Internal electron donor compound for preparing α-olefin polymerization catalyst component

Patent metadata

Field	Value
Publication number	US-10287371-B2
Application number	US-201615132050-A
Country	US
Kind code	B2
Filing date	Apr 18, 2016
Priority date	Oct 18, 2013
Publication date	May 14, 2019
Grant date	May 14, 2019

Abstract

An internal electron donor compound for preparing α-olefin polymerization catalyst component, including two kinds of electron donors; the proportion of the two kinds of electron donors in the compounding preparation of the catalyst is determined via designed experiments so as to obtain a catalyst component having good comprehensive performance or a particular performance. The electron donor compound of the present invention can be used in the preparation of α-olefin polymerization and co-polymerization catalyst component, particular the preparation of propylene polymerization catalyst component, and is applicable to prepare the propylene polymerization catalyst component by reacting magnesium chloride-ethanols complex compound carrier with titanium tetrachloride and electron donors, or to directly prepare the propylene polymerization catalyst component by reacting magnesium chloride, alcohols, titanium tetrachloride, and internal electron donor. In addition, also provided is a theoretical basis for selecting a proper electron donor combination from a plurality of electron donors.

First claim

The invention claimed is:

1. A method for determining a ratio of electron donors in an α-olefin polymerization catalyst component, wherein the catalyst component comprises an internal electron donor A and an internal electron donor B, the method comprising:
(1) adding an amount (“adding amount”) of the internal electron donor A to a catalyst carrier and measuring a corresponding amount loaded to the catalyst carrier (“load amount”) of the internal electron donor A;
(2) repeating step (1) to obtain a plurality of the adding amounts and the corresponding load amounts of the internal electron donor A, and constructing a first load curve showing a relationship between the adding amounts (x-axis) and the corresponding load amounts (y-axis) of the internal electron donor A, x-axis and y-axis forming a coordinate plane;
(3) adding an amount (“adding amount”) of the internal electron donor B into the catalyst carrier and measuring a corresponding amount loaded to the catalyst carrier (“load amount”) of the internal electron donor B;
(4) repeating step (3) to obtain a plurality of the adding amounts and the corresponding load amounts of the internal electron donor B, and constructing a second load curve showing a relationship between the adding amounts (x-axis) and the corresponding load amounts (y-axis) of the internal electron donor B, x-axis and y-axis forming a coordinate plane;
(5) fitting the first load curve by a least squares method by
drawing a straight line p1 in a front portion passing a point where the adding amount and the load amount both read zero (“zero point”),
drawing a straight line q1 in a rear portion passing the end point of the first load curve, and
drawing a first arc line between the front portion and the rear portion of the first load curve;

(6) fitting the second load curve by a least squares method by
drawing a straight line p2 in a front portion passing a point where the adding amount and the load amount both read zero (“zero point”),
drawing a straight line q2 in a rear portion passing the end point of the load curve, and
drawing a second arc line in between the front portion and the rear portion of the second load curve, wherein an intersection of p1 and q1 has a load amount of a, wherein an intersection of p2 and q2 has a load amount of b, and a≥b, wherein an intersection of q1 and the first arc line has a load amount of a+m and an intersection of q2 and the second arc line has a load amount of b+n;

(7) mixing an adding amount x of A and an adding amount y of B with the catalyst carrier;
(8) measuring a compound competition load amount of A loaded to the catalyst carrier as x i and a compound competition load amount of B loaded to the catalyst carrier as y i , wherein 0<x i <a and 0<y i <b and b≤x i +y i ≤a,
(9) constructing a first compound competition load curve for the internal electron donor A and a second compound competition load curve for the internal electron donor B;
(10) respectively selecting a load amount x k of the internal electron donor A from the first compound competition load curve and a load amount y k of the internal electron donor B from the second compound competition load curve, wherein b≤x k +y k ≤a;
(11) determining the adding amount of the internal electron donor A corresponding to x k based on the first compound competition load curve and the adding amount of the internal electron donor B corresponding to y k based on the second compound competition load curve;
(12) preparing the catalyst component by adding to the carrier the adding amount of the internal electron donor A corresponding to x k and the adding amount of the internal electron donor B corresponding to y k ;
(13) testing the catalyst component obtained in step (12) in α-olefin polymerization, screening the catalyst component and determining the corresponding ratio of A to B; and
(14) determining the load amounts of A and B in catalyst component as being x i and y i , respectively; adjusting x i and y i to x t and y t , respectively, provided that amount sum x i +y i follows a formula x i +y i ≤x t +y t ≤a+m+b+n to prepare the catalyst component and testing the catalyst component in α-olefin polymerization, and determining the corresponding ratio of A and B,
wherein lines p1 and p2 pass the zero point of the coordinate plane, line q1 passes the end point of the first load curve, line q2 passes the end point of the second load curve,
wherein the adding amount is the amount of the internal electron donor A or B added to the carrier,
the load amount is the amount of the internal electron donor A or B loaded onto the carrier when only A or B is added to the carrier, and
the competition load amount is the amount of the internal electron donor A or B loaded onto the carrier when both A and B are added to the carrier;
wherein the internal electron donors A and B are different and independently selected from the group consisting of ethyl benzoate, ethyl p-methylbenzoate, ethyl p-Anisate, butyl benzoate, p-ethyl butyl benzoate, p-ethoxy butyl benzoate, dibutyl phthalate, diisobutyl phthalate, dibenzoate-2,4-pentanediol ester, di-m-chlorobenzoic-2,4-pentanediol ester, di-p-butylbenzoic-2,4-pentanediol ester, di-t-butylbenzoic-3-methyl-2,4-pentanediol ester, 2-(1-trifluoromethyl ethyl)-2-methyl diethyl malonate, 2-(1-trifluoromethyl ethylidene)diethyl malonate, 2-isopropylidene diethyl malonate, diethyl succinate, methyl diethyl succinate, 2,3-diisopropyl-2-ethyl diethyl succinate, dibutyl succinate, 2,3-diisopropyl dibutyl succinate, diisobutyl succinate, 2,3-diisopropyl diisobutyl succinate, 3,3-diisobutyl diethyl glutarate, 3-isopropyl-3-methyl diethyl glutarate, 3,3-dimethyl diisobutyl glutarate, 3-methyl diisobutyl glutarate, 2-methyl-diethyl glutarate, diisobutyl glutarate, 9,9-bis(methoxymethyl)fluorene, 5,5-bis(methoxymethyl)cyclopentadiene, 2,2′-dimethoxy-1,1′-biphenyl, 2,2′-dimethoxy-1,1′-binaphthyl, 2,2′-dimethoxy-1,1′-biphenanthrol, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-di-t-butyl-1,3-dimethoxypropane, 2,2-diisoamyl-1,3-dimethoxypropane, 2,2-di-t-pentyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2-n-propyl-2-cyclohexyl-1,3-dimethoxypropane, 2-n-butyl-2-cyclohexyl-1,3-dimethoxypropane, 2-n-pentyl-2-cyclohexyl-1,3-dimethoxypropane, 2-isopentyl-2-isopropyl-1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, diethyl maleate, 2-cyclohexyl diethyl maleate, 2-isobutyl diethyl maleate, 2-n-amyl diethyl maleate, and 2-cyclopentyl diethyl maleate, and wherein the carrier comprises MgCl 2 .

2. The method according to claim 1 , wherein the electron donors A and B are applicable for preparing propylene polymerization catalyst component.

3. The method according to claim 2 , wherein the internal electron donors A and B are different and independently selected from the group consisting of 9,9-bis(methoxymethyl)fluorine, dibutyl phthalate, diisobutyl phthalate, 2,3-diisopropyldibutyl succinate, and 2,2′-dimethoxy-1,1′-binaphthyl.

4. The method according to claim 2 , wherein a combination of internal electron donors A and B is one of the following combinations: 9,9-bis(methoxymethyl)fluorene and dibutyl phthalate, 9,9-bis(methoxymethyl)fluorene and diisobutyl phthalate, 9,9-bis(methoxymethyl)fluorene and 2,3-diisopropyldibutyl succinate, 9,9-bis(methoxymethyl)fluorene and 2,2′-dimethoxy-1,1′-binaphthyl, dibutyl phthalate and 2,3-diisopropyldibutyl succinate, dibutyl phthalate and 2,2′-dimethoxy-1,1′-binaphthyl, diisobutyl phthalate and 2,3-diisopropyldibutyl succinate, or diisobutyl phthalate and 2, 2′-dimethoxy-1,1′-binaphthyl.

5. The method according to claim 1 , wherein a combination of the internal electron donors A and B is one of the following combinatio

Assignees

• Yingkou Xiangyang Catalyst Co Ltd
• Univ Dalian Tech

Inventors

• Wang Licai
• Gao Zhanxian
• Han Rubing
• Gao Tianxiang
• Chen Qiuju
• Yu Limei
• Li Wei
• Zheng Guotong
• Dong Qingxin

Classifications

• C08F4/651

  Pretreating with non-metals or metal-free compounds · CPC title

• C08F2500/18

  Bulk density · CPC title

• C08F2500/24

  Polymer with special particle form or size · CPC title

• C07C43/168

  containing six-membered aromatic rings and other rings · CPC title

• C08F10/00

  Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond · CPC title