Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Plural component system comprising a - group i to iv metal...
Reexamination Certificate
2000-12-06
2004-03-09
Bell, Mark L. (Department: 1755)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Plural component system comprising a - group i to iv metal...
Reexamination Certificate
active
06703339
ABSTRACT:
CROSS-REFERENCE TO RELATED APPLICATION
This application claims priority of China patent Application No. 99125567.4, filed on Dec. 6, 1999.
BACKGROUND OF THE INVENTION
The present invention relates to components and catalysts system for the (co)polymerization of olefins.
In recent years, a study of a catalyst for olefinic polymerization has been greatly developed and properties of the catalyst have been greatly improved. Meanwhile, olefinic polymerization catalysts with better properties are desired as the demand for the processability of the polymer product become higher and higher.
U.S. Pat. No. 4,784,983 discloses a catalyst system for olefinic polymerization comprising components (A), (B) and (C). Component (A) is prepared by dissolving a halide of magnesium in a solvent mixture of an organic epoxy compound and an organic phosphorus compound to form a homogeneous solution; mixing the homogeneous solution with a liquid halide of titanium; adding an auxiliary precipitant such as organic carboxylic acid anhydrides, organic carboxylic acids, ethers and ketones to form a precipitate; adding at least one polycarboxylic acid ester when the precipitate appears; and separating the precipitate from the mixture and treating the separated precipitate with the halide of titanium or a mixture of the halide of titanium in an inert diluent. The activity of the catalyst system of the patent is a very high. The resultant polymer using the catalyst system has very high stereospecificity and a narrow particle size distribution.
However, adjustment to stereospecificity of the polymer by changing the ratio of the organic aluminum compound to the organic silicon compound in the catalyst system of U.S. Pat. No. 4,784,983 is not ideal.
In some applications, there is a need for polymers with high and adjustable stereospecificity and broad molecular weight distribution.
Two attempts have been made to broaden the molecular weight of polymer: 1) The polymerization was carried out in multistage, 2) two or more external electron-donors were added in the polymerization system (see CN 1156999A). However, the production costs of two methods are very expensive.
A catalyst that can be used to produce the polymer with high and adjustable stereospecificity and broad molecular weight distribution would be highly desirous.
SUMMARY OF THE INVENTION
The present invention provides a catalyst component for the (co)polymerization of olefins comprising titanium, magnesium, halogen and a mixed electron-donor and prepared by dissolving a halide of magnesium in a solvent system consisting of an organic epoxy compound, an organic phosphorus compound and optionally an inert diluent to form a homogeneous solution; mixing the homogeneous solution with titanium tetrahalide or its derivatives to form a mixture; precipitating a solid from the mixture in the presence of at least one auxiliary precipitant; treating the solid with the mixed electron-donor to load the mixed electron-donor on the solid; and treating the mixed electron-donor loaded solid with titanium tetrahalide or its derivatives and the inert diluent.
The present invention also provides a catalyst for the (co)polymerization of olefins comprising:
(A) A catalyst component described the above;
(B) An organic aluminum compound having the formula AlR
n
X
3−n
wherein each R is independently hydrogen or a hydrocarbyl group having 1-20 carbon atoms, X is a halogen, and n is a number of from 1 to 3; and
(C) An organic silicon compound having the formula R
n′
Si(OR′)
4−n′
wherein n′ is an integer of from 0 to 3; R and R′ each is independently is alkyl, cycloalkyl, aryl, or haloalkyl group.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in details as follows.
The halide of Magnesium solution, titanium tetrahalide or its derivatives and auxiliary precipitant have been disclosed in U.S. Pat. No. 4,784,983 which is incorporated herein by reference.
The halide of Magnesium solution herein means a uniform solution obtained by dissolving a halide of magnesium in a solvent system consisting essentially of organic epoxy compounds and organic phosphorus compounds. The solvent system may include inert diluents.
Suitable halide of magnesium includes magnesium halide such as magnesium chloride, magnesium bromide and magnesium iodide; a complex of magnesium halide with water or alcohol; a derivative of magnesium halide wherein a halogen atom is substituted by a hydrocarboxyl or halohydrocarboxyl group; and like.
Suitable organic epoxy compound includes oxides of aliphatic olefins, aliphatic diolefins, halogenated aliphatic olefins, and halogenated aliphatic diolefins, glycidyl ethers, cyclic ethers and the like having 2-8 carbon atoms. Examples of suitable organic epoxy compounds are ethylene oxide, propylene oxide, butylene oxide, butadiene dioxide, epoxy chloropropane, methylglycidyl ether, diglycidyl ether, tetrahydrofuran, and the like.
Suitable organic phosphorus compounds include hydrocarbyl or halohydrocarbyl esters of phosphoric acid or phosphorous acid, e.g. trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, triphenyl phosphite and the like; with tributyl, phosphate being preferred.
The halide of titanium used in the preparation of the catalyst component of the invention is a compound having the formula TiX
n
(OR)
4−n
wherein X is a halogen, each R is independently a hydrocarbyl and n is an integer of from 0 to 4. Examples of the compounds are titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxy titanium, tetraethoxy titanium, chlorotriethoxy titanium, dichlorodiethoxy titanium, trichloroethoxy titanium and the like.
The halide of magnesium solution and liquid titanium tetrahalide or its derivatives used in the present invention have been disclosed in U.S. Pat. No. 4,784,983 which is incorporated herein by reference.
The auxiliary precipitant according to this invention includes organic acid anhydrides, organic acids, ketones, aldehydes, ethers and any combination thereof, such as acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic dianhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone benzophenone, dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, diamyl ether and the like.
The mixed electron-donor used in the catalyst component of this invention consists of (1) an o-phthalic acid ester, and (2) a mono- or poly-carboxylic acid ester other than o-phthalic acid ester or ether.
The specific examples of the o-phthalic acid ester include diethyl o-phthalate, dipropyl o-phthalate, di-n-butyl o-phthalate, diisobutyl o-phthalate, diamyl o-phthalate, dihexyl o-phthalate, diheptyl o-phthalate, dioctyl o-phthalate and any combination thereof, wherein di-n-butyl o-phthalate and diisobutyl o-phthalate are preferred.
The specific examples of the mono- or poly-carboxylic acid ester other than o-phthalic acid ester include diethyl malonate, dibutyl malonate, diethyl adipate, dibutyl adipate, diethyl sebacate, dibutyl sebacate, diethyl maleate, di-n-butyl maleate, diethyl p-phthalate, dipropyl p-phthalate, diisopropyl p-phthalate, dibutyl p-phthalate, diamyl p-phthalate, dihexyl p-phthalate, diheptyl p-phthalate, dioctyl p-phthalate, diethyl m-phthalate, dipropyl m-phthalate, diisopropyl m-phthalate, dibutyl m-phthalate, diamyl m-phthalate, dihexyl m-phthalate, diheptyl m-phthalate, dioctyl m-phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, tributyl trimellitate, trioctyl trimellitate, triethyl hemimellitate, tributyl hemimellitate, tetraethyl pyromellitate, tetrabutyl pyromellitate and any combination thereof, wherein dibutyl p-phthalate, dioctyl p-phthalate, tributyl trimellitate and trioctyl trimellitate are preferred.
The specific examples of the ether include di-n-butyl ether, di-iso-butyl ether, di-isoamyl ether, di(2-ethyl-hexyl)
Ding Chunmin
Gao Mingzhi
Li Zhulan
Liu Kunzheng
Mao Bingquan
Bell Mark L.
Brown Jennine
China Petro-Chemical Corporation
Christie Parker & Hale LLP
LandOfFree
Components and catalysts for the (co)polymerization of olefins does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Components and catalysts for the (co)polymerization of olefins, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Components and catalysts for the (co)polymerization of olefins will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-3187799