'₁And R'₂Are the same or different and are each independently selected from C₁-C₁₀Alkyl radical, C₂-C₁₀Alkenyl radical, C₂-C₁₀Alkynyl, C₃-C₂₀Cycloalkyl radical, C₆-C₂₀Aryl radical, C₇-C₂₀Aralkyl and C₇-C₂₀Alkylaryl, preferably selected from C₁-C₆Alkyl radical, C₂-C₆Alkenyl radical, C₂-C₆Alkynyl, C₃-C₁₀Cycloalkyl radical, C₆-C₁₀Aryl radical, C₇-C₁₀Aralkyl and C₇-C₁₀Alkylaryl, said alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl being optionally substituted by one or more substituents selected from halogen, C₁-C₆Alkyl and C₁-C₆One or more substituents in alkoxy; r'₃、R’₄、R’₅、R’₆And R'¹-R’²ⁿThe same or different, each is independently selected from hydrogen, halogen and C₁-C₂₀Alkyl radical, C₂-C₁₀Alkenyl radical, C₂-C₁₀Alkynyl, C₃-C₂₀Cycloalkyl radical, C₆-C₂₀Aryl radical, C₇-C₂₀Alkylaryl group, C₇-C₂₀Aralkyl and C₁₀-C₂₀Condensed ring aryl, preferably selected from hydrogen, halogen, C₁-C₁₀Alkyl radical, C₂-C₆Alkenyl radical, C₂-C₆Alkynyl, C₃-C₁₀Cycloalkyl radical, C₆-C₁₀Aryl radical, C₇-C₁₀Alkylaryl group, C₇-C₁₀Aralkyl and C₁₀-C₁₅A fused ring aryl, said alkyl, alkenyl, alkynyl, cycloalkyl, aryl, alkaryl, aralkyl and fused ring aryl optionally substituted with a substituent selected from halogen, C₁-C₆Alkyl and C₁-C₆One or more substituents in alkoxy; r'₃、R’₄、R’₅、R’₆And R'¹-R’²ⁿOptionally containing heteroatoms, which are one or more of nitrogen, oxygen, sulfur, silicon, halogen and phosphorus; or, R'₃、R’₄、R’₅、R’₆And R'¹-R’²ⁿTwo or two ofMore than one of which are bonded to each other to form a saturated or unsaturated monocyclic ring or a saturated or unsaturated polycyclic ring; wherein n is an integer of 0 to 10, preferably an integer of 1 to 8, more preferably an integer of 2 to 6, and when n is 0, the substituent is R'₃And R'₄Is R 'to carbon atom and substituent'₅And R'₆To the carbon atom of (a);

more preferably, the glycol ester compound is selected from the group consisting of 2, 4-pentanediol dibenzoate, 3-methyl-2, 4-pentanediol dibenzoate, 3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 3, 5-heptanediol di-p-methylbenzoate, 3, 5-heptanediol di-o-methylbenzoate, 3, 5-heptanediol di-p-chlorobenzoate, 3, 5-heptanediol di-p-methoxybenzoate, 3, 5-heptanediol di-o-methoxybenzoate, 3, 5-heptanediol di-m-methoxybenzoate, 2-methyl-3, 5-heptanediol dibenzoate, 4-methyl-3, 5-heptanediol dibenzoate, 6-methyl-3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 5-ethyl-3, 5-heptanediol dibenzoate, 4-propyl-3, 5-heptanediol dibenzoate, 4-butyl-3, 5-heptanediol dibenzoate, 2, 4-dimethyl-3, 5-heptanediol dibenzoate, 2, 6-dimethyl-3, 5-heptanediol dibenzoate, 4-dimethyl-3, 5-heptanediol dibenzoate, 6-dimethyl-3, 5-heptanediol dibenzoate, 4, 4-dimethyl-3, 5-heptanediol dibenzoate, 6-dimethyl-3, 5-heptanediol dibenzoate, 2-methyl-4-ethyl-3, 5-heptanediol dibenzoate, 4-methyl-4-ethyl-3, 5-heptanediol dibenzoate, 2-methyl-4-propyl-3, 5-heptanediol dibenzoate, 4-methyl-4-propyl-3, 5-heptanediol dibenzoate, 6-methyl-2, 4-heptanediol di (p-chlorobenzoic acid) ester, 6-methyl-2, 4-heptanediol di (p-methylbenzoic acid) ester, 6-methyl-2, 4-heptanediol di (m-methylbenzoic acid) ester, 6-methyl-3, 5-heptanediol di (m-methylbenzoic acid) ester, 6-methyl-2, 4-heptanediol di (m-methylbenzoic acid) ester, 2-heptanediol di (p-methylbenzoic acid) ester, and a mixture thereof, 2,2,6, 6-tetramethyl-3, 5-heptanediol dibenzoate, 4-methyl-3, 5-octanediol dibenzoate, 4-ethyl-3, 5-octanediol dibenzoate, 4-propyl-3, 5-octanediol dibenzoate, 4-butyl-3, 5-octanediol dibenzoate, 4-dimethyl-3, 5-octanediol dibenzoate, 4-methyl-4-ethyl-3, 5-octanediol dibenzoate, 2-methyl-6-ethyl-3, 5-octanediol dibenzoate, 5-methyl-4, 6-nonanediol dibenzoate, 5-ethyl-4, 6-nonanediol dibenzoate, 5-propyl-4, 6-nonanediol dibenzoate, 5-butyl-4, 6-nonanediol dibenzoate, 5-dimethyl-4, 6-nonanediol dibenzoate, 5-methyl-4-ethyl-4, 6-nonanediol dibenzoate, 5-phenyl-4, 6-nonanediol dibenzoate, 4, 6-nonanediol dibenzoate and 4-butyl-3, 5-heptanediol dibenzoate, 1, 2-phenylene dibenzoate, 3-methyl-5-tert-butyl-1, 2-phenylene dibenzoate, 3, 5-diisopropyl-1, 2-phenylene dibenzoate, methyl-4, 6-nonanediol dibenzoate, 5-dimethyl-4, 6-nonanediol dibenzoate, 5-methyl-4-ethyl-4, 6-nonanediol dibenzoate, 5-methyl-4-tert-butyl-1, 2-phenylene dibenzoate, 3, 5-diisopropyl-1, 2-dibenzoate, 2-phenylene dibenzoate, and mixtures thereof, 3, 6-dimethyl-1, 2-phenylene dibenzoate, 4-tert-butyl-1, 2-phenylene dibenzoate, 1, 2-naphthalene dibenzoate, 2, 3-naphthalene dibenzoate, 1, 8-naphthyl di-4-methylbenzoate, 1, 8-naphthyl di-3-methylbenzoate, 1, 8-naphthyl di-2-methylbenzoate, 1, 8-naphthyl di-4-ethylbenzoate, 1, 8-naphthyl di-4-n-propylbenzoate, 1, 8-naphthyl di-4-isopropylbenzoate, 1, 8-naphthyl di-4-n-butylbenzoate, 8-naphthyl ester, 1, 8-naphthyl bis-4-isobutylbenzoate, 1, 8-naphthyl bis-4-tert-butylbenzoate, 1, 8-naphthyl bis-4-phenylbenzoate, 1, 8-naphthyl bis-4-fluorobenzoate, 1, 8-naphthyl bis-3-fluorobenzoate, 1, 8-naphthyl bis-2-fluorobenzoate.

5. The solid catalyst according to any one of claims 1 to 4, wherein the aromatic carboxylic acid ester compound is selected from compounds represented by the formula (IV),

in the formula (IV), each R³Identical or different, each independently selected from the group consisting of₁-C₆C of substituents of alkyl radicals and halogen atoms₁-C₈Alkyl, with or without C₁-C₆C of substituents of alkyl radicals and halogen atoms₅-C₁₀Cycloalkyl, with or without the option ofFrom C₁-C₆C of substituents of alkyl radicals and halogen atoms₆-C₁₅Aryl, with or without C₁-C₆C of substituents of alkyl radicals and halogen atoms₇-C₁₅Alkylaryl or with or without C₁-C₆C of substituents of alkyl radicals and halogen atoms₇-C₁₅Aralkyl group of (1); r₄-R₇Can be the same or different, and are independently selected from hydrogen, halogen, with or without C₁-C₆C of substituents of alkyl radicals and halogen atoms₁-C₈Alkyl, with or without C₁-C₆C of substituents of alkyl radicals and halogen atoms₅-C₁₀Cycloalkyl, with or without C₁-C₆C of substituents of alkyl radicals and halogen atoms₆-C₂₀Aryl, with or without C₁-C₆C of substituents of alkyl radicals and halogen atoms₇-C₂₀Alkylaryl or with or without C₁-C₆C of substituents of alkyl radicals and halogen atoms₇-C₂₀An aralkyl group,

preferably, the aromatic carboxylic acid ester compound is preferably a phthalic acid carboxylic acid ester compound; more preferably, the aromatic carboxylic acid ester compound is one or more selected from the group consisting of diethyl phthalate, dipropyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, dipentyl phthalate, dihexyl phthalate, diheptyl phthalate and dioctyl phthalate, and further preferably, the aromatic carboxylic acid ester compound is diisobutyl phthalate,

the diether compound is selected from 1, 3-diether compounds, more preferably from 1, 3-diether compounds represented by formula (V),

r 'in the formula (V)'₁、R'₂、R'₃、R'₄、R'₅And R'₆The same or different, each independentlySelected from hydrogen, halogen, C with or without substituents₁-C₂₀Alkyl, C with or without substituents₃-C₂₀Cycloalkyl, C with or without substituents₆-C₂₀Aryl, C with or without substituents₇-C₂₀Aralkyl and C with or without substituents₇-C₂₀An alkaryl group; r'₇And R'₈Identical or different, each independently selected from C with or without substituents₁-C₂₀Alkyl, C with or without substituents₃-C₂₀Cycloalkyl, C with or without substituents₆-C₂₀Aryl, C with or without substituents₇-C₂₀Aralkyl and C with or without substituents₇-C₂₀Alkylaryl, said substituents selected from hydroxy, halogen, cyano, nitro, amino, mono-C₁-C₁₀Alkylamino radical, bis-C₁-C₁₀Alkylamino groups, aldehyde groups, carboxyl groups, and heteroatoms; optionally, R'₁、R'₂、R'₃、R'₄、R'₅And R'₆Two or more of which are bonded to each other to form a saturated or unsaturated monocyclic or polycyclic ring,

preferably, the diether compound is selected from the group consisting of 2- (2-ethylhexyl) 1, 3-dimethoxypropane, 2-isopropyl-1, 3-dimethoxypropane, 2-butyl-1, 3-dimethoxypropane, 2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-1, 3-dimethoxypropane, 2-phenyl-1, 3-dimethoxypropane, 2- (2-phenylethyl) -1, 3-dimethoxypropane, 2- (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2- (p-chlorophenyl) -1, 3-dimethoxypropane, 2- (diphenylmethyl) -1, 3-dimethoxypropane, 2- (1-naphthyl) -1, 3-dimethoxypropane, 2- (2-fluorophenyl) -1, 3-dimethoxypropane, 2-dicyclohexyl-1, 3-dimethoxypropane, 2-dicyclopentyl-1, 3-dimethoxypropane, 2-diethyl-1, 3-dimethoxypropane, 2-dipropyl-1, 3-dimethoxypropane, 2-diisopropyl-1, 3-dimethoxypropane, 2-dibutyl-1, 3-dimethoxypropane, 2-methyl-2-propyl-1, 3-dimethoxypropane, 2-methyl-2-benzyl-1, 3-dimethoxypropane, 2-methyl-2-ethyl-1, 3-dimethoxypropane, 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-phenyl-1, 3-dimethoxypropane, 2-methyl-2-cyclohexyl-1, 3-dimethoxypropane, 2-bis (p-chlorophenyl) -1, 3-dimethoxypropane, 2-bis (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2-methyl-2-isobutyl-1, 3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane, 2-diphenyl-1, 3-dimethoxypropane, 2-dibenzyl-1, 3-dimethoxypropane, 2-bis (cyclohexylmethyl) -1, 3-dimethoxypropane, 2-isobutyl-2-isopropyl-1, 3-dimethoxypropane, 2- (1-methylbutyl) -2-sec-butyl-1, 3-dimethoxypropane, 2-di-sec-butyl-1, 3-dimethoxypropane, 2, 2-di-tert-butyl-1, 3-dimethoxypropane, 2-dineopentyl-1, 3-dimethoxypropane, 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, 2-isopropyl-2-phenyl-1, 3-dimethoxypropane, 2-phenyl-2-sec-butyl-1, 3-dimethoxypropane, 2-isopropyl-2-benzyl-1, 3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-1, 3-dimethoxypropane, 2-cyclopentyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1, 3-dimethoxypropane, 2-sec-butyl-2-cyclohexyl-1, 3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1, 3-dimethoxypropane, 1-bis (methoxymethyl) -cyclopentadiene, 1-bis (methoxymethyl) -2,3,4, 5-tetramethylcyclopentadiene, 1-bis (methoxymethyl) -2,3,4, 5-tetraphenylcyclopentadiene, 1-bis (methoxymethyl) -2,3,4, 5-tetrafluorocyclopentadiene, 1, 1-bis (methoxymethyl) -3, 4-dicyclopentylcyclopentadiene, 1, 1-bis (methoxymethyl) indene, 1, 1-bis (methoxymethyl) -2, 3-dimethoxyindene, 1, 1-bis (methoxymethyl) -2,3,6, 7-tetrafluoroindene, 1, 1-bis (methoxymethyl) -4,5,6, 7-tetrafluoroindene, 1, 1-bis (methoxymethyl) -4, 7-dimethylindene, 1, 1-bis (methoxymethyl) -3, 6-dimethylindene, 1, 1-bis (methoxymethyl) -4-phenylindene, 1, 1-bis (methoxymethyl) -4-phenyl-2-methylindene, 1-bis (methoxymethyl) -4-phenylindene, 2-methylindene, 2-dimethylindene, 1, 1-bis (methoxymethyl) -4-phenylindene, 1, 1-bis (methoxymethyl) -2-dimethylindene, and the like, 1, 1-bis (methoxymethyl) -4-tetracyclohexylindene, 1-bis (methoxymethyl) -7- (3,3, 3-trifluoropropyl) phenylindene, 1-bis (methoxymethyl) -7-cyclopentylindene, 1-bis (methoxymethyl) -7-isopropylindene, 1-bis (methoxymethyl) -7-cyclohexylindene, 1-bis (methoxymethyl) -7-tert-butylindene, 1-bis (methoxymethyl) -7-tert-butyl-2-methylindene, 1-bis (methoxymethyl) -7-phenylindene, 1-bis (methoxymethyl) -2-phenylindene, 1-bis (methoxymethyl) -7-phenylindene, 1-bis (methoxymethyl) -2-phenylindene, 1-bis (methoxymethyl) -7-phenylindene, 2-phenylindene, 1-bis (methoxymethyl) indene, 1-bis (methoxymethyl) -7-phenylindene, and, 9, 9-bis (methoxymethyl) fluorene, 9-bis (methoxymethyl) -2, 7-dicyclopentylfluorene, 9-bis (methoxymethyl) -1, 8-dichlorofluorene, 9-bis (methoxymethyl) -1, 8-difluorofluorene, 9-bis (methoxymethyl) -1,2,3, 4-tetrahydrofluorene, 9-bis (methoxymethyl) -4-tert-butylfluorene, 1-bis- (methoxymethyl) -2, 5-cyclohexadiene, 1-bis- (methoxymethyl) -benzonaphthalene, 7-bis- (methoxymethyl) -2, 5-norbornadiene, 9-bis- (methoxymethyl) -1, 4-methanodihydronaphthalene, 9-bis- (methoxymethyl) -1, 4-methanodihydroanthracene, 4-bis- (methoxymethyl) -1-phenyl-1, 4-dihydronaphthalene, 4-bis- (methoxymethyl) -1-phenyl-3, 4-dihydronaphthalene, 5-bis- (methoxymethyl) -1,3, 6-cycloheptatriene, and 1-methoxymethyl-1- (1' -methoxyethyl) -2,3,4, 5-tetramethylcyclopentadiene.

6. The solid catalyst according to any one of claims 1 to 5, characterized in that,

the content of the first internal electron donor is 0.001 wt% to 30 wt%, preferably 0.01 wt% to 20 wt%, and more preferably 0.1 wt% to 15 wt%, based on the total amount of the solid catalyst; and/or

The content of the second internal electron donor is 0.001 wt% to 30 wt%, preferably 1 wt% to 30 wt%, more preferably 1 wt% to 25 wt%,

preferably, in the solid catalyst, the molar ratio of the first internal electron donor to the second internal electron donor is (1-100): (100-1), preferably (1-50): (50-1), and more preferably (1-20): (20-1).

7. A catalyst system for the polymerization of olefins comprising the following components or the reaction product of the following components:

1) a solid catalyst component comprising the solid catalyst of any one of claims 1-6;

2) a co-catalyst component comprising an organoaluminum compound; and

optionally, 3) an external electron donor compound.

8. The catalyst system of claim 7, wherein the organoaluminum compound has the formula AlR¹ _dX¹ _3-dIn the formula, R¹Is hydrogen or C_l～C₂₀Hydrocarbyl radical, X¹Is halogen atom, d is more than 0 and less than or equal to 3; preferably, the organoaluminium compound is selected from Al (CH)₃)₃、Al(CH₂CH₃)₃、Al(i-Bu)₃、AlH(CH₂CH₃)₂、AlCl(CH₂CH₃)₂、AlH(i-Bu)₂、AlCl_1.5(CH₂CH₃)_1.5、AlCl(CH₂CH₃)₂And AlCl₂(CH₂CH₃) More preferably Al (CH)₂CH₃)₃And/or Al (i-Bu)₃More preferably, the molar ratio of the aluminum element in the organoaluminum compound to the titanium element in the solid catalyst component is (5-5000): 1, preferably (20-2000): 1.

9. Use of a solid catalyst according to any one of claims 1 to 6 or of a catalyst system according to claim 7 or 8 in the field of olefin polymerization, in particular in the field of propylene polymerization.

10. An olefin polymerization process comprising: subjecting an olefin to a polymerization reaction in the presence of the catalyst system of claim 7 or 8, preferably under conditions comprising: the temperature is 0-150 ℃, preferably 50-90 ℃; the pressure is 0.01MPa to 10MPa, preferably 0.1MPa to 5 MPa; the time is 0.1h to 5h, preferably 0.2h to 3 h.

Technical Field

The invention relates to the field of olefin polymerization, in particular to a solid catalyst and a solid catalyst system for preparing an olefin polymer.

Background

As is well known, when a solid titanium catalyst component containing magnesium, titanium, halogen and an internal electron donor compound as basic components is used in olefin polymerization, the internal electron donor compound plays a decisive role in important indexes such as polymerization activity, isotactic index of polymer, molecular weight and the like, and the development of the internal electron donor compound has an extraordinary significance in the updating of catalysts.

At present, the research on internal electron donors at home and abroad mainly focuses on fatty acid ester and aromatic acid ester compounds (such as patent CN85100997A and derived patents); diethers and diketones (as in patents CN1042547A and CN 1054139A); succinate compounds (as in patent CN 1313869A); glycol ester compounds (such as patent CN1453298A), etc.

Although the catalyst prepared by taking the compound as the internal electron donor is widely applied, the compound has certain problems in practical application. For example, the catalyst using the binary aromatic carboxylic ester compound has low catalytic activity, and the molecular weight distribution of the obtained polymer is narrow; although the catalyst using the 1, 3-diether compound has higher activity and good hydrogen regulation sensitivity, the molecular weight distribution of the obtained polymer is narrow, which is not beneficial to the development of different grades of the polymer; the succinate compound is used as an internal electron donor, and the method has the advantages that the molecular weight distribution of the synthesized polypropylene is wider, and the defect that the stereospecificity of the polymer needs to be improved.

Disclosure of Invention

In view of the problems in the prior art, an object of the present invention is to provide a solid catalyst for preparing an olefin polymer, wherein a pillared aromatic hydrocarbon compound represented by formula (I) or a derivative thereof is introduced as an internal electron donor into a solid catalyst component, so that the stereospecificity of the catalyst can be improved, and the molecular weight of a polymerization product can be increased.

It is a second object of the present invention to provide a catalyst system for the polymerization of olefins comprising the solid catalyst component provided for the first object.

The third object of the present invention is to provide an application corresponding to the first object and the second object.

The fourth object of the present invention is to provide a process for polymerizing olefins corresponding to the second object.

In order to achieve one of the purposes, the technical scheme adopted by the invention is as follows:

a solid catalyst for the polymerization of olefins comprising the following components or the reaction product of the following components: magnesium element, titanium element, halogen, a first internal electron donor and a second internal electron donor,

wherein the first internal electron donor comprises a columnar aromatic hydrocarbon compound shown as a formula (I),

in the formula (I), the compound is shown in the specification,

is a basic unit, wherein M₁、M₂、M₃、M₄、R₁And R₂The same or different, each independently selected from hydrogen, hydroxy, cyano, nitro, amino, -CHO, -R₃CHO、-C(O)R₄、-C(O)OH、-R₃C(O)OH、-C(O)OR₄、-R₃C(O)OR₄、-OR₄、-R₃OR₄Halogen atom, C with or without substituents₁-C₁₀Alkyl and C with or without substituents₁-C₁₀Alkoxy, wherein R₃Is C with or without substituents₁-C₆Alkylene radical, R₄Is C with or without substituents₁-C₆Alkyl, the substituents being selected from the group consisting of hydroxy, amino, -CHO, -C (O) OH, halogen, C₁-C₆Alkyl radical, C₁-C₆Alkoxy and heteroatoms;

n represents the number of basic units and is an integer of 3-20;

when the adjacent groups within or between adjacent base units are-C (O) R₄、-C(O)OR₄、-R₃C(O)OR₄、-OR₄、-R₃OR₄C with or without substituents₁-C₁₀Hydrocarbyl and C with or without substituents₁-C₁₀Hydrocarbyloxy, two adjacent groups are optionally linked to each other to form a cyclic structure selected from the group consisting of a saturated or unsaturated monocyclic ring, a saturated or unsaturated polycyclic ring, and combinations thereof,

the second internal electron donor is selected from one or more of alcohol ester compounds, aromatic carboxylic acid ester compounds, diether compounds and succinate compounds.

According to the present invention, the base unit may also be head-to-head connected as shown in the following formula (a), thereby forming an isomer. Said isomers are also intended to be within the scope of the present invention.

The inventor of the present application has found that by introducing a columnar aromatic hydrocarbon compound represented by formula (I) or a derivative thereof as an internal electron donor into a solid catalyst component, the stereospecificity of the catalyst can be improved, and the molecular weight of a polymerization product can be increased.

According to the invention, M on different base units₁、M₂、M₃、M₄、R₁And R₂May be the same or different.

In some preferred embodiments of the invention, in formula (I), M₁、M₂、M₃And M₄The same or different, each independently selected from hydrogen, hydroxy, amino, -CHO, fluoro, chloro, bromo, iodo, C₁-C₁₀Alkyl, halogen atom substituted C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy and halogen substituted C₁-C₁₀An alkoxy group.

In some preferred embodiments of the invention, R₁And R₂The same or different, each independently selected from hydrogen, C with or without substituent₁-C₁₀Alkyl and C with or without substituents₁-C₁₀An alkoxy group.

In some preferred embodiments of the invention, n is an integer from 4 to 10, such as 4,5,6,7, 8, 9, 10. In some preferred embodiments of the invention, n is an integer from 4 to 7.

In some preferred embodiments of the invention, in formula (I), M₁、M₂、M₃And M₄The same or different, each independently selected from hydrogen and hydroxylAmino, -CHO, fluorine, chlorine, bromine, iodine, C₁-C₆Alkoxy and halogen substituted C₁-C₆An alkoxy group.

In some preferred embodiments of the invention, R₁And R₂The same or different, each independently selected from hydrogen, C with or without substituent₁-C₆Alkyl and C with or without substituents₁-C₆An alkoxy group.

In some preferred embodiments of the invention, in formula (I), M₁And M₂Are the same or different and are each independently selected from C₁-C₆An alkoxy group.

In some preferred embodiments of the invention, in formula (I), M₃And M₄Are all hydrogen.

In some preferred embodiments of the present invention, the column arene compound represented by formula (I) is selected from one or more of the following compounds:

compound a 1: m₁＝M₂＝OCH₃；M₃＝M₄＝H；R₁＝R₂＝H；n＝5；

Compound a 2: m₁＝M₂＝OCH₃；M₃＝M₄＝H；R₁＝R₂＝H；n＝6；

Compound a 3: m₁＝M₂＝OCH₃；M₃＝M₄＝H；R₁＝R₂＝H；n＝7；

Compound B1: m₁＝M₂＝OCH₂CH₃；M₃＝M₄＝H；R₁＝R₂＝H；n＝5；

Compound B2: m₁＝M₂＝OCH₂CH₃；M₃＝M₄＝H；R₁＝R₂＝H；n＝6；

Compound B3: m₁＝M₂＝OCH₂CH₃；M₃＝M₄＝H；R₁＝R₂＝H；n＝7；

Compound C1: m₁＝M₂＝OCH₂CH₂CH₃；M₃＝M₄＝H；R₁＝R₂＝H；n＝5；

Compound C2: m₁＝M₂＝OCH₂CH₂CH₃；M₃＝M₄＝H；R₁＝R₂＝H；n＝6；

Compound C3: m₁＝M₂＝OCH₂CH₂CH₃；M₃＝M₄＝H；R₁＝R₂＝H；n＝7；

Compound D1: m₁＝M₂＝OCH(CH₃)₂；M₃＝M₄＝H；R₁＝R₂＝H；n＝5；

Compound D2: m₁＝M₂＝OCH(CH₃)₂；M₃＝M₄＝H；R₁＝R₂＝H；n＝6；

Compound D3: m₁＝M₂＝OCH(CH₃)₂；M₃＝M₄＝H；R₁＝R₂＝H；n＝7；

Compound E1: m₁＝OCH₃；M₂＝OCH₂CH₂CH₃；M₃＝M₄＝H；R₁＝R₂＝H；n＝5；

Compound E2: m₁＝OCH₃；M₂＝OCH₂CH₂CH₃；M₃＝M₄＝H；R₁＝R₂＝H；n＝6；

Compound E3: m₁＝OCH₃；M₂＝OCH₂CH₂CH₃；M₃＝M₄＝H；R₁＝R₂＝H；n＝7；

Compound F1: m₁＝OCH₃；M₂＝CHO；M₃＝M₄＝H；R₁＝R₂＝H；n＝5；

Compound F2: m₁＝OCH₃；M₂＝CHO；M₃＝M₄＝H；R₁＝R₂＝H；n＝6；

Compound F3: m₁＝OCH₃；M₂＝CHO；M₃＝M₄＝H；R₁＝R₂＝H；n＝7；

Compound G1: m₁＝OCH₃；M₂＝OCH₂CH₂Cl；M₃＝M₄＝H；R₁＝R₂＝H；n＝5；

Compound G2: m₁＝OCH₃；M₂＝OCH₂CH₂Cl；M₃＝M₄＝H；R₁＝R₂＝H；n＝6；

Compound G3: m₁＝OCH₃；M₂＝OCH₂CH₂Cl；M₃＝M₄＝H；R₁＝R₂＝H；n＝7；

Compound H1: m₁＝OCH₃；M₂＝I；M₃＝M₄＝H；R₁＝R₂＝H；n＝5；

Compound H2: m₁＝OCH₃；M₂＝I；M₃＝M₄＝H；R₁＝R₂＝H；n＝6；

Compound H3: m₁＝OCH₃；M₂＝I；M₃＝M₄＝H；R₁＝R₂＝H；n＝7；

Compound I1: m₁＝M₃＝OCH₃；M₂＝M₄＝H；R₁＝R₂＝H；n＝5；

Compound I2: m₁＝M₃＝OCH₃；M₂＝M₄＝H；R₁＝R₂＝H；n＝6；

Compound I3: m₁＝M₃＝OCH₃；M₂＝M₄＝H；R₁＝R₂＝H；n＝7；

Compound J1: m₁＝M₂＝OCH₃；M₃＝M₄＝OCH₂CH₂CH₃；R₁＝R₂＝H；n＝5；

Compound J2: m₁＝M₂＝OCH₃；M₃＝M₄＝OCH₂CH₂CH₃；R₁＝R₂＝H；n＝6；

Compound J3: m₁＝M₂＝OCH₃；M₃＝M₄＝OCH₂CH₂CH₃；R₁＝R₂＝H；n＝7；

Compound K1: m₁＝M₂＝OCH₃；M₃＝M₄＝H；R₁＝R₂＝CH₃；n＝5；

Compound K2: m₁＝M₂＝OCH₃；M₃＝M₄＝H；R₁＝R₂＝CH₃；n＝6；

Compound K3: m₁＝M₂＝OCH₃；M₃＝M₄＝H；R₁＝R₂＝CH₃；n＝7；

Compound L1: m₁＝OH；M₃＝H；M₂＝M₄＝Br；R₁＝R₂＝H；n＝5；

Compound L2: m₁＝OH；M₃＝H；M₂＝M₄＝Br；R₁＝R₂＝H；n＝6；

Compound L3: m₁＝OH；M₃＝H；M₂＝M₄＝Br；R₁＝R₂＝H；n＝7；

Compound M1: m₁＝M₂＝CHO；M₃＝M₄＝H；R₁＝R₂＝H；n＝5；

Compound M2: m₁＝M₂＝CHO；M₃＝M₄＝H；R₁＝R₂＝H；n＝6；

Compound M3: m₁＝M₂＝CHO；M₃＝M₄＝H；R₁＝R₂＝H；n＝7；

Compound N1: m₁＝OCH₃；M₂＝M₃＝M₄＝H；R₁＝R₂＝H；n＝5；

Compound N2: m₁＝OCH₃；M₂＝M₃＝M₄＝H；R₁＝R₂＝H；n＝6；

Compound N3: m₁＝OCH₃；M₂＝M₃＝M₄＝H；R₁＝R₂＝H；n＝7；

Compound O1: m₁＝OH；M₂＝M₃＝M₄＝H；R₁＝R₂＝H；n＝5；

Compound O2: m₁＝OH；M₂＝M₃＝M₄＝H；R₁＝R₂＝H；n＝6；

Compound O3: m₁＝OH；M₂＝M₃＝M₄＝H；R₁＝R₂＝H；n＝7；

Compound P1: m₁＝OCH₃；M₂＝OH；M₃＝M₄＝H；R₁＝R₂＝H；n＝5；

Compound P2: m₁＝OCH₃；M₂＝OH；M₃＝M₄＝H；R₁＝R₂＝H；n＝6；

Compound P3: m₁＝OCH₃；M₂＝OH；M₃＝M₄＝H；R₁＝R₂＝H；n＝7；

Compound Q1: m₁＝OCH₃；M₂＝CH₃COO；M₃＝M₄＝H；R₁＝R₂＝H；n＝5；

Compound Q2: m₁＝OCH₃；M₂＝CH₃COO；M₃＝M₄＝H；R₁＝R₂＝H；n＝6；

Compound Q3: m₁＝OCH₃；M₂＝CH₃COO；M₃＝M₄＝H；R₁＝R₂＝H；n＝7；

Compound R1: m₁＝OCH₃；M₂＝Ph；M₃＝M₄＝H；R₁＝R₂＝H；n＝5；

Compound R2: m₁＝OCH₃；M₂＝Ph；M₃＝M₄＝H；R₁＝R₂＝H；n＝6；

Compound R3: m₁＝OCH₃；M₂＝Ph；M₃＝M₄＝H；R₁＝R₂＝H；n＝7。

In some preferred embodiments of the present invention, the alcohol ester compound is selected from the group consisting of glycol ester compounds represented by formula (II),

in the formula (II), R¹And R²Identical or different, each independently selected from C with or without substituents₁-C₂₀Alkyl, C with or without substituents₂-C₂₀Alkenyl, C with or without substituents₂-C₂₀Alkynyl, C with or without substituents₃-C₂₀Cycloalkyl, C with or without substituents₆-C₂₀Aryl, C with or without substituents₇-C₂₀Alkylaryl, C with or without substituents₇-C₂₀Aralkyl and C with or without substituents₁₀-C₂₀The condensed ring aromatic groups are preferably each independently selected from C having or not having a substituent₁-C₁₀Alkyl radicalC with or without substituents₂-C₁₀Alkenyl, C with or without substituents₃-C₁₀Cycloalkyl, C with or without substituents₆-C₁₀Aryl, C with or without substituents₇-C₁₀Alkylaryl, C with or without substituents₇-C₁₀Aralkyl and C with or without substituents₁₀-C₁₅A condensed ring aryl group, the substituent is selected from hydroxyl, halogen atom, cyano, nitro, amino, mono-C₁-C₆Alkylamino radical, bis-C₁-C₆One or more of alkylamino, aldehyde, carboxyl and heteroatom; m is a divalent linking group, preferably selected from C with or without substituents₁-C₂₀Alkylene, C with or without substituents₃-C₂₀Cycloalkylene and C with or without substituents₆-C₂₀Arylene group, the substituents being selected from nitrogen, oxygen, sulfur, silicon, phosphorus, halogen atoms and C₁-C₂₀Alkyl when the substituent is multiple C₁-C₂₀When alkyl, the substituents are optionally bonded to one or more rings.

In some preferred embodiments of the present invention, the alcohol ester compound is selected from the group consisting of glycol ester compounds represented by formula (III),

r 'in the formula (III)'₁And R'₂Are the same or different and are each independently selected from C₁-C₁₀Alkyl radical, C₂-C₁₀Alkenyl radical, C₂-C₁₀Alkynyl, C₃-C₂₀Cycloalkyl radical, C₆-C₂₀Aryl radical, C₇-C₂₀Aralkyl and C₇-C₂₀Alkylaryl, preferably selected from C₁-C₆Alkyl radical, C₂-C₆Alkenyl radical, C₂-C₆Alkynyl, C₃-C₁₀Cycloalkyl radical, C₆-C₁₀Aryl radical, C₇-C₁₀Aralkyl and C₇-C₁₀Alkylaryl group, eSaid alkyl, alkenyl, cycloalkyl, aryl, aralkyl or alkaryl being optionally substituted by a halogen, C₁-C₆Alkyl and C₁-C₆One or more substituents in alkoxy; r'₃、R’₄、R’₅、R’₆And R'¹-R’²ⁿThe same or different, each is independently selected from hydrogen, halogen and C₁-C₂₀Alkyl radical, C₂-C₁₀Alkenyl radical, C₂-C₁₀Alkynyl, C₃-C₂₀Cycloalkyl radical, C₆-C₂₀Aryl radical, C₇-C₂₀Alkylaryl group, C₇-C₂₀Aralkyl and C₁₀-C₂₀Condensed ring aryl, preferably selected from hydrogen, halogen, C₁-C₁₀Alkyl radical, C₂-C₆Alkenyl radical, C₂-C₆Alkynyl, C₃-C₁₀Cycloalkyl radical, C₆-C₁₀Aryl radical, C₇-C₁₀Alkylaryl group, C₇-C₁₀Aralkyl and C₁₀-C₁₅A fused ring aryl, said alkyl, alkenyl, alkynyl, cycloalkyl, aryl, alkaryl, aralkyl and fused ring aryl optionally substituted with a substituent selected from halogen, C₁-C₆Alkyl and C₁-C₆One or more substituents in alkoxy; r'₃、R’₄、R’₅、R’₆And R'¹-R’²ⁿOptionally containing heteroatoms, which are one or more of nitrogen, oxygen, sulfur, silicon, halogen and phosphorus; or, R'₃、R’₄、R’₅、R’₆And R'¹-R’²ⁿTwo or more of which are bonded to each other to form a saturated or unsaturated monocyclic ring or a saturated or unsaturated polycyclic ring; wherein n is an integer of 0 to 10, preferably an integer of 1 to 8, more preferably an integer of 2 to 6, and when n is 0, the substituent is R'₃And R'₄Is R 'to carbon atom and substituent'₅And R'₆Is bonded to the carbon atom(s) of (a).

In some preferred embodiments of the present invention, the glycol ester compound is selected from the group consisting of 2, 4-pentanediol dibenzoate, 3-methyl-2, 4-pentanediol dibenzoate, 3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 3, 5-heptanediol di-p-methylbenzoate, 3, 5-heptanediol di-o-methylbenzoate, 3, 5-heptanediol di-p-chlorobenzoate, 3, 5-heptanediol di-o-chlorobenzoate, 3, 5-heptanediol di-p-methoxybenzoate, 3, 5-heptanediol di-o-methoxybenzoate, 3, 5-heptanediol di-m-methoxybenzoate, 2-methyl-3, 5-heptanediol dibenzoate, 4-methyl-3, 5-heptanediol dibenzoate, 6-methyl-3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 5-ethyl-3, 5-heptanediol dibenzoate, 4-propyl-3, 5-heptanediol dibenzoate, 4-butyl-3, 5-heptanediol dibenzoate, 2, 4-dimethyl-3, 5-heptanediol dibenzoate, 2, 6-dimethyl-3, 5-heptanediol dibenzoate, 4-dimethyl-3, 5-heptanediol dibenzoate, 6-dimethyl-3, 5-heptanediol dibenzoate, 4, 6-dimethyl-3, 5-heptanediol dibenzoate, a salt thereof, and a salt thereof, 4, 4-dimethyl-3, 5-heptanediol dibenzoate, 6-dimethyl-3, 5-heptanediol dibenzoate, 2-methyl-4-ethyl-3, 5-heptanediol dibenzoate, 4-methyl-4-ethyl-3, 5-heptanediol dibenzoate, 2-methyl-4-propyl-3, 5-heptanediol dibenzoate, 4-methyl-4-propyl-3, 5-heptanediol dibenzoate, 6-methyl-2, 4-heptanediol di (p-chlorobenzoic acid) ester, 6-methyl-2, 4-heptanediol di (p-methylbenzoic acid) ester, 6-methyl-2, 4-heptanediol di (m-methylbenzoic acid) ester, 6-methyl-3, 5-heptanediol di (m-methylbenzoic acid) ester, 6-methyl-2, 4-heptanediol di (m-methylbenzoic acid) ester, 6-methyl-4-heptanediol di (p-methylbenzoic acid) ester, 2, 5-heptanediol dibenzoate, 2-methyl-4-heptanediol di (p-methylbenzoic acid) ester, 4-methylbenzoic acid, 4-methyl ester, 4-heptanediol di (m-methylbenzoic acid) ester, 4-methylbenzoic acid, and mixtures thereof, 2,2,6, 6-tetramethyl-3, 5-heptanediol dibenzoate, 4-methyl-3, 5-octanediol dibenzoate, 4-ethyl-3, 5-octanediol dibenzoate, 4-propyl-3, 5-octanediol dibenzoate, 4-butyl-3, 5-octanediol dibenzoate, 4-dimethyl-3, 5-octanediol dibenzoate, 4-methyl-4-ethyl-3, 5-octanediol dibenzoate, 2-methyl-6-ethyl-3, 5-octanediol dibenzoate, 5-methyl-4, 6-nonanediol dibenzoate, 5-ethyl-4, 6-nonanediol dibenzoate, 5-propyl-4, 6-nonanediol dibenzoate, 5-butyl-4, 6-nonanediol dibenzoate, 5-dimethyl-4, 6-nonanediol dibenzoate, 5-methyl-4-ethyl-4, 6-nonanediol dibenzoate, 5-phenyl-4, 6-nonanediol dibenzoate, 4, 6-nonanediol dibenzoate and 4-butyl-3, 5-heptanediol dibenzoate, 1, 2-phenylene dibenzoate, 3-methyl-5-tert-butyl-1, 2-phenylene dibenzoate, 3, 5-diisopropyl-1, 2-phenylene dibenzoate, methyl-4, 6-nonanediol dibenzoate, 5-dimethyl-4, 6-nonanediol dibenzoate, 5-methyl-4-ethyl-4, 6-nonanediol dibenzoate, 5-methyl-4-tert-butyl-1, 2-phenylene dibenzoate, 3, 5-diisopropyl-1, 2-dibenzoate, 2-phenylene dibenzoate, and mixtures thereof, 3, 6-dimethyl-1, 2-phenylene dibenzoate, 4-tert-butyl-1, 2-phenylene dibenzoate, 1, 2-naphthalene dibenzoate, 2, 3-naphthalene dibenzoate, 1, 8-naphthyl di-4-methylbenzoate, 1, 8-naphthyl di-3-methylbenzoate, 1, 8-naphthyl di-2-methylbenzoate, 1, 8-naphthyl di-4-ethylbenzoate, 1, 8-naphthyl di-4-n-propylbenzoate, 1, 8-naphthyl di-4-isopropylbenzoate, 1, 8-naphthyl di-4-n-butylbenzoate, 8-naphthyl ester, 1, 8-naphthyl bis-4-isobutylbenzoate, 1, 8-naphthyl bis-4-tert-butylbenzoate, 1, 8-naphthyl bis-4-phenylbenzoate, 1, 8-naphthyl bis-4-fluorobenzoate, 1, 8-naphthyl bis-3-fluorobenzoate, 1, 8-naphthyl bis-2-fluorobenzoate.

In some preferred embodiments of the present invention, the aromatic carboxylic acid ester compound is selected from compounds represented by formula (IV),

in the formula (IV), each R³Identical or different, each independently selected from the group consisting of₁-C₆C of substituents of alkyl radicals and halogen atoms₁-C₈Alkyl, with or without C₁-C₆C of substituents of alkyl radicals and halogen atoms₅-C₁₀Cycloalkyl, with or without C₁-C₆C of substituents of alkyl radicals and halogen atoms₆-C₁₅Aryl, with or without C₁-C₆C of substituents of alkyl radicals and halogen atoms₇-C₁₅Alkylaryl or with or without C₁-C₆C of substituents of alkyl radicals and halogen atoms₇-C₁₅Aralkyl group of (1); r₄-R₇Can be the same or different, and are independently selected from hydrogen, halogen, with or without C₁-C₆C of substituents of alkyl radicals and halogen atoms₁-C₈Alkyl, with or without C₁-C₆C of substituents of alkyl radicals and halogen atoms₅-C₁₀Cycloalkyl, with or without C₁-C₆C of substituents of alkyl radicals and halogen atoms₆-C₂₀Aryl, with or without C₁-C₆C of substituents of alkyl radicals and halogen atoms₇-C₂₀Alkylaryl or with or without C₁-C₆C of substituents of alkyl radicals and halogen atoms₇-C₂₀An aralkyl group.

In some preferred embodiments of the present invention, the aromatic carboxylic acid ester-based compound is preferably a phthalic acid carboxylic acid ester-based compound; more preferably, the aromatic carboxylic acid ester compound is one or more selected from the group consisting of diethyl phthalate, dipropyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, dipentyl phthalate, dihexyl phthalate, diheptyl phthalate and dioctyl phthalate, and still more preferably, the aromatic carboxylic acid ester compound is diisobutyl phthalate.

In some preferred embodiments of the present invention, the diether compound is selected from 1, 3-diether compounds, more preferably from 1, 3-diether compounds represented by formula (V),

r 'in the formula (V)'₁、R'₂、R'₃、R'₄、R'₅And R'₆The same or different, each independently selected from hydrogen, halogen, C with or without substituent₁-C₂₀Alkyl, C with or without substituents₃-C₂₀Cycloalkyl, C with or without substituents₆-C₂₀Aryl, C with or without substituents₇-C₂₀Aralkyl and C with or without substituents₇-C₂₀An alkaryl group; r'₇And R'₈Identical or different, each independently selected from C with or without substituents₁-C₂₀Alkyl, C with or without substituents₃-C₂₀Cycloalkyl, C with or without substituents₆-C₂₀Aryl, C with or without substituents₇-C₂₀Aralkyl and C with or without substituents₇-C₂₀Alkylaryl, said substituents selected from hydroxy, halogen, cyano, nitro, amino, mono-C₁-C₁₀Alkylamino radical, bis-C₁-C₁₀Alkylamino groups, aldehyde groups, carboxyl groups, and heteroatoms; optionally, R'₁、R'₂、R'₃、R'₄、R'₅And R'₆Two or more of which are bonded to each other to form a saturated or unsaturated monocyclic or polycyclic ring.

In some preferred embodiments of the invention, the diether compound is selected from the group consisting of 2- (2-ethylhexyl) 1, 3-dimethoxypropane, 2-isopropyl-1, 3-dimethoxypropane, 2-butyl-1, 3-dimethoxypropane, 2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-1, 3-dimethoxypropane, 2-phenyl-1, 3-dimethoxypropane, 2- (2-phenylethyl) -1, 3-dimethoxypropane, 2- (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2- (p-chlorophenyl) -1, 3-dimethoxypropane, 2- (diphenylmethyl) -1, 3-dimethoxypropane, 2- (1-naphthyl) -1, 3-dimethoxypropane, 2- (2-fluorophenyl) -1, 3-dimethoxypropane, 2-dicyclohexyl-1, 3-dimethoxypropane, 2-dicyclopentyl-1, 3-dimethoxypropane, 2-diethyl-1, 3-dimethoxypropane, 2-dipropyl-1, 3-dimethoxypropane, 2-diisopropyl-1, 3-dimethoxypropane, 2-dibutyl-1, 3-dimethoxypropane, 2-methyl-2-propyl-1, 3-dimethoxypropane, 2-methyl-2-benzyl-1, 3-dimethoxypropane, 2-methyl-2-ethyl-1, 3-dimethoxypropane, 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-phenyl-1, 3-dimethoxypropane, 2-methyl-2-cyclohexyl-1, 3-dimethoxypropane, 2-bis (p-chlorophenyl) -1, 3-dimethoxypropane, 2-bis (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2-methyl-2-isobutyl-1, 3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane, 2-diphenyl-1, 3-dimethoxypropane, 2-dibenzyl-1, 3-dimethoxypropane, 2-bis (cyclohexylmethyl) -1, 3-dimethoxypropane, 2-isobutyl-2-isopropyl-1, 3-dimethoxypropane, 2- (1-methylbutyl) -2-sec-butyl-1, 3-dimethoxypropane, 2-di-sec-butyl-1, 3-dimethoxypropane, 2, 2-di-tert-butyl-1, 3-dimethoxypropane, 2-dineopentyl-1, 3-dimethoxypropane, 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, 2-isopropyl-2-phenyl-1, 3-dimethoxypropane, 2-phenyl-2-sec-butyl-1, 3-dimethoxypropane, 2-isopropyl-2-benzyl-1, 3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-1, 3-dimethoxypropane, 2-cyclopentyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1, 3-dimethoxypropane, 2-sec-butyl-2-cyclohexyl-1, 3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1, 3-dimethoxypropane, 1-bis (methoxymethyl) -cyclopentadiene, 1-bis (methoxymethyl) -2,3,4, 5-tetramethylcyclopentadiene, 1-bis (methoxymethyl) -2,3,4, 5-tetraphenylcyclopentadiene, 1-bis (methoxymethyl) -2,3,4, 5-tetrafluorocyclopentadiene, 1, 1-bis (methoxymethyl) -3, 4-dicyclopentylcyclopentadiene, 1, 1-bis (methoxymethyl) indene, 1, 1-bis (methoxymethyl) -2, 3-dimethoxyindene, 1, 1-bis (methoxymethyl) -2,3,6, 7-tetrafluoroindene, 1, 1-bis (methoxymethyl) -4,5,6, 7-tetrafluoroindene, 1, 1-bis (methoxymethyl) -4, 7-dimethylindene, 1, 1-bis (methoxymethyl) -3, 6-dimethylindene, 1, 1-bis (methoxymethyl) -4-phenylindene, 1, 1-bis (methoxymethyl) -4-phenyl-2-methylindene, 1-bis (methoxymethyl) -4-phenylindene, 2-methylindene, 2-dimethylindene, 1, 1-bis (methoxymethyl) -4-phenylindene, 1, 1-bis (methoxymethyl) -2-dimethylindene, and the like, 1, 1-bis (methoxymethyl) -4-tetracyclohexylindene, 1-bis (methoxymethyl) -7- (3,3, 3-trifluoropropyl) phenylindene, 1-bis (methoxymethyl) -7-cyclopentylindene, 1-bis (methoxymethyl) -7-isopropylindene, 1-bis (methoxymethyl) -7-cyclohexylindene, 1-bis (methoxymethyl) -7-tert-butylindene, 1-bis (methoxymethyl) -7-tert-butyl-2-methylindene, 1-bis (methoxymethyl) -7-phenylindene, 1-bis (methoxymethyl) -2-phenylindene, 1-bis (methoxymethyl) -7-phenylindene, 1-bis (methoxymethyl) -2-phenylindene, 1-bis (methoxymethyl) -7-phenylindene, 2-phenylindene, 1-bis (methoxymethyl) indene, 1-bis (methoxymethyl) -7-phenylindene, and, 9, 9-bis (methoxymethyl) fluorene, 9-bis (methoxymethyl) -2, 7-dicyclopentylfluorene, 9-bis (methoxymethyl) -1, 8-dichlorofluorene, 9-bis (methoxymethyl) -1, 8-difluorofluorene, 9-bis (methoxymethyl) -1,2,3, 4-tetrahydrofluorene, 9-bis (methoxymethyl) -4-tert-butylfluorene, 1-bis- (methoxymethyl) -2, 5-cyclohexadiene, 1-bis- (methoxymethyl) -benzonaphthalene, 7-bis- (methoxymethyl) -2, 5-norbornadiene, 9-bis- (methoxymethyl) -1, 4-methanodihydronaphthalene, 9-bis- (methoxymethyl) -1, 4-methanodihydroanthracene, 4-bis- (methoxymethyl) -1-phenyl-1, 4-dihydronaphthalene, 4-bis- (methoxymethyl) -1-phenyl-3, 4-dihydronaphthalene, 5-bis- (methoxymethyl) -1,3, 6-cycloheptatriene, and 1-methoxymethyl-1- (1' -methoxyethyl) -2,3,4, 5-tetramethylcyclopentadiene.

In some preferred embodiments of the present invention, the first internal electron donor is present in an amount of 0.001 wt% to 30 wt%, preferably 0.01 wt% to 20 wt%, and more preferably 0.1 wt% to 15 wt%, based on the total amount of the solid catalyst.

In some preferred embodiments of the present invention, the second internal electron donor is present in an amount of 0.001 wt% to 30 wt%, preferably 1 wt% to 30 wt%, more preferably 1 wt% to 25 wt%, based on the total amount of the solid catalyst.

In some preferred embodiments of the present invention, the molar ratio of the first internal electron donor to the second internal electron donor in the solid catalyst is (1-100): (100-1), preferably (1-50): (50-1), and more preferably (1-20): (20-1).

According to the invention, the solid catalyst component comprises a titanium element, a magnesium element and an internal electron donor, and is a reaction product of a titanium compound, a magnesium compound and the internal electron donor. Since the present invention improves the performance of the olefin polymerization catalyst by changing the external electron donor, the method of preparing the solid catalyst component by the reaction as described above in the present invention may be performed according to a method conventionally used in the art, for example, methods disclosed in CN1506384, CN1091748, CN85100997, CN102399326A, US4540679, and the like, the disclosure of which is incorporated herein by reference.

The preparation method of the solid catalyst component in the present invention includes, but is not limited to, the following methods:

the method comprises the following steps: adding an inert solvent into a magnesium compound, adding an organic epoxy compound and an organic phosphorus compound, dissolving, adding a precipitation aid and a titanium compound, and precipitating a solid; adding an internal electron donor to make it be carried on the solid, and treating with titanium tetrahalide and inert diluent.

The method 2 comprises the following steps: dissolving solid magnesium compound in organic alcohol compound such as 2-ethylhexanol in inert solvent such as decane or toluene, adding precipitation assistant and titanium compound after dissolving, and precipitating solid; adding an internal electron donor to make it be carried on the solid, and treating with titanium compound and inert diluent.

The method 3 comprises the following steps: dispersing a magnesium halide alcohol compound into a titanium compound at a low temperature (such as below-5 ℃), heating to a high temperature (such as above 50 ℃), adding an internal electron donor compound during heating, filtering, treating the obtained precipitate with a titanium compound, and washing the precipitate to obtain the solid catalyst component.

The method 4 comprises the following steps: preparing an alkoxy magnesium carrier and an inert diluent into a suspension, then reacting with a mixture formed by a titanium compound and the inert diluent, filtering, carrying out contact reaction on the obtained precipitate, the titanium compound and an internal electron donor compound, and washing the precipitate to obtain the solid catalyst component.

According to a preferred embodiment of the present invention, a titanium compound or a mixture of a titanium compound and an inert solvent (such as hexane, heptane, octane, decane, toluene, etc.) precooled to-15 to-40 ℃ is mixed with a magnesium compound, and the temperature of the mixture is raised to 90 to 110 ℃ in stages and maintained for 0.1 to 2 hours, and an internal electron donor is added during the raising of the temperature. Then solid-liquid separation is carried out, the obtained solid phase is treated for at least 2 times by using the titanium compound again, and is washed by using a solvent, and finally, the solid catalyst component is obtained by vacuum drying.

According to the present invention, the magnesium compound may be various magnesium compounds conventionally used in the art for preparing olefin polymerization catalysts, and for example, the magnesium compound may be selected from at least one of magnesium dihalides, alkoxy magnesium, alkyl magnesium, hydrates of magnesium dihalides, alcoholates of magnesium dihalides, and derivatives in which one halogen atom in the molecule of magnesium dihalide is substituted with hydrocarbyloxy group or halohydrocarbyloxy group. According to a preferred embodiment of the invention, the magnesium compound is an alcoholate of magnesium dihalide.

According to a preferred embodiment of the invention, the alcoholate of magnesium dihalide has a spherical magnesium alcoholate of formula (VI),

MgX₂·m(R’OH)·nE·qH₂o type (VI)

In formula (VI): x is chlorine or bromine; r' is C₁-C₄Alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl), m is 0.5 to 4.0; e is an ether or ester electron donor compound, n is 0-1.0, wherein the ether or ester can be an ether or ester which can be used as an electron donor and is known in the art, and can also be an internal electron donor and/or an external electron donor used in the invention; q is 0 to 0.8.

According to a preferred embodiment of the invention, in formula (VI), X is chlorine or bromine; r' is C1-C4 alkyl, m is 1.5-3.5; n and q are both 0.

According to a preferred embodiment of the invention, the magnesium compound is MgCl₂·m(CH₃CH₂OH), m is 1.5-3.5.

According to some embodiments of the present invention, the preparation of said alcoholate of magnesium dihalide can be carried out according to methods known in the art, for example with reference to the method disclosed in CN 1330086A.

According to a preferred embodiment of the invention, the preparation process of the alcoholate of magnesium dihalide comprises: (1) mixing anhydrous magnesium dihalide with alcohol compound (R' OH), and reacting at 90-140 deg.C to obtain magnesium halide alcohol compound; (2) shearing the magnesium halide alcohol compound in a dispersion medium, and cooling in an inert medium after shearing to obtain the spherical magnesium halide alcohol compound. The mixing ratio of the anhydrous magnesium dihalide and the alcohol compound may be determined according to the actual need of the alcohol compound supported on the anhydrous magnesium dihalide. Wherein, the dispersion medium can adopt hydrocarbon inert solvent, such as kerosene, white oil, silicone oil, paraffin oil, vaseline oil, etc. The inert medium may be selected from pentane, hexane, heptane, petroleum ether, raffinate oil, and the like. Wherein the shearing means shearing the alcoholic product of the magnesium halide by external shearing force, for example, high-speed stirring method (e.g. CN1330086), spraying method (e.g. US6020279) and super-gravity rotating bed (e.g. CN1580136A) and emulsifier method (CN1463990A) and the like.

According to a preferred embodiment of the present invention, in order to further increase the purity of the magnesium compound, the obtained alcohol hydrate of spherical magnesium halide is further subjected to washing and drying steps.

According to the invention, the alkoxy magnesium is prepared by reacting metal magnesium, ethanol, isooctyl alcohol (2-ethylhexanol) and a mixed halogenating agent under an inert atmosphere. The mixed halogenating agent is a combination of a halogen and a halogen compound, a non-limiting selection of which are: iodine, bromine, chlorine, magnesium chloride, magnesium bromide, magnesium iodide, potassium chloride, potassium bromide, potassium iodide, calcium chloride, calcium bromide, calcium iodide, mercuric chloride, mercuric bromide, mercuric iodide, ethoxymagnesium iodide, methoxymagnesium iodide, isopropylmagnesium iodide, hydrogen chloride, chloroacetyl chloride, and the like.

According to the present invention, the titanium compound may be various titanium compounds conventionally used in the art for preparing olefin polymerization catalysts. According to a preferred embodiment of the present invention, the titanium compound has a structure represented by formula (VII),

Ti(OR”)_4-kX_kformula (VII)

In formula (VII): r' is C1-C20 alkyl, and X is F, Cl or Br; k is an integer of 0 to 4.

According to a preferred embodiment of the invention, in formula (VII): r' is C1-C10 alkyl.

According to a preferred embodiment of the invention, in formula (VII): r' is C1-C5 alkyl.

According to a preferred embodiment of the invention, for example, in formula (VII): r' is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl.

According to a preferred embodiment of the invention, in formula (VII): and X is Cl.

According to a preferred embodiment of the present invention, the titanium compound is at least one selected from the group consisting of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotris butoxytitanium, dichlorodibutoxytitanium, trichloro-monobutoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium, trichloro-monoethoxytitanium and titanium trichloride.

In the present invention, the inert solvent and the inert diluent are solvents commonly used in the art, and specifically, for example, one or more of toluene, ethylbenzene, benzene, xylene, chlorobenzene, hexane, heptane, octane and decane may be used, and hexane is preferable. According to a preferred embodiment of the invention, the titanium compound is titanium tetrachloride.

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

a catalyst system for the polymerization of olefins comprising the following components or the reaction product of the following components:

1) a solid catalyst component comprising the above solid catalyst;

2) a co-catalyst component comprising an organoaluminum compound; and

optionally, 3) an external electron donor compound.

In some preferred embodiments of the present invention, the organoaluminum compound has the formula AlR⁸ _dX¹ _3-dIn the formula, R⁸Is hydrogen or C_l～C₂₀Hydrocarbyl radical, X¹Is halogen atom, d is more than 0 and less than or equal to 3; preferably, the organoaluminium compound is selected from Al (CH)₃)₃、Al(CH₂CH₃)₃、Al(i-Bu)₃、AlH(CH₂CH₃)₂、AlCl(CH₂CH₃)₂、AlH(i-Bu)₂、AlCl_1.5(CH₂CH₃)_1.5、AlCl(CH₂CH₃)₂And AlCl₂(CH₂CH₃) More preferably Al (CH)₂CH₃)₃And/or Al (i-Bu)₃More preferably, the molar ratio of the aluminum element in the organoaluminum compound to the titanium element in the solid catalyst component is (5-5000): 1, preferably (20-2000): 1.

Since only the internal electron donor component of the olefin polymerization catalyst component is improved in the olefin polymerization catalyst of the present invention, the kind and content of the external electron donor in the olefin polymerization catalyst of the present invention are not particularly limited. Preferably, the molar ratio of the aluminum in the alkyl aluminum compound to the external electron donor compound is (0.1-500): 1, more preferably (1-200): 1; or no external electron donor is used.

According to the present invention, the external electron donor compound may be any of various external electron donor compounds commonly used in the art for achieving the above object, such as: one or more of carboxylic acids, carboxylic acid anhydrides, carboxylic acid esters, ketones, ethers, alcohols, lactones, organophosphorus compounds, and organosilicon compounds. The organosilicon compound is preferred, and the silane compound is more preferred.

According to the invention, the silane compound is selected from compounds shown in a formula (II),

in the formula (II), R₅To R₈The same or different, each independently selected from hydrogen and C₁-C₁₀Alkyl radical, C₂-C₁₀Alkenyl radical, C₁-C₁₀Alkoxy radical, C₂-C₁₀Alkenyloxy radical, C₂-C₁₀Alkynyl, C₂-C₁₀Alkynyloxy, C₃-C₁₀Cycloalkyl radical, C₆-C₁₅Aryl and amino, preferably hydrogen, C₁-C₆Alkyl radical, C₃-C₆Cycloalkyl radical, C₆-C₁₀Aryl and amino, saidR₃To R₆Optionally containing substituents selected from halogen atoms, C₁-C₆Alkyl radical, C₃-C₆Cycloalkyl radical, C₆-C₁₀One or more of aryl and amino.

According to the invention, the silane compound is selected from tetramethoxysilane, tetraethoxysilane, diisopropyldimethoxysilane, isopropyltrimethoxysilane, di-n-propyldimethoxysilane, n-propyltrimethoxysilane, di-n-butyldimethoxysilane, di-t-butyldimethoxysilane, diisobutyldimethoxysilane, cyclopentyltrimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexyldimethoxysilane, cyclohexylethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, vinylmethoxysilane, vinylethoxysilane, vinylpropoxysilane, vinyldimethoxysilane, vinyldiethoxysilane, vinyldipropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyldimethoxysilane, vinyltrimethoxysilane, vinyldimethoxysilane, vinyltrimethoxysilane, vinyldimethoxysilane, vinyltrimethoxysilane, vinyldimethoxysilane, vinyl, One or more of vinyltripropoxysilane, allylmethoxysilane, allylethoxysilane, allylpropoxysilane, allyldimethoxysilane, allyldiethoxysilane, allyldipropoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allyltripropoxysilane, aminotrimethylsilane, aminotriethylsilane, aminotripropylsilane, aminotri-butylsilane, aminotriisobutylsilane, methylaminotrimethylsilane, methylaminotriethylsilane, methylaminotripropylsilane, methylaminotri-n-butylsilane, methylaminotriisobutylsilane, ethylaminotrimethylsilane, ethylaminotriethylsilane, ethylaminotripropylsilane, ethylaminotri-n-butylsilane, and ethylaminotriisobutylsilane.

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

the application of the solid catalyst or the catalyst system in the field of olefin polymerization, especially propylene polymerization.

According to the present invention, the olefin polymerization includes homopolymerization and copolymerization of olefins.

According to the invention, the olefin has the general formula CH₂Wherein R is hydrogen or C₁-C₆And the olefin polymerization can be homopolymerization of a single olefin or copolymerization of a plurality of olefins, and can also be a combination of a single olefin homopolymerization process and a plurality of olefin copolymerization processes.

According to some preferred embodiments of the present invention, the olefin is selected from at least one of ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene.

According to some preferred embodiments of the invention, the olefin is ethylene, propylene and/or 1-butene.

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

an olefin polymerization process comprising: the olefin is polymerized in the presence of the catalyst system described above.

In some preferred embodiments of the present invention, the polymerization conditions include: the temperature is 0-150 ℃, preferably 50-90 ℃; the pressure is 0.01MPa to 10MPa, preferably 0.1MPa to 5 MPa; the time is 0.1h to 5h, preferably 0.2h to 3 h.

According to some embodiments of the invention, both the catalyst system and the prepolymerized catalyst composition may be used in the polymerization of olefins.

According to some preferred embodiments of the present invention, both the catalyst system and the prepolymerized catalyst composition may be used in the homopolymerization of propylene or in the copolymerization with other olefins.

According to the present invention, the catalyst system of the present invention may be directly added to a reactor for use in a polymerization process, or the catalyst system and a prepolymerized catalyst composition obtained by prepolymerizing an olefin may be added to the reactor for polymerization.

According to the invention, the olefin polymerization can be carried out according to known polymerization methods, in liquid or gas phase, or in a combination of liquid and gas phase polymerization stages, or using conventional techniques such as slurry processes, gas phase fluidized beds, etc.

According to the invention, the polymerization can be carried out in the presence of a solvent. Wherein the concentration of the catalyst system in the solvent may be 0.1X 10 in terms of the titanium element in the solid catalyst component^-5-5×10^-5Mol/l.

According to some preferred embodiments of the present invention, the concentration of the catalyst system in the solvent may be 0.2X 10 based on the titanium element in the solid catalyst component^-5-2×10^-5Mol/l.

In the present invention, the hydrocarbon group may be selected from the group consisting of alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl and alkaryl groups.

In the present invention, alkyl means a straight or branched alkyl group, non-limiting examples of which include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, tetrahydrogeranyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-octadecyl, n-nonadecyl and n-eicosyl.

In the present invention, examples of the alkenyl group may include, but are not limited to: ethenyl, propenyl, butenyl, pentenyl, octenyl.

In the present invention, examples of alkynyl groups may include, but are not limited to: ethynyl and propargyl.

In the present invention, examples of the cycloalkyl group may include, but are not limited to: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, 4-n-butylcyclohexyl, cycloundecyl and cyclododecyl.

In the present invention, examples of the halogen include, but are not limited to, fluorine, chlorine, bromine and iodine.

In the present invention, examples of the aryl group may include, but are not limited to: phenyl, methylphenyl, ethylphenyl, 4-tert-butylphenyl, naphthyl.

In the present invention, aralkyl means an alkyl group having an aryl substituent, and examples may include, but are not limited to: phenylmethyl, phenylethyl, phenyl-n-propyl, phenyl-n-butyl, phenyl-t-butyl and phenyl-isopropyl.

In the present invention, the alkylaryl group means an aryl group having an alkyl substituent group with a carbon number of 7 to 20, and examples thereof may include, but are not limited to: methylphenyl, ethylphenyl.

In the present invention, examples of alkoxy groups may include, but are not limited to: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, tert-pentoxy, and hexoxy.

In the present invention, examples of the condensed ring aryl group may include, but are not limited to: naphthyl, anthryl, phenanthryl, pyrenyl.

In the present invention, the hetero atom means an atom usually contained in a molecular structure other than a halogen atom, a carbon atom and a hydrogen atom, for example, O, N, S, P, Si and B, etc.

The invention adopts the columnar aromatic hydrocarbon compound shown in the formula (I) or the derivative thereof as the internal electron donor, and the columnar aromatic hydrocarbon compound or the derivative thereof is compounded with other types of internal electron donors for use, thereby improving the molecular weight of the prepared polymerization product.

Detailed Description

The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to the following description.

In the present invention, the compounds represented by the formula (I) can be prepared by referring to the existing literature, for example, the compounds F1, L1, N1 and O1 can be prepared by referring to the literature Angew.chem.int.Ed.2020,59, 3994-; the compounds P1, Q1, R1 can be prepared by reference to org.Lett.2019,21, 3976-3979 (DOI: 10.1021/acs.orglett.9b01123).

In the following examples, the test methods involved are as follows:

1. composition of the catalyst component: using liquid nuclear magnetism¹H-NMR；

2. Determination of titanium content in catalyst: carrying out colorimetric determination by adopting an ultraviolet-visible spectrophotometer type 722;

3. polymerization activity of catalyst: the amount of polymer obtained in kg over time is divided by the amount of catalyst added in g.

4. Weight average molecular weight: high temperature sol gel chromatography, measured with reference to standard GB/T36214.4-2018.

5. Polymer isotactic index: reference is made to the standard GB/T2412-.

Preparation example 1

This preparation example is intended to illustrate the preparation of a magnesium compound.

Mixing anhydrous magnesium chloride and ethanol according to a molar ratio of 1:2.6, heating to 120 ℃ for reaction to generate magnesium chloride alcoholate melt, stirring at a high speed in white oil and silicone oil serving as dispersion media, then putting into cooled hexane to form spherical magnesium chloride alcoholate particles, and washing and drying to obtain the spherical carrier.

Preparation example 2

This preparation example is intended to illustrate the preparation of the solid catalyst component.

Adding 100mL of titanium tetrachloride into a 300mL glass reaction bottle with a stirrer, fully replacing with high-purity nitrogen, cooling to-20 ℃, adding 8g of the spherical magnesium chloride alcoholate prepared in preparation example 1, slowly heating to 110 ℃, adding 0.3mmol of compound B3 and 5mmol of diisobutyl phthalate as internal electron donors in the heating process, keeping the temperature at 110 ℃ for 0.5h, filtering out liquid, adding titanium tetrachloride twice, washing with hexane five times, and drying in vacuum to obtain the titanium-containing solid catalyst component Z1.

Preparation example 3

The solid catalyst component Z2 was prepared in the manner of preparation example 2. The only difference from preparation example 2 was that compound L1 was used in place of compound B3 in preparation example 2.

Preparation example 4

Adding 100mL of titanium tetrachloride into a 300mL glass reaction bottle with stirring, fully replacing with high-purity nitrogen, cooling to-20 ℃, adding 8g of the spherical magnesium chloride alcoholate prepared in preparation example 1, slowly heating to 110 ℃, adding 6mmol of diisobutyl phthalate as an internal electron donor in the heating process, keeping the temperature at 110 ℃ for 0.5h, filtering to remove liquid, adding titanium tetrachloride for two times, washing with hexane for five times, and drying in vacuum to obtain the titanium-containing solid catalyst component D1.

Preparation example 5

This preparation example is intended to illustrate the preparation of the solid catalyst component.

Sequentially adding 6.0g of magnesium chloride, 119mL of toluene, 5mL of epichlorohydrin and 15.6mL of tributyl phosphate (TBP) into a reactor fully replaced by high-purity nitrogen, heating to 50 ℃ under stirring, and maintaining for 2.5 hours until the solid is completely dissolved; 1.7g of phthalic anhydride is added and the mixture is maintained for 1 hour; cooling the solution to below-25 ℃, and dripping TiCl within 1 hour₄70mL, slowly heating to 80 ℃, and gradually separating out solids in the heating process; adding 0.3mmol of compound F1 and 5mmol of 3-methyl-2, 4-pentanediol dibenzoate as internal electron donor, maintaining the temperature for 1 hour, filtering, adding 80mL of toluene, and washing twice to obtain solid precipitate. Then 60mL of toluene and TiCl were added₄40mL, heating to 100 ℃, treating for 2 hours, discharging the filtrate, then adding 60mL of toluene and TiCl₄40mL, heating to 100 ℃, treating for 2 hours, and discharging the filtrate; adding 60mL of toluene, washing for three times in a boiling state, adding 60mL of hexane, washing for two times in a boiling state, adding 60mL of hexane, and washing for two times at normal temperature to obtain a solid catalyst component Z3.

Preparation example 6

A solid catalyst component Z4 was prepared in the manner of preparation example 5. The only difference from preparation example 5 was that compound G1 was used instead of compound F1 in preparation example 5.

Preparation example 7

A solid catalyst component Z5 was prepared in the manner of preparation example 5. The only difference from preparation example 5 was that compound Q1 was used in place of compound F1 in preparation example 5.

Preparation example 8

This preparation example is intended to illustrate the preparation of the solid catalyst component.

Sequentially adding 6.0g of magnesium chloride, 119mL of toluene, 5mL of epichlorohydrin and 15.6mL of tributyl phosphate (TBP) into a reactor fully replaced by high-purity nitrogen, heating to 50 ℃ under stirring, and maintaining for 2.5 hours until the solid is completely dissolved; 1.7g of phthalic anhydride is added and the mixture is maintained for 1 hour; cooling the solution to below-25 ℃, and dripping TiCl within 1 hour₄70mL, slowly heating to 80 ℃, and gradually separating out solids in the heating process; adding 6mmol of 3-methyl-2, 4-pentanediol dibenzoate as an internal electron donor, maintaining the temperature for 1 hour, filtering, adding 80mL of toluene, and washing twice to obtain a solid precipitate. Then 60mL of toluene and TiCl were added₄40mL, heating to 100 ℃, treating for 2 hours, discharging the filtrate, then adding 60mL of toluene and TiCl₄40mL, heating to 100 ℃, treating for 2 hours, and discharging the filtrate; adding 60mL of toluene, washing for three times in a boiling state, adding 60mL of hexane, washing for two times in a boiling state, adding 60mL of hexane, and washing for two times at normal temperature to obtain a solid catalyst component D2.

Preparation example 9

This preparation example is intended to illustrate the preparation of the solid catalyst component.

Adding 100mL of titanium tetrachloride into a 300mL glass reaction bottle with a stirrer, which is fully replaced by high-purity nitrogen, cooling to-20 ℃, adding 8g of the spherical magnesium chloride alcoholate prepared in preparation example 1, slowly heating to 110 ℃, adding 0.3mmol of the mixture J and 5mmol of 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane as internal electron donors in the heating process, keeping the temperature at 110 ℃ for 0.5h, filtering to remove liquid, adding titanium tetrachloride for treatment twice, washing with hexane five times, and drying in vacuum to obtain a titanium-containing solid catalyst component Z6.

Preparation example 10

A solid catalyst component Z7 was prepared in the manner of preparation example 9. The only difference from preparation 9 is that compound R1 is used instead of mixture J in preparation 9.

Preparation example 11

This preparation example is intended to illustrate the preparation of the solid catalyst component.

Adding 100mL of titanium tetrachloride into a 300mL glass reaction bottle with a stirrer, which is fully replaced by high-purity nitrogen, cooling to-20 ℃, adding 8g of the spherical magnesium chloride alcoholate prepared in preparation example 1, slowly heating to 110 ℃, adding 6mmol of 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane as an internal electron donor in the heating process, keeping the temperature at 110 ℃ for 0.5h, filtering out liquid, adding titanium tetrachloride for treatment twice, washing with hexane for five times, and drying in vacuum to obtain a titanium-containing solid catalyst component D3.

Preparation example 12

Anhydrous chloroform (50mL) was added to 3mmol of 1, 4-diethoxybenzene, and stirred uniformly, 9mmol of paraformaldehyde and 0.45mmol of ferric chloride were added to the mixture, and the mixture was reacted at 30 ℃ for 2 to 3 hours, washed with 50mL of water, the aqueous phase was extracted with dichloromethane, the organic phase was dried over anhydrous sodium sulfate, concentrated, and subjected to column chromatography (petroleum ether/ethyl acetate: 30: 1) to obtain compound B3.

Preparation example 13

Compound G1 was prepared in the manner of preparation 12. Except that 1-methoxy-4-2-chloroethoxybenzene in preparation example 12 was replaced with 1, 4-diethoxybenzene in preparation example 12.

Preparation example 14

This preparation serves to illustrate the preparation of mixture J.

Anhydrous chloroform (50mL) was added to 3mmol of 1, 4-dimethoxy-2, 5-diethoxybenzene, and stirred uniformly, 9mmol of paraformaldehyde and 0.45mmol of ferric chloride were added to the mixture, and the mixture was reacted at 30 ℃ for 2 to 3 hours, washed with 50mL of water, the aqueous phase was extracted with dichloromethane, the organic phase was dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography (petroleum ether/ethyl acetate ═ 30: 1) to obtain a mixture J containing compound J1, compound J2, and compound J3. Nuclear magnetic analysis revealed that the molar ratio of J1: J2: J3 in mixture J was 1: 0.68: 0.04.

for the purpose of analysis, the component contents of the solid catalysts prepared in the above preparation examples are shown in Table 1.

TABLE 1

Examples 1 to 7 and comparative examples 1 to 3

Examples 1-7 and comparative examples 1-3 are provided to illustrate the catalyst systems provided by the present invention and their applications.

A48-channel parallel pressure reactor (reaction volume 20mL) was charged with 5mNL hydrogen; filling propylene gas to about 1MPa, and adding 5mL of liquid propylene; based on triethyl aluminum (calculated by aluminum element): external electron donor: adding triethyl aluminum, an external electron donor and a heptane solution of the solid catalyst component into the solid catalyst component (calculated by titanium element) in a molar ratio of 500:20:1 to prepare a mixed solution; injecting a certain amount of mixed liquid (containing 0.02mg of solid catalyst component) into a reactor; the reaction was carried out at 70 ℃ for 1 hour.

Discharging and calculating the activity of the catalyst; the isotactic index and the weight-average molecular weight of the polymer were measured, and the results are shown in Table 2.

TABLE 2

Note: the external electron donor is cyclohexylmethyldimethoxysilane.

As can be seen from Table 2, the introduction of the compound of formula (I) or its derivative into the olefin polymerization catalyst component can significantly improve the stereospecificity of the catalyst and the molecular weight of the polymer while maintaining a high polymerization activity. According to the characteristics, the catalyst system provided by the invention has higher activity and is particularly suitable for high-rigidity polyolefin products with low melt index and high isotactic index.

Examples 8 to 9

Examples 8-9 illustrate the effect of adjusting the molar ratio of compound B3 and diisobutylphthalate on the results of the experiment. Different solid catalyst components were prepared in the same manner as in preparation example 2 by changing the amount of the compound B3 added, and tested in the same manner as in example 1. Calculating the activity of the catalyst; the isotactic index and the weight-average molecular weight of the polymer were also measured, and the results are shown in Table 3.

TABLE 3

From the data in Table 3, it is clear that the amount of compound B3 added can be adjusted, and that the properties of the polymer product can be adjusted by changing the amount of compound B3 added.

It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.