MAGNESIUM HALIDE REGENERATION PRODUCT, CATALYTIC COMPONENT AND CATALYST COMPRISING SAME, AND THEIR P

专利摘要:
The present invention relates to a magnesium halide adduct. It also relates to a catalytic component comprising said magnesium halide adduct, an olefin polymerization catalyst comprising said catalyst component. Application: use of the magnesium halide adduct for the preparation of the catalyst component, use of the catalyst component in a catalyst for the polymerization of olefins and use of the catalyst in the polymerization of olefins; and process for the polymerization of olefins.
公开号:BE1022065B1
申请号:E2012/0343
申请日:2012-05-23
公开日:2016-02-15
发明作者:Xianzhi Xia；Yuexiang Liu；Jin Zhao；Jigui Zhang；Yongtai Ling；Weili Li；Suzhen Qiao；Yang Tan；Renqi Peng；Ping Gao；Futang Gao；Zhihui Zhang
申请人:China Petroleum & Chemical Corporation；Beijing Research Institute Of Chemical Industry, China Petroleum & Chemical Corporation；
IPC主号:

专利说明:

Magnesium halide adduct, catalytic component and catalyst comprising same, and their preparation
FIELD OF THE INVENTION
The present invention relates to a magnesium halide adduct, a catalyst component comprising the magnesium halide adduct, and a catalyst comprising the catalyst component for the polymerization of olefins; the respective processes for preparing the magnesium halide adduct and the catalyst component; the use of the magnesium halide adduct for the preparation of the catalyst components, the use of the catalyst component in a catalyst for the polymerization of olefins, and the use of the catalyst in the polymerization of olefins; and a process for polymerizing olefins.
BACKGROUND OF THE INVENTION
Ziegler-Natta catalysts prepared by attaching titanium compounds and electron donor compounds to active magnesium halide supports are well known in the art. In general, the active magnesium halides are magnesium-alcohol halide adducts which, as carriers, react with titanium halides and electron donor compounds to obtain spherical catalysts. When used in the polymerization of olefins, particularly in the polymerization of propylene, these spherical catalysts lead to relatively high polymerization activities and relatively high stereospecificity and the resulting polymers have good particle morphology.
The known magnesium-alcohol halide adducts generally comprise binary constituents consisting of magnesium chloride and alcohol. In some cases, the magnesium halide-alcohol adducts comprise a small amount of water. These magnesium halide-alcohol adducts can be prepared by known methods, such as a spray-drying method, a spray-cooling method, a high-pressure extrusion process, or a process of the invention. stirring under high pressure. The magnesium chloride-alcohol adducts are described, for example, in U.S. Patent No. 4,421,674, U.S. Patent No. 4,469,648, US Pat. WO 87/07620, 93/11166, U.S. Patent No. 5,100,849, U.S. Patent No. 6,020,279, US Pat. No. 4,399,054, EP 0 395 383, U.S. Patent No. 6,127,304, U.S. Patent No. 6,323,152 and CN 1 226. 901A. Among them, for example, CN 1 226 901A discloses an adduct MgCl 2 * mROH, nH 2 O, wherein R is C 1 -C 10 alkyl, 2 <m <4.2 and 0 <n <0.7. However, when the catalysts prepared from these magnesium halide-alcohol adducts are used in the polymerization of olefins, a phenomenon of cracking of the polymer particles occurs so easily that there is a large amount of fine powders of the polymer. The main reason could be that the catalytically active sites formed are the supports consisting of adducts during the reaction of the adducts with titanium halides and electron donor compounds are not evenly distributed.
In order to overcome this drawback, it has been attempted to introduce in advance the electron donor compounds during the preparation of the supports consisting of the magnesium chloride-alcohol adducts. For example, as disclosed in Chinese Patents CN 1397568A and CN 1563112A, the internal electron donors well known in the art, such as phthalates, are introduced during the preparation of the carriers to form component supports. multiple "spherical magnesium-alcohol-phthalate", which then react with titanium tetrachloride to form catalysts. The spherical supports described have mean particle diameters, D 50, in the range of 70 to 200 microns. When used in the polymerization of propylene, the catalysts exhibit a relatively low polymerization activity of 406 g PP / g cat.
In addition, another patent CN 101050245A discloses a magnesium halide adduct represented by the formula: MgX2-mROH-nE-pH20, wherein E represents a dihydrocarbyloxy hydrocarbon group, R represents a C1-C8 alkyl group, C12, C3-10 cycloalkyl or 0-10 aryl, m is in the range of 1-5, n is in the range of 0.005-1.0 and p is in the range of 0-0. 8. The magnesium halide adduct is prepared by a process comprising the steps of: (1) in a sealed reactor, mixing the magnesium halide, the alcohol, the dihydrocarbyloxy hydrocarbon compound, and optionally , an inert medium, and heating the resulting mixture to a temperature of 100 to 140 ° C with stirring, to form a melt of a magnesium halide adduct, wherein the magnesium halide is added in an amount of 0.1 to 1.0 mole / liter of the liquid medium, and the alcohol and the dihydrocarbyloxy-functional hydrocarbon compound are added in an amount of 1 to 5 moles and 0.005 to 1 mole, respectively, relative to one mole of magnesium; (2) subjecting the aforementioned melt of the magnesium halide adduct to a shearing action and then discharging the product into a cooling medium to form spherical particles of the halide adduct; magnesium, said cooling medium being adjusted to a temperature of -40 ° C to 0 ° C. However, the magnesium halide adduct prepared by the process of this patent comprises a large amount of non-spherical particles, for example acicular particles and baguette particles. When the catalyst comprising this magnesium halide adduct as carrier is used in the polymerization of olefins, the resulting polymer will also undoubtedly comprise a large amount of nonspherical particles.
SUMMARY OF THE INVENTION
The first aspect of the present invention is to provide a preferably spherical magnesium halide adduct having a relatively regular spatial structure, which will overcome the aforementioned disadvantages of existing magnesium halide adducts. The magnesium halide adduct comprises a compound represented by the formula MgXY, a compound represented by the formula ROH, methanol and a modifier selected from a DOE and o-hydroxybenzoates and, optionally, water, where MgXY, ROH and the modifier are as defined below.
The second aspect of the present invention is to provide a catalyst component for the polymerization of olefins, prepared using the magnesium halide adduct. The catalyst component comprises a reaction product of the preferably spherical magnesium halide adduct of the present invention, a titanium compound and an internal electron donor compound.
The third aspect of the present invention is to provide a catalyst comprising the catalyst component for the polymerization of olefins. The catalyst comprises: (1) the catalytic component of the present invention for the polymerization of olefins; (2) an alkylaluminum compound; and (3) optionally, an external electron donor compound.
The fourth aspect of the present invention is to provide a process for the preparation of the magnesium halide adduct.
The fifth aspect of the present invention is to provide a process for the preparation of the catalyst component.
The sixth aspect of the present invention relates to the use of the catalyst component in a catalyst for the polymerization of olefins.
The seventh aspect of the present invention relates to the use of the catalyst in the polymerization of olefins.
The eighth aspect of the present invention is to provide an olefin polymerization process. The process comprises contacting one or more olefins with the catalyst prepared in accordance with the present invention under olefin polymerization conditions, wherein the catalyst comprises: (1) the catalytic component of the present invention for the polymerization of olefins; (2) an alkylaluminum compound; and (3) optionally, an external electron donor compound. Other aspects of the present invention can be clearly established by those skilled in the art from the contents described in the description below.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 shows an optical microscope photograph of the spherical magnesium halide adduct prepared in Example 1; Figure 2 shows an optical microscope photograph of the magnesium halide adduct prepared in Comparative Example 1; Figure 3 shows an optical microscope photograph of the particles of the catalyst component for the polymerization of olefins prepared in Example 1; Figure 4 shows an optical microscope photograph of the spherical magnesium halide adduct prepared in Example 5; Figure 5 shows an optical microscope photograph of the magnesium halide adduct prepared in Comparative Example 3; Figure 6 shows an optical microscope photograph of the olefin polymerization catalyst prepared in Example 5; Figure 7 shows a light microscopic photograph of the olefin polymerization catalyst prepared in Comparative Example 3.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The first aspect of the present invention is to provide a preferably spherical magnesium halide adduct bound to a relatively regular spatial structure, which will overcome the aforementioned disadvantages of existing magnesium halide adducts. The magnesium halide adduct comprises a compound represented by the formula MgXY, a compound represented by the formula ROH, methanol and a modifier selected from a DOE and o-hydroxybenzoates and, optionally, water. The magnesium halide adduct in the present invention is characterized by good particle morphology, smooth surface, good fluidity, and little or no nonspherical particles. In addition, the catalyst prepared using the magnesium halide adduct as the catalyst support can be used for the polymerization of olefins with relatively good hydrogen sensitivity.
1. The compound represented by the formula MgXY
The main constituent in the magnesium halide adduct of the present invention is the compound represented by the formula MgXY, which is supplemented with an alcohol. In the compound represented by the formula MgXY used in the present invention, X represents a halogen atom and Y, being independently of X, represents a halogen atom, a C1-C14 alkyl group or a C1-C14 alkoxy group; , C 1 -C 14 aryl or C 6 -C 14 aryloxy ·
In a preferred embodiment, X and Y are each a halogen atom; or X represents a halogen atom and Y may represent a C1-C6 alkyl, C1-C6 alkoxy, C6-C12 aryl or C6-C12 aryloxy group. The halogen atom is preferably chlorine or bromine. The C1-C6 alkyl group may be, for example, methyl, ethyl, propyl, isopropyl, butyl or isobutyl. The C1-C6 alkoxy group may be, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy. The C6-C12 aryl group may be, for example, phenyl, o-tolyl, m-tolyl p-tolyl, o-ethylphenyl, m-ethyl-phenyl, p-ethylphenyl or naphthyl. The C6 to C12 aryloxy group may be, for example, a phenoxy or naphthoxy group.
In a further preferred embodiment, the compound represented by the formula MgXY may be one or more compounds selected from the group consisting of magnesium dichloride, magnesium dibromide, phenoxymagnesium chloride, isopropoxy magnesium chloride, and butoxymagnesium chloride.
2. The compound represented by the ROH formula
In the compound represented by the formula ROH used in the present invention, R represents a C 2 -C 12 alkyl, C 3 -C 10 cycloalkyl or C 6 -C 10 aryl group.
In the present invention, the compound represented by the formula ROH denotes alcohols other than methanol. In a preferred embodiment, in the formula ROH, R is C 2 -C 8 alkyl, C 3 -C 8 cycloalkyl or C 6 -C 10 aryl. The C 2 -C 8 alkyl group may be, for example, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl or isooctyl. The C3-C8 cycloalkyl group may be, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. The C 6 -C 10 aryl group may be, for example, phenyl, o-tolyl, m-tolyl, p-tolyl, o-ethyl-phenyl, m-ethylphenyl, p-ethylphenyl or naphthyl.
In another preferred embodiment, the compound represented by the formula ROH may be one or more compounds selected from the group consisting of ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, Isopentanol, n-hexanol, n-octanol and 2-ethylhexanol. 3. The modifier
The magnesium halide adduct of the present invention comprises especially a compound selected from DOE and o-hydroxybenzoates as a modifier. As a first embodiment, DOE is a polyol ester represented by the formula (I)
(I) wherein R 1 and R 2, which may be the same or different, may independently of one another represent a halogen atom, a substituted or unsubstituted linear or branched C 1 -C 20 alkyl group, cycloalkyl C3-C20, C6-C20 aryl, C7-C20 aralkyl or C2-C20 alkenyl; R3-R6 and R1-R2k, which may be the same or different, may represent, independently of one another, a hydrogen atom, a halogen atom, a linear or branched C1-C20 alkyl group; substituted or unsubstituted C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 aralkyl, C2-C20 alkenyl, C2-C20 ester, C1-C20 alkyl containing a heteroatom, C3-C20 cycloalkyl containing a heteroatom, Cç to C20 aryl containing a heteroatom, C7 to C20 aralkyl containing a heteroatom, C2 to C20 alkenyl containing a heteroatom, wherein the heteroatom may consist of one or more heteroatoms selected from the group consisting of an atom halogen, a nitrogen atom, an oxygen atom, a sulfur atom, a silicon atom or a phosphorus atom; alternatively, two or more of R3-R6 and R1-R2k are linked to form a saturated or unsaturated ring structure; the grouping between the parentheses "[]" represents k bonded carbon atoms in sequence, and each of the carbon atoms is further bound to two substituents, which means that there are k carbon atoms and 2k substituents R1, R2 , R3. . . R2k between parentheses; k represents an integer in the range of 0 to 10; when k = 0, in the polyol ester represented by formula (I), the carbon atom substituted with R3 and R4 is bonded directly to the carbon atom substituted with R5 and R6.
In a preferred embodiment of the present invention, R 1 and R 2, which are the same or different, represent, independently of one another, a halogen atom, a C 1 -C 12 alkyl group, a C 3 -C cycloalkyl group, C12, C6 to C12 aryl, C7 to C12 aralkyl or C2 to C12 alkenyl. More preferably, R 1 and R 2, which are the same or different, independently of one another are C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 6 -C 6 aryl or C 7 or C 7 aralkyl, for example a group chosen from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, cyclopropyl, cyclo-butyl, cyclopentyl, cyclohexyl, phenyl, tolyl, dimethylphenyl, ethylphenyl, benzyl, methylbenzyl or phenylethyl.
According to a preferred embodiment of the present invention, R3-R6 and R1-R2k which are the same or different, represent, independently of one another, a hydrogen atom, a halogen atom, an alkyl group C1 to C12, C3 to C12 cycloalkyl, C6 to C12 aryl, C7 to C12 aralkyl, C2 to C12 alkenyl or C2 to C12 ester. More preferably, R3-R6, which are the same or different, represent, independently of each other, a hydrogen atom, a C1-C6 alkyl group or a C3-C6 cycloalkyl, for example a group selected from a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclo-pentyl and cyclohexyl groups; R 1 -R 2k, which are identical or different, represent, independently of one another, a hydrogen atom or a C 1 -C 4 alkyl group, for example a group chosen from a hydrogen atom, and a methyl group ethyl, n-propyl, isopropyl, n-butyl or tert-butyl.
In a preferred embodiment, the DOE is a diol ester represented by the formula (Ia):
wherein R 1 and R 2 are the same as those defined in formula (I); R3 '-Rβ', R7 and R8, which may be the same or different, may independently of one another be a hydrogen atom, a halogen atom, a linear C1-C20 alkyl group or branched C 3 -C 20 cycloalkyl, C 8 -C 20 aryl, C 7 -C 20 aralkyl, C 2 -C 20 alkenyl, C 1 -C 20 alkyl containing a heteroatom, C 3 -C 20 cycloalkyl containing a heteroatom, aryl
C20-C20-containing heteroatom, C2-C20 aralkyl containing a heteroatom, C2-C20 alkenyl containing a heteroatom, or two or more of R3 '-R6' and R7-R8 are linked to form a cyclic structure saturated or unsaturated; wherein the heteroatom may be one or more heteroatoms selected from the group consisting of halogen, nitrogen, oxygen, sulfur, silicon, and phosphorus.
In a further preferred embodiment of formula (Ia), R 1 and R 2, which are the same or different, represent, independently of one another, a halogen atom, a C 1 -C 12 alkyl group, cyclo C3-C12alkyl, C6-C12aryl, C7-C12alkyl or C2-C12alkenyl; R3 '-R6', R7-Rg, which are the same or different, represent, independently of one another, a hydrogen atom, a halogen atom, a C1-C12 alkyl group or a C3 cycloalkyl group; to C22, C6 to C12 aryl, C7 to C12 aralkyl or C2 to C12 alkenyl.
More preferably, in formula (Ia), R 1 and R 2, which are the same or different, represent, independently of one another, a C 1 to C 6 alkyl, C 3 to C 6 cycloalkyl, C 6 to C 6 aryl group. or aralkyl. C7 to C8, for example a group selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, cyclo-propyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, tolyl, dimethylphenyl, ethylphenyl, benzyl, methylbenzyl or phenylethyl; similarly, more preferably, in formula (Ia), R3 '-R6', which are the same or different, represent, independently of each other, a hydrogen atom, a C1-C6 alkyl group or cycloalkyl C3 to C6, for example a group selected from a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclo-pentyl, cyclohexyl; R7-R8, which are identical or different, represent, independently of one another, a hydrogen atom or a C1-C4 alkyl group, for example a group chosen from a hydrogen atom, methyl groups or ethyl, n-propyl, isopropyl, n-butyl or tert-butyl.
In the present invention, a suitable DOE, primarily, may be readily selected by those skilled in the art from the above description, but the aforementioned diol ester represented by formula (Ia) is preferred. Some examples of DOE are illustrated as follows: one or more compounds selected from 1,3-propanediol dibenzoate, 2-methyl-1,3-propanediol dibenzoate, 2-ethyl-1,3-propanediol dibenzoate, 2,2-dimethyl-1,3-propanediol dibenzoate, (R) -1-phenyl-1,3-propanediol dibenzoate, 1,3-diphenyl-1,3-propanediol dibenzoate, di-n- 1,3-diphenyl-1,3-propanediol propionate, 1,3-diphenyl-2-methyl-1,3-propanediol dipropionate, 1,3-diphenyl-2-methyl-1,3-diacetate propanediol, 1,3-diphenyl-2,2-dimethyl-1,3-propanediol dibenzoate, 1,3-diphenyl-2,2-dimethyl-1,3-propanediol dipropionate, 1,3-di-dibenzoate 3-tert-butyl-2-ethyl-1,3-propanediol, 1,3-diphenyl-1,3-propanediol diacetate, 1,3-diisopropyl-1,3-propanediol di- (4-butylbenzoate) , 1-phenyl-2-amino-1,3-propanediol dibenzoate, 1-phenyl-2-methyl-1,3-butanediol dibenzoate, 2,4-pentanediol dibenzoate, 3-butyl-2-dibenzoate , 4-pentanediol, 3,3-dimethyl-2,4-pentanediol dibenzoate, 2,4-pentanediol di- (p-chlorobenzoate), 2,4-pentanediol di- (m-chlorobenzoate), di- (p) -bromobenzoate) 2,4-pentanediol, 2,4-pentanediol di- (o-bromobenzoate), 2,4-pentanediol di- (p-methylbenzoate), di- (p-tert-butylbenzoate) 2 4-pentanediol, 2,4-pentanediol di- (p-butylbenzoate), 2-methyl-1,3-pentanediol di- (p-methylbenzoate), di- (p-methylbenzoate) 2- methyl-1,3-pentanediol, 2-butyl-1,3-pentanediol di- (p-methylbenzoate), 2-methyl-1,3-pentanediol di- (p-tert-butylbenzoate), neopentanoate 2 1-methyl-1,3-pentanediol, 2-methyl-1,3-pentanediol benzoate cinnamate, 2,2-dimethyl-1,3-pentanediol dibenzoate, 2,2-dimethyl-1 benzoate cinnamate, 3-pentanediol, 2-ethyl-1,3-pentanediol dibenzoate, 2-butyl-1,3-pentanediol dibenzoate, 2-allyl-1,3-pentanediol dibenzoate, 2-methyl dibenzoate, and 1,3-pentanediol, the dibenzoate of 2-ethyl-1,3-pentanediol, 2-propyl-1,3-pentanediol dibenzoate, 2-butyl-1,3-pentanediol dibenzoate, 1,3-di (p-chloro-benzoate) pentanediol, 1,3-pentanediol di- (m-chlorobenzoate), 1,3-pentanediol di- (p-bromobenzoate), 1,3-pentanediol di- (o-bromobenzoate), di 1,3-pentanediol (p-methylbenzoate), 1,3-pentanediol di- (p-tert-butylbenzoate), 1,3-pentanediol di- (p-butylbenzoate), benzoate cinnamate, 1,3-pentanediol, 1,3-pentanediol dicinnamate, 1,3-pentanediol dipropionate, 2,2,4-trimethyl-1,3-pentanediol diisopropylformate, 1-trifluoromethyl-3-methyl-2 dibenzoate, 4-pentanediol, 2,4-pentanediol di-p-fluoromethylbenzoate, 2,4-pentanediol di- (2-furanformate), 2-methyl-6-heptene-2,4-heptanediol dibenzoate, dibenzoate 3-methyl-6-heptene-2,4-heptanediol, 4-methyl-6-heptene-2,4-heptanediol dibenzoate, 5-methyl-6-heptene-2,4-heptanediol dibenzoate, Ie dibenz 6-methyl-6-heptene-2,4-heptanediol oate, 3-ethyl-6-heptene-2,4-heptanediol dibenzoate, 4-ethyl-6-heptene-2,4-heptanediol dibenzoate, 5-ethyl-6-heptene-2,4-heptanediol dibenzoate, 6-ethyl-6-heptene-2,4-heptanediol dibenzoate, 3-propyl-6-heptene-2,4-heptanediol dibenzoate , 4-propyl-6-heptene-2,4-heptanediol dibenzoate, 5-propyl-6-heptene-2,4-heptanediol dibenzoate, 6-propyl-6-heptene-2,4-dibenzoate heptanediol, 3-butyl-6-heptene-2,4-heptanediol dibenzoate, 4-butyl-6-heptene-2,4-heptanediol dibenzoate, 2,4-butyl-6-heptene-2,4-dibenzoate -heptanediol, 6-butyl-6-heptene-2,4-heptanediol dibenzoate, 3,5-dimethyl-6-heptene-2,4-heptanediol dibenzoate, 3,5-diethyl-6-dibenzoate heptene-2,4-heptanediol, 3,5-dipropyl-6-heptene-2,4-heptanediol dibenzoate, 3,5-dibutyl-6-heptene-2,4-heptanediol dibenzoate, dibenzoate of 3 , 3-dimethyl-6-heptene-2,4-heptanediol, dibenzoate 3, 3-diethyl-6-heptene-2,4-heptanediol, 3,3-dipropyl-6-heptene-2,4-heptanediol dibenzoate, 3,3-dibutyl-6-heptene-2,4-dibenzoate heptanediol, 3-ethyl-3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, 3-propyl-3,5-heptanediol dibenzoate, 4-propyl-3 dibenzoate, 5-heptanediol, 3-butyl-3,5-heptanediol dibenzoate, 2,3-dimethyl-3,5-heptanediol dibenzoate, 2,4-dimethyl-3,5-heptanediol dibenzoate, dibenzoate 2,5-dimethyl-3,5-heptanediol, 4,4-dimethyl-3,5-heptane-diol dibenzoate, 4,5-dimethyl-3,5-heptanediol dibenzoate, 4,6-dimethyl dibenzoate -3,5-heptanediol, 6,6-dimethyl-3,5-heptanediol dibenzoate, 2-methyl-3-ethyl-3,5-heptanediol dibenzoate, 2-methyl-4-ethyl dibenzoate 3,5-heptanediol, 2-methyl-5-ethyl-3,5-heptanediol dibenzoate, 3-methyl-4-ethyl-3,5-heptane-diol dibenzoate, 3-methyl-5-ethyl dibenzoate -3,5-heptanediol, 4-methyl dibenzoate 1-3-ethyl-3,5-heptanediol, 4-methyl-4-ethyl-3,5-heptanediol dibenzoate, 9,9-bis (benzoyloxymethyl) -fluorene, 9,9-bis- ( (m-Methoxy-benzoyloxy) methyl) -fluorene, 9,9-bis - ((m-chloro-benzoyloxy) methyl) -fluorene, 9,9-bis - ((p-chloro-benzoyloxy) methyl) -fluorene 9,9-bis (cinnamoyloxy-methyl) -fluorene, 9- (benzoyloxymethyl) -9- (propyl-carboxymethyl) -fluorene, 9,9-bis (propylcarboxymethyl) -fluorene, 9.9 -bis- (acryloxymethyl) -fluorene and 9,9-bis- (neopentylcarboxymethyl) -fluorene. The DOE compounds as illustrated, particularly the diol esters, are commercially available or can be synthesized using methods well known in the art (e.g., the method described in CN 1169845C).
As a second embodiment, an o-hydroxybenzoate can be used as a modifier of the magnesium halide adduct. The o-hydroxybenzoate is represented by the following formula (II):
wherein R represents a linear or branched C1-C12 alkyl, C3-C10 cycloalkyl, C6-C10 aryl or C7-C10 arylalkyl group.
In the o-hydroxybenzoate represented by the formula (II), R represents a linear or branched C1-C12 alkyl, C3-C10 cycloalkyl, C6-C10 aryl or C7-C10 arylalkyl group. Said linear or branched C1-C12 alkyl group may be, for example, a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, hexyl or isohexyl group, said C3-C10 cycloalkyl group may be, for example, a cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl group. Said C 6 -C 10 aryl group may be, for example, phenyl, o-benzyl, m-benzyl, p-benzyl, o-ethylphenyl, m-ethylphenyl, p-ethylphenyl or naphthyl. Said C 7 -C 10 arylalkyl group may be, for example, an indenyl, benzyl or phenylethyl group. In a further preferred embodiment, said o-hydroxybenzoate is one or more compounds selected from the group consisting of methyl o-hydroxybenzoate, ethyl o-hydroxybenzoate, o-hydroxybenzoate and the like. n-propyl benzoate, isopropyl o-hydroxybenzoate, n-butyl o-hydroxybenzoate and isobutyl o-hydroxybenzoate. 4. Methanol
The magnesium halide adduct of the present invention comprises methanol as a component. This component is preferably generated in situ during the contact reaction by treatment with dimethoxypropane in the process for preparing the magnesium halide adduct as described below.
According to one embodiment of the present invention, the formula of said magnesium halide adduct can be represented by MgXY-mROH-nCH3OH-tM-qH20, wherein MgXY and ROH are in preferred definitions and definitions, respectively , described above; M represents a modifier selected from DOE and o-hydroxybenzoate; m is 1 to 2.4, n is 0.1 to 1.0, ta is 0.0001 to 0.1, and q is 0 to 0.8.
In a preferred embodiment, in the aforesaid formula of said magnesium halide adduct, ma is 1.5 to 2.2, n is 0.3 to 0.8, and a value of 0.0002 to 0.01 and q has a value of 0 to 0.5.
In an illustrative embodiment of the present invention, if an o-hydroxy benzoate is used as a modifier, it may advantageously be from 0.001 to 0.05, more preferably from 0.002 to 0.04.
In a preferred embodiment of the present invention, regardless of the modifier, i.e. either said DOE or said o-hydroxy-benzoate, which is used, said magnesium halide adduct is preferably spherical particles, and said spherical particles may have a diameter of 10 to 100 μm, preferably 20 to 80 μm. In the preferred embodiment, the olefin polymerization catalyst formed using said magnesium halide adduct as a catalyst support has excellent anti-breakage property and excellent hydrogen sensitivity. In the present invention, the average diameter of the spherical particles can be measured using a Mastersizer 2000 laser particle size analyzer.
The second aspect of the present invention is to provide a catalyst component for the polymerization of olefins, prepared using the magnesium halide adduct. The catalyst component comprises a reaction product of the preferably spherical magnesium halide adduct of the present invention, a titanium compound and an internal electron donor compound. A titanium halide can be used, for example, as a titanium compound in this case.
In the present invention, in the catalyst component for the polymerization of olefins, the weight ratio of the titanium element, the magnesium element and the internal electron donor compound may be 1: 5-15: 2 15, preferably 1: 6-13: 3-12.
In the present invention, there is no particular limitation with respect to the conditions of the contact reaction between the spherical magnesium halide adduct and the titanium halide. Preferably, the conditions of the contact reaction may include: a reaction temperature of 80 to 130 ° C and a reaction time of 0.5 to 10 hours.
In the present invention, the titanium compound may be any titanium halide conventionally used in the process for preparing an olefin polymerization catalyst. In general, the titanium compound may be, for example, a compound represented by the general formula Ti (ORa) 3-aZa and / or Ti (ORa) 4-bZb, wherein Ra represents a C 1 -C 20 alkyl group, Z represents a halogen atom, a represents an integer from 1 to 3 and b represents an integer from 1 to 4. Preferably, the titanium compound consists of one or more compounds selected from titanium tetrachloride or tetrabromide. titanium, titanium tetraiodide, tributoxytitanium chloride, dibutoxytitanium dichloride, butoxytitanium trichloride, triethoxytitanium chloride, diethoxytitanium dichloride, ethoxytitanium trichloride and titanium trichloride, more preferably titanium tetrachloride. and / or titanium tetrabromide.
In the present invention, the internal electron donor compound may be any internal electron donor compound conventionally used in the process for preparing an olefin polymerization catalyst, which may consist, for example, of a or more compounds selected from carboxylates, alcohol esters, ethers, ketones, amines and silanes, preferably one or more compounds selected from monohydroxylic or polyhydroxyl aliphatic carboxylates, aromatic monhydroxylic or polyhydroxy carboxylates, esters dihydroxy alcohols and diethers.
The aliphatic monohydroxylic or polyhydroxyl carboxylates may consist, for example, of one or more compounds selected from diethyl malonate, dibutyl malonate, diethyl 2,3-diisopropyl succinate, di-n-butyl 2,3-diisopropyl succinate , diisobutyl 2,3-diisopropylsuccinate, dimethyl 2,3-diisopropylsuccinate, diisobutyl 2,2-dimethylsuccinate, diisobutyl 2-ethyl-2-methylsuccinate, diethyl 2-ethyl-2-methylsuccinate, diethyl adipate, dibutyl adipate, diethyl sebacate, dibutyl sebacate, diethyl maleate, di-n-butyl maleate, diethyl naphthalene dicarboxylate and dibutyl naphthalene dicarboxylate.
The aromatic monohydroxylic or polyhydroxy carboxylates may consist, for example, of one or more compounds selected from ethyl benzoate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, diisooctyl phthalate, di-n-octyl phthalate, triethyl trimellitate, tributyl trimellitate, triethyl hemimellitate, tributyl hemimellitate, tetraethyl pyromellitate and tetrabutyl pyromellitate. The dihydroxyalcohol ester may be a compound represented by the formula (I):
Wherein R1 and R2, R3-R6 and R'-R2k as well as k, which may be the same or different, may have one of the definitions given above for the various substituents and symbols in formula (I).
Preferably, the dihydroxyalcohol ester may be a compound represented by the formula (III):
wherein each of R14, R15, R16, R17, R11, R11, R12 and R13 has one of the definitions given above for the respective substituents and corresponding symbols at the corresponding positions of the formula ).
Specifically, the esters of dihydroxy alcohols as internal electron donor compounds may be, for example, one or more compounds selected from 1,3-propanediol dibenzoate, 2-methyl-1,3-propanediol dibenzoate, 2-ethyl-1,3-propanediol dibenzoate, 2,2-dimethyl-1,3-propanediol dibenzoate, (R) -1-phenyl-1,3-propanediol dibenzoate, 1,3-dibenzoate 1,3-diphenyl-1,3-propanediol di-n-propionate, 1,3-diphenyl-2-methyl-1,3-propanediol dipropionate, diacetate of 1,3-diphenyl-1,3-propanediol, 1,3-diphenyl-2-methyl-1,3-propanediol, 1,3-diphenyl-2,2-dimethyl-1,3-propanediol dibenzoate, 1,3-diphenyl-2,2-dimethyl-dipropionate 1,3-dipropanediol, 1,3-di-tert-butyl-2-ethyl-1,3-propanediol dibenzoate, 1,3-diphenyl-1,3-propanediol diacetate, di- (4-butylbenzoate) 1,3-diisopropyl-1,3-propanediol, 1-phenyl-2-amino-1,3-propanediol dibenzoate, 1-phenyl-2-methyl-1,3-butyl dibenzoate anediol, 2,4-pentanediol dibenzoate, 3-butyl-2,4-pentanediol dibenzoate, 3,3-dimethyl-2,4-pentanediol dibenzoate, 2,4-pentanediol di- (p-chlorobenzoate), 2,4-pentanediol di- (m-chlorobenzoate), 2,4-pentanediol di- (p-bromobenzoate), 2,4-pentanediol di- (o-bromobenzoate), di- p-methylbenzoate) 2,4-pentanediol, 2,4-pentanediol di- (p-tert-butylbenzoate), 2,4-pentanediol di- (p-butylbenzoate), di- (p-chlorobenzoate) 2-methyl-1,3-pentanediol, 2-methyl-1,3-pentanediol di- (p-methylbenzoate), 2-butyl-1,3-pentanediol di- (p-methylbenzoate), diol 2-methyl-1,3-pentanediol (p-tert-butylbenzoate), 2-methyl-1,3-pentanediol neopentanoate, 2-methyl-1,3-pentanediol benzoate-cinnamate, dibenzoate of 2, 2-dimethyl-1,3-pentanediol, 2,2-dimethyl-1,3-pentanediol benzoate-cinnamate, 2-ethyl-1,3-pentanediol dibenzoate, 2-butyl-1,3-dibenzoate -pentanediol, 2-allyl-1,3-pe dibenzoate ntanediol, 2-methyl-1,3-pentanediol dibenzoate, 2-ethyl-1,3-pentanediol dibenzoate, 2-propyl-1,3-pentanediol dibenzoate, 2-butyl-1 dibenzoate, 3-pentanediol, 1,3-pentanediol di- (p-chloro-benzoate), 1,3-pentanediol di- (m-chlorobenzoate), 1,3-pentanediol di- (p-bromobenzoate) 1,3-pentanediol di- (o-bromobenzoate), 1,3-pentanediol di- (p-methylbenzoate), 1,3-pentanediol di- (p-tert-butylbenzoate), 1,3-pentanediol-1,3-p-butylbenzoate, 1,3-pentanediol benzoate-cinnamate, 1,3-pentanediol dicinnamate, 1,3-pentanediol dipropionate, 2,2,4-trimethyl diisopropylformate 1,3-pentanediol, 1-trifluoromethyl-3-methyl-2,4-pentanediol dibenzoate, 2,4-pentanediol di-p-fluoromethylbenzoate, 2,4-pentanediol di- (2-furanformate), 2-methyl-6-heptene-2,4-heptanediol dibenzoate, 3-methyl-6-heptene-2,4-heptanediol dibenzoate, 4-methyl-6-heptene-2,4-heptaned dibenzoate iol, 5-methyl-6-heptene-2,4-heptanediol dibenzoate, 6-methyl-6-heptene-2,4-heptanediol dibenzoate, 2,4-ethyl-6-heptene-2,4-dibenzoate heptanediol, 4-ethyl-6-heptene-2,4-heptanediol dibenzoate, 5-ethyl-6-heptene-2,4-heptanediol dibenzoate, 6-ethyl-6-heptene-2 dibenzoate, 4-heptanediol, 3-propyl-6-heptene-2,4-heptanediol dibenzoate, 4-propyl-6-heptene-2,4-heptanediol dibenzoate, 5-propyl-6-heptene-2 dibenzoate , 4-heptanediol, 6-propyl-6-heptene-2,4-heptanediol dibenzoate, 3-butyl-6-heptene-2,4-heptanediol dibenzoate, 4-butyl-6-heptene-dibenzoate 2,4-heptanediol, 5-butyl-6-heptene-2,4-heptanediol dibenzoate, 6-butyl-6-heptene-2,4-heptanediol dibenzoate, 3,5-dimethyl-6-dibenzoate -heptene-2,4-heptanediol, 3,5-diethyl-6-heptene-2,4-heptanediol dibenzoate, 3,5-dipropyl-6-heptene-2,4-heptanediol dibenzoate, dibenzoate 3,5-dibutyl-6-heptene-2,4-heptanediol, dibenz 3,3-dimethyl-6-heptene-2,4-heptanediol oate, 3,3-diethyl-6-heptene-2,4-heptanediol dibenzoate, 3,3-dipropyl-6-heptene dibenzoate 2,4-heptanediol, 3,3-dibutyl-6-heptene-2,4-heptanediol dibenzoate, 3-ethyl-3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate , 3-propyl-3,5-heptanediol dibenzoate, 4-propyl-3,5-heptanediol dibenzoate, 3-butyl-3,5-heptanediol dibenzoate, 2,3-dimethyl-3-dibenzoate , 5-heptanediol, 2,4-dimethyl-3,5-heptanediol dibenzoate, 2,5-dimethyl-3,5-heptanediol dibenzoate, 4,4-dimethyl-3,5-heptanediol dibenzoate, dibenzoate 4,5-dimethyl-3,5-heptanediol, 4,6-dimethyl-3,5-heptanediol dibenzoate, 6,6-dimethyl-3,5-heptanediol dibenzoate, 2-methyl dibenzoate, and 3-ethyl-3,5-heptanediol, 2-methyl-4-ethyl-3,5-heptanediol dibenzoate, 2-methyl-5-ethyl-3,5-heptanediol dibenzoate, 3-methyl-4-dibenzoate -ethyl-3,5-heptanediol, the diben 3-methyl-5-ethyl-3,5-heptanediol zoate, 4-methyl-3-ethyl-3,5-heptanediol dibenzoate, 4-methyl-4-ethyl-3,5-heptanediol dibenzoate, 9,9-bis- (benzoyloxymethyl) -fluorene, 9,9-bis - ((m-methoxybenzoyloxy) methyl) -fluorene, 9,9-bis - ((m-chloro-benzoyl-oxy) methyl) -fluorene, 9,9-bis - ((p-chloro-benzoyloxy) -methyl) -fluorene, 9,9-bis (cinnamoyloxy-methyl) -fluorene, 9- (benzoyloxymethyl) -9- (propyl-carboxymethyl) -fluorene, 9,9-bis (propylcarboxymethyl) -fluorene, 9,9-bis (acryloxymethyl) -fluorene and 9,9-bis (neopentyl-carboxymethyl) -fluorene. Some of the dihydroxy alcohol esters listed above are commercially available and others may be synthesized by reference to the methods described in CN 1436796A.
The diether may be a compound represented by the formula (IV):
(IV) wherein Ris and Ri9, which may be the same or different, may independently of one another be a linear or branched C1 to C20 alkyl, C3 to C20 cycloalkyl, C6 to C20 aryl; or C 7 -C 20 arylalkyl; R2o_R2s / which may be the same or different may independently of one another be a hydrogen atom, a halogen atom, a linear or branched C1-C20 alkyl group, a C3-C20 cycloalkyl group, an aryl group, C 2 -C 20 arylalkyl, C 2 -C 20 arylalkyl, or two or more of R 2o-R 25 are linked to form a ring structure. Preferably, Ris and R19, which are identical or different, represent, independently of one another, a linear or branched C 1 -C 10 alkyl group; R 20, R 21, R 24 and R 25 are all hydrogen atoms, R 22 and R 23, which are the same or different, independently of one another are straight or branched C 1 -C 18 alkyl, C 3 cycloalkyl C 18 -C 18 aryl or C 7 -C 18 arylalkyl, or R 22 and R 23 are linked to form a ring structure. In the present invention, the diethers may consist, for example, of one or more compounds selected from 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-dimethylpropane) phenylethyl) -1,3-dimethoxypropane, 2- (2-cyclohexylethyl) -1,3-dimethoxypropane, 2- (p-chlorophenyl) -1,3-dimethoxypropane, 2- (diphenyl-methyl) -1 , 3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1.3 dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-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, 2,2-bis (2-cyclohexylethyl) -1,3-dimethoxypropane, 2-methyl-2-isobutyl-1, 3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2- (1- methyl-butyl) -2-isopropyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2-phenyl-2-isopropyl-1,3-dimethoxypropane, 2-phenyl-2- sec-butyl-1,3-dimethoxypropane, 2-benzyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-sec. -butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2-sec-butyl-1,3-dimethoxypropane, 2-isopropyl-2 -sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmetal hyl-1,3-dimethoxypropane and 9,9-dimethoxymethyl-fluorene. Preferably, the diethers are 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and / or 9,9-dimethoxymethylfluorene.
The third aspect of the present invention is to provide a catalyst comprising the catalyst component for the polymerization of olefins. The catalyst comprises: (1) the catalytic component of the present invention for the polymerization of olefins; (2) an alkylaluminum compound; and (3) optionally, an external electron donor compound.
The catalyst for the olefin polymerization of the present invention utilizes the catalyst component for the olefin polymerization of the present invention. The catalyst for the polymerization of olefins of the present invention, in the form of particles having a smooth surface and a regular morphology, then has a relatively strong anti-rupture property during the polymerization when used as a catalyst for the polymerization of olefins, not only exhibits a relatively large polymerization activity but also excellent hydrogen sensitivity and steric orientation ability and can lead to the formation of polymer particles having a good morphology. Accordingly, there is no particular limitation with respect to the types and amounts of the alkylaluminum compound and the external electron donor compound used in the catalyst for the olefin polymerization of the present invention.
The alkylaluminum compound may be any alkylaluminium compound commonly used in this field. For example, the alkylaluminum compound may consist of one or more compounds selected from triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, monochloro-diethylaluminum, monochloro-diisobutylaluminum, and the like. monochloro-di-n-butylaluminum, monochloro-di-n-hexylaluminum, dichloro-monoethylaluminum, dichloroisobutylaluminum, dichloro-mono-n-butylaluminum and dichloro-mono-n-hexylaluminum.
The external electron donor compound may be any external electron donor compound commonly used in this field. For example, the external electron donor compound may consist of one or more compounds selected from carboxylic acids, anhydrides, esters, ketones, ethers, alcohols, organic phosphorus compounds and organic silicon compounds. Preferably, the external electron donor compound is an organic silicon compound. Examples of organic silicon compounds may include, but are not limited to, cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, diphenyldimethoxysilane, methyl tertiobutyl dimethoxy silane, dicyclopentyl-dimethoxy-silane, 2-ethylpiperidinyl-2-tert-butyl-dimethoxy-silane, (1,1,1-trifluoro-2-propyl) -2-ethyl-piperidinyl dimethoxy-silane and , 1-trifluoro-2-propyl) -méthyldiméthoxy silane.
In the catalyst for the polymerization of olefins, the molar ratio of the catalyst component for the polymerization of olefins measured as a titanium element to the aluminum alkyl compound measured as aluminum element is 1: 1-2000, preferably 1: 10-500 or 1: 20-500, more preferably 1: 20-400; the molar ratio of the external electron donating compound to the alkylaluminum compound measured as titanium is 1: 2200, preferably 1: 2.5-100, more preferably 1: 10-80.
The fourth aspect of the present invention is to provide a process for the preparation of the magnesium halide adduct. The process for the preparation preferably of the spherical magnesium halide adduct may comprise the following steps: (1) mixing a compound represented by the formula MgXY and a compound represented by the formula ROH and, optionally, a liquid medium inert, and heating the resulting mixture with stirring to obtain a melt of magnesium halide adduct; (2) adding the magnesium halide adduct melt after shear dispersion to a cooling medium to form spherical solid particles; (3) allowing the spherical solid particles and dimethoxypropane to carry out the contact reaction in an inert dispersion medium; (4) allowing the product obtained by the contact reaction of step (3) to carry out the contact reaction with DOE or o-hydroxybenzoate in an inert dispersing medium, to obtain a halide adduct of spherical magnesium.
Above, the compound represented by the formula MgXY, the compound represented by the formula ROH, DOE and o-hydroxy-benzoate all meet the above definitions.
In the process for the preparation of the spherical magnesium halide adduct in step (1), the amounts of the compound represented by the formula MgXY and the compound represented by the formula ROH can be suitably selected according to the proportions various components in the desired spherical magnesium halide adduct. Preferably, the molar ratio of the amount of the compound represented by the formula MgXY and the amount of the compound represented by the formula ROH is 1: 1-8, preferably 1: 2-6. The compound represented by the formula MgXY and the compound represented by the formula ROH are as defined above.
In the process for preparing the spherical magnesium halide adduct in step (1), the purpose of the heating is to allow the magnesium halide, the alcohol and the inert liquid medium to form. a melt of the magnesium halide adduct and the alcohol. The heating conditions are not concretely limited and can be determined from the concrete magnesium halide used. The heating conditions can generally comprise: a heating temperature above 80 ° C, a heating time greater than one hour. In a preferred embodiment, the heating conditions include: a heating temperature of 100 to 140 ° C, a heating time of 1 to 5 hours.
In the process for the preparation of the spherical magnesium halide adduct, the inert liquid medium used in step (1) can be any liquid medium commonly used in this non-interacting field. chemical with the spherical magnesium halide adduct, for example organic silicon compounds and / or aliphatic hydrocarbon compounds. Concretely, the inert liquid medium may consist of one or more media chosen from n-pentane, n-hexane, n-heptane, petroleum ether, gasoline, a methylsilicone oil or an ethylsilicone oil. , a methylethylsilicone oil, a phenylsilicone oil, a methylphenylsilicone oil, kerosene, a paraffinic oil, petrolatum and white oil. More preferably, the inert liquid medium is a white oil or a silicone oil. There is no particular limitation with respect to the amount of the inert liquid medium. In general, the inert liquid medium is used in an amount of 0.8 to 10 liters per one mole of compound of formula MgXY (i.e., the magnesium halide added in step (1)), measured as magnesium element.
In the process for the preparation of the spherical magnesium halide adduct, in step (2), the shear dispersion can be carried out using a conventional method, for example the high speed stirring method described in CN 1330086C (i.e., agitation of the magnesium halide adduct in an inert liquid medium at a speed of 2000 to 5000 rpm); the rotational dispersion of a mixture of a magnesium halide adduct and an inert liquid medium in a high gravity bed as described in CN 1267508C (the rotational speed can range from 1000 to 3000 rpm); forming a mixture of a magnesium halide adduct, a silicone oil and a white oil with an emulsifier at a speed of 1500 to 8000 rpm in the manner described in CN 1463990A; and emulsifying a mixture containing a magnesium halide adduct using an atomization method as described in US 6,020,279.
In the process for preparing the spherical magnesium halide adduct, in step (2), the addition of the melt of the magnesium halide adduct, after dispersion by shearing, the medium The purpose of the cooling circuit is to deactivate the magnesium halide adduct melt to form spherical solid particles. In the present invention, the cooling medium is preferably an inert hydrocarbon solvent, more preferably a low boiling inert hydrocarbon solvent, for example one or more solvents selected from the group consisting of pentane, hexane, hexane and the like. heptane, gasoline and petroleum ether. The temperature of the cooling medium can range from -40 ° C to 0 ° C, preferably from -30 ° C to -10 ° C.
In the method of preparing the spherical magnesium halide adduct, after deactivation and before allowing the spherical solid particles and dimethoxypropane to effect the contact reaction, the process for preparing the spherical magnesium halide adduct Spherical magnesium halide further preferably comprises washing the solid particles obtained by quenching with an inert organic solvent 1 to 10 times. The inert organic solvent may be, for example, one or more solvents selected from the group consisting of pentane, hexane, heptane, gasoline and petroleum ether.
In the process for preparing the spherical magnesium halide adduct, there is no particular limitation with respect to the conditions of the contact reaction in step (3). Preferably, the conditions of the contact reaction are as follows: the reaction temperature is 40 to 65 ° C, more preferably 45 to 60 ° C, the reaction time is 1 to 5 hours, more preferably 2 to 4 hours with respect to one mole of the compound represented by the formula MgXY measured as a magnesium element (i.e., the magnesium halide as added in step (1)), the the amount of dimethoxypropane added in step (3) is 0.1 to 1.5 moles, more preferably 0.2 to 1 moles. Under the preferred contact reaction conditions above, the morphology of the spherical magnesium halide adduct as finally prepared can be further improved.
In the process for preparing the spherical magnesium halide adduct, the inert dispersing medium in step (3) may be, for example, at least one medium selected from pentane, hexane and heptane. .
In the process for preparing the magnesium halide adduct, in order to obtain spherical particles of the magnesium halide adduct, the process may further comprise filtering the product obtained after the contact reaction. and washing this product with an inert organic solvent 1 to 10 times. The inert organic solvent may be the same as or different from the aforementioned inert organic solvent.
In the process for preparing the spherical magnesium halide adduct, there is no particular limitation with respect to the conditions of the contact reaction in step (4), as long as they allow form the spherical magnesium halide adduct. Preferably, the conditions of the contact reaction are as follows: the reaction temperature is 40 to 65 ° C, more preferably 45 to 60 ° C, the reaction time is 1 to 5 hours, more preferably 2 to 4 hours. In the case of contacting the product, which was obtained by the contact reaction of the particles of the spherical magnesium halide adduct and dimethoxypropane, with a polyol ester DOE, the molar ratio of the amount from the polyol ester DOE to the amount of the compound represented by the formula MgXY may range from 0.01 to 0.5, preferably from 0.02 to 0.2. In the case of contacting the product, which has been obtained by the contact reaction of the particles of the spherical magnesium halide adduct and dimethoxypropane, with an o-hydroxy benzoate, the molar ratio of amount of the o-hydroxybenzoate to the amount of the compound represented by the formula MgXY may be 0.001: 0.05: 1, preferably 0.002: 0.04: 1. In this case, the DOE polyol ester is a polyol ester represented by the above formula (I), preferably a diol ester represented by the formula (la) above.
In the process for preparing the spherical magnesium halide adduct, there is no particular limitation with respect to the inert dispersing medium in step (4) as long as it allows the DOE to dissolve. and o-hydroxybenzoate. The inert dispersing medium may be identical to or different from the inert medium used in step (3). The inert dispersing medium may be, for example, at least one medium selected from pentane, hexane and heptane.
In the process for preparing the magnesium halide adduct to obtain spherical particles of the magnesium halide adduct, the process may further comprise filtering the product obtained after the contact reaction. washing this product with an inert organic solvent 1 to 10 times and then drying. The inert organic solvent may be the same as or different from the aforementioned inert organic solvent.
The fifth aspect of the present invention is to provide a process for the preparation of the catalyst component. The catalyst component is prepared by the following step on the basis of the preferably spherical magnesium halide adduct obtained above: (5) reaction of the preferably spherical magnesium halide adduct with a titanium compound, and adding an internal electron donor compound in one or more time periods before, during and after the reaction of the spherical magnesium halide adduct with a titanium compound. The suitable internal electron donor compound includes those described above.
In the process for preparing the catalyst component used for the polymerization of olefins, steps (1) to (4) are identical to steps (1) to (4) in the process for preparing the halide adduct spherical magnesium described above.
In the process for preparing the catalyst component useful for the polymerization of olefins, the reaction of the spherical magnesium halide adduct with a titanium compound in step (5) can be carried out according to the process described in US Pat. prior art. Specifically, for example, in step (5), the reaction of the spherical magnesium halide adduct with a titanium compound comprises: cooling a titanium compound to a temperature below 0 ° C (preferably cooling to a temperature of -5 to -25 ° C), adding the spherical magnesium halide adduct obtained in step (4), mixing under conditions of stirring at this temperature for 10 to 60 minutes, then raising the temperature to the reaction temperature (i.e., about 80-130 ° C), and maintaining at this reaction temperature for 0.5 to 10 hours. In the process for preparing the catalyst component useful for the polymerization of olefins, the internal electron donor compound is added in one or more time periods before, during and after the reaction of the spherical magnesium halide adduct with the titanium compound, preferably before the reaction of the spherical magnesium halide adduct with the titanium compound. The time period before the reaction of the spherical magnesium halide adduct with the titanium compound refers to the time period between the introduction of the spherical magnesium halide adduct into the reactor and the elevation from the temperature to the reaction temperature.
In the process for preparing the catalyst component useful for the polymerization of olefins, in step (5), the molar ratio of the amount of the spherical magnesium halide adduct measured as magnesium the amount of the titanium compound measured as titanium element and the amount of the internal electron donor compound may be 1: 20-150: 0.005-1, preferably 1: 30-120: 0.01- 0.6.
In the process for preparing the catalyst component useful for the polymerization of olefins, the titanium compound and the inner electron donor compound are respectively identical to the titanium compound and the internal electron donor compound described above.
The sixth aspect of the present invention relates to the use of the catalyst component in a catalyst for the polymerization of olefins.
The seventh aspect of the present invention relates to the use of the catalyst in the polymerization of olefins.
The eighth aspect of the present invention is to provide an olefin polymerization process. The process comprises: contacting one or more olefins with the catalyst prepared in accordance with the present invention under olefin polymerization conditions, wherein the catalyst comprises: (1) the catalyst component of the present invention for the polymerization olefins; (2) an alkylaluminum compound; and (3) optionally, an external electron donor compound.
According to the olefin polymerization process of the present invention, a polymer having excellent particle morphology can be prepared using the olefin polymerization catalyst of the present invention. There is no particular limitation with respect to the olefin polymerization conditions and the olefin used in the olefin polymerization process of the present invention. The olefin may consist, for example, of one or more olefins selected from the group consisting of ethylene, propylene, 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl 1-butene, 2-methyl-2-butene, 1-pentene, 2-pentene, 1-hexene and styrene, preferably one or more olefins selected from the group consisting of ethylene, propylene 1-butene, 2-butene and styrene.
According to the olefin polymerization process of the present invention, the polymerization of olefins can be carried out according to a conventional method in this field. For example, the polymerization of olefins can be bulk polymerization, gas phase polymerization or suspension polymerization. According to the olefin polymerization process of the present invention, the olefin polymerization conditions may be conventional conditions in this field. For example, the polymerization temperature may range from 0 to 150 ° C, preferably from 60 to 90 ° C; the polymerization pressure may be a normal pressure or a high pressure.
The following examples are provided to further illustrate the present invention. However, it should be understood that these examples are used solely for purposes of illustration and interpretation of the present invention but are not used to limit the present invention.
Examples PART I: Using a DOE as a Modifier Example 1
This example is intended to illustrate the olefin polymerization catalyst component and process for its preparation as well as the olefin polymerization catalyst and its use as provided in the present invention. (1) Preparation of a spherical magnesium chloride adduct
In a 300-liter autoclave, 90 liters of white oil, 90 liters of silicone oil, 9.0 kg (94.7 moles) of magnesium chloride and 14.5 liters (249.0 moles) of ethanol were introduced, heated with stirring to 125 ° C and further stirred at this temperature for 2.5 hours. Then the resulting mixed liquid was transferred by a high gravity rotating bed to hexane which had been previously cooled to -30 ° C. After removing the liquid by filtration, the filter cake was washed five times with hexane and dried under vacuum at 40 ° C for 2 hours to obtain 18 kg of a solid ( i.e., an alcohol adduct of magnesium chloride).
In a 1.6 liter reactor, 900 ml of hexane and 90 g of the solid substance prepared above were introduced, followed by a solution of 45 ml of dimethoxypropane dissolved in 180 ml of hexane (the amount of dimethoxypropane in this solution is equal to 0.37 moles) was added. The system was then heated to 60 ° C and stirred at this temperature for 3 hours. The reaction product was subjected to press filtration. The filter cake was washed twice with hexane to which 800 ml of hexane was added and then 8 ml of 2,4-pentanediol dibenzoate dissolved in 100 ml of hexane. Then the system was heated to 60 ° C and allowed to react at this temperature with stirring for 2 hours. The reaction product was subjected to press filtration. The filter cake was washed twice with hexane and then dried at 60 ° C for 4 hours to obtain a spherical magnesium chloride adduct.
The Mg content of the spherical magnesium chloride adduct was measured by compleximetry and the amounts of ethanol, methanol and 2,4-pentanediol dibenzoate in the spherical magnesium chloride adduct were measured respectively by liquid chromatography. The results showed that the molar ratio of magnesium chloride of ethanol, methanol and 2,4-pentanediol dibenzoate in the spherical magnesium chloride adduct was 1: 1, 6: 0, 6: 0.0005. As measured using a Mastersizer 2000 laser granulometer (produced by Malvern Instruments Ltd), the average particle size of the magnesium chloride adduct was 43 μm. (2) Preparation of the catalyst component for the polymerization of olefins
In a 2000 ml glass reaction bottle, 500 ml of titanium tetrachloride was introduced and cooled to -20 ° C, 40 g of the magnesium chloride adduct prepared in step (1) of the example 1 having been added. The system was then heated to 110 ° C, during which time 6.5 ml of 2,4-pentanediol dibenzoate and 6.5 ml of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane were added. . After holding at 110 ° C for 30 minutes, the liquid was removed by filtration. The filter cake was washed twice with titanium tetrachloride and was washed five times with hexane and then dried under vacuum at 40 ° C for 2 hours to obtain a Cl catalyst component for olefin polymerization. . The amount of Ti element in the catalyst component was measured spectrophotometrically using a grating spectrophotometer; the amount of Mg element in the catalytic component was measured by compleximetry; and the amounts of 2,4-pentanediol dibenzoate and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane in the catalyst component were respectively measured by liquid chromatography. The results showed that the mass ratio of Ti, Mg, 2,4-pentanediol dibenzoate and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane in the catalyst component was 1: 4.5 : 3.1: 1.2. As observed using an optical microscope system of the Nikon Eclipse E200-color video camera type JVC, the optical microphotograph of the catalytic component C1 is shown in Fig. 3. (3) Polymerization of propylene
In a 5 liter autoclave, after flushing with a stream of N2, 1 ml of a triethylaluminum solution in hexane (the concentration of triethylaluminum was 0.5 mmol / ml), 0.1 ml of solution of cyclohexyl-methyldimethoxy-silane (CHMMS) in hexane (the concentration of CHMMS was 0.1 mmol / ml), 10 ml of anhydrous hexane and 4 mg of the catalyst component Cl were introduced into the stream of N2. After sealing the autoclave, 2.0 liters of hydrogen (standard volume) and 2.3 liters of liquid propylene were added, heated to 70 ° C and allowed to react at that temperature for one hour.
Example 2
The preparation of the magnesium chloride adduct and the catalyst component for olefin polymerization and propylene polymerization were carried out according to methods identical to those described in Example 1, except that the amount of hydrogen added during the polymerization of propylene was equal to 6.5 liters.
Comparative Example 1 (1) Preparation of a magnesium chloride adduct
In a 300 liter autoclave, 90 liters of white oil, 90 liters of silicone oil, 9.0 kg of magnesium chloride and 14.5 liters of ethanol were introduced, heated with stirring up to 125 ° C. C and further stirred at this temperature for 2.5 hours. The resulting mixed liquid was then transferred through a high gravity spin bed to hexane which had been previously cooled to -30 ° C. After removing the liquid by filtration, the cake was washed five times with hexane and dried to give 18 kg of a solid (i.e. magnesium chloride alcohol). (2) Preparation of the catalyst component for the polymerization of olefins
The catalyst component of olefin polymerization was prepared using a method identical to that described in Example 1, except that the magnesium chloride adduct prepared in step (1) of Comparative Example 1 was used to obtain a catalytic constituent DC1. (3) Polymerization of propylene
The polymerization of propylene was carried out using a method identical to that described in Example 1 except that the catalyst component prepared in step (2) of Comparative Example 1 was used. Comparative Example 2
The preparation of the magnesium chloride adduct and the catalyst component for olefin polymerization and propylene polymerization were carried out according to methods identical to those described in Comparative Example 1, except that the amount of hydrogen added during the polymerization of propylene was 6.5 liters.
Example 3
This example is intended to illustrate the catalyst component for olefin polymerization and its method of preparation as well as its use in the polymerization of olefins as set forth in the present invention. (1) Preparation of a magnesium chloride adduct
The magnesium chloride adduct was prepared using a method identical to that described in Example 1 except that the amount of dimethoxypropane was 10 ml.
The Mg content of the spherical magnesium chloride adduct was measured by compleximetry and the amounts of ethanol, methanol and 2,4-pentanediol dibenzoate in the spherical magnesium chloride adduct were measured respectively by liquid chromatography. The results show that the molar ratio of magnesium chloride of ethanol, methanol and 2,4-pentanediol dibenzoate in the spherical magnesium chloride adduct was 1: 2.2: 0.2 : 0.0002. As measured using a Mastersizer 2000 laser granulometer (produced by Malvern Instruments Ltd), the average diameter of the magnesium chloride adduct particle is 43 μm. (2) Preparation of the catalyst component for the polymerization of olefins
The catalyst component for the polymerization of olefins was prepared using a method identical to that described in Example 1, except that the magnesium chloride adduct as prepared in step (1) ) of Example 1 was used to obtain a catalytic component C2. The amount of Ti element in the catalyst component was measured by spectrophotography using a grating spectrophotometer; the amount of Mg element in the catalytic component was measured by compleximetry; and the amounts of 2,4-pentanediol dibenzoate and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane in the catalyst component were respectively measured by liquid chromatography. The results show that the mass ratio of Ti, Mg, 2,4-pentanediol dibenzoate and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane in the catalyst component was 1: 7.2: 3.6: 2. (3) Polymerization of propylene
The polymerization of propylene was carried out using a method identical to that described in Example 1 except that the catalyst component as prepared in step (2) of Example 3 was used.
Example 4
The preparation of the magnesium chloride adduct and the catalyst component for olefin polymerization and propylene polymerization were carried out by methods identical to those described in Example 3, except that the amount of hydrogen added during the polymerization of propylene is equal to 6.5 liters.
Test example 1
Using an optical microscope system of the Nikon Eclipse E200-JVC color video camera type, the magnesium chloride adducts as prepared in Example 1 and Comparative Example 1 were observed. The optical microphotograph of the magnesium chloride adduct prepared in Example 1 is as shown in Figure 1, and the optical microphotograph of the magnesium chloride adduct prepared in Comparative Example 1 is such that shown in Figure 2.
As can be seen from Figure 1 and Figure 2, the particles of the magnesium chloride adduct prepared in Example 1 were characterized by regular morphology, a substantially spherical shape, and a relatively narrow particle size distribution. and were substantially free of non-spherical particles and also lacked obvious broken particles, while particles of the magnesium chloride adduct prepared in Comparative Example 1 included overt broken particles.
Test Example 2 (1) The melt index of the polymer is measured by the method of ASTM D1238-99. (2) The isotacticity of the polymer is measured by the heptane extraction method carried out as follows: 2 g of a dry polymer sample are extracted with boiling heptane in a continuous extractor 6 hours, then the residual substance is dried to constant weight. The ratio of the weight of the residual polymer (g) to 2 is considered isotacticity.
The results obtained by the aforementioned methods are presented in Table 1 below.
Table 1
As can be seen from the results in Table 1, the catalyst which has been prepared using the magnesium chloride adduct prepared according to the process of the present invention as a catalyst support has a relatively low hydrogen sensitivity. good in the polymerization of propylene. Specifically, by comparing the polymer melt flow rates prepared by polymerization of propylene using the catalytic constituents C1 and C2 with the melt index of the polymer prepared by polymerization of propylene using the catalytic component DC1, it can be seen that the catalytic constituents C1 and C2 resulted in better hydrogen sensitivity than the DC1 catalytic component.
Test example 3
The polymers prepared in Example 1 and Comparative Example 1 were tested, the results being shown below in Table 2. The test selected in this test example was a national standard test having the following specifications: No. 10 mesh size corresponding to a sieve pore diameter of 1.651 mm No. 20 mesh size corresponding to a sieve pore diameter of 0.850 mm No. 40 sieve mesh corresponding to a sieve pore diameter of 0.425 sieve mesh No. 60 corresponding to a sieve pore diameter of 0.250 mm mesh size No. 80 corresponding to a sieve pore diameter of 0.180 mm sieve mesh No. 100 corresponding to a sieve pore diameter of 0.150 mm
Table 2
As can be seen from the results shown in Table 2, the propylene polymer prepared during the polymerization of propylene in the presence of the catalyst which was prepared using the magnesium chloride adduct according to the present invention as the The catalyst support had a relatively low content of fine powder (particles having a particle diameter corresponding to mesh sizes greater than 80 were generally considered to be fine powders). Clearly, the catalyst prepared using the magnesium chloride adduct provided by the present invention was not easy to break and thus resulted in a relatively good anti-breakage property. PART II: Use of an o-hydroxybenzoate as a modifier
Example 5
This example is used to illustrate the catalyst component for olefin polymerization and its method of preparation as well as the catalyst for olefin polymerization and its use as indicated in the present invention. (1) Preparation of a spherical magnesium chloride adduct
In a 300 liter autoclave, 90 liters of white oil, 90 liters of silicone oil, 9.0 kg of magnesium chloride and 14.5 liters (249.0 moles) of ethanol were introduced, heated under stirring at 125 ° C and further stirring at this temperature for 2.5 hours. Then the resulting mixed liquid was transferred, after sufficient shear dispersion with a high gravity spin bed, to hexane which had been previously cooled to -30 ° C. After removal of the liquid by filtration, the solid was washed five times with hexane and dried, yielding 18 kg of a spherical solid (i.e. magnesium chloride).
In a 1.6 liter reactor, 900 ml of hexane and 90 g of the solid substance prepared above were introduced, followed by a solution of 45 ml of dimethoxypropane dissolved in 180 ml of hexane (the amount of dimethoxypropane in this solution is equal to 0.37 moles) was added. The system was then heated to 60 ° C and stirred at this temperature for 3 hours. The reaction product was subjected to press filtration and the filter cake was washed twice with hexane. The washed solid was introduced into a reactor, into which 800 ml of hexane and then 7 ml of ethyl o-hydroxybenzoate dissolved in 100 ml of hexane (the amount of o-hydroxy-benzoate had been introduced. ethyl in this solution was 0.048 mol). Then the system was heated to 60 ° C and allowed to react at that temperature for 2 hours. The reaction product was subjected to press filtration. The filter cake was washed five times with hexane and then dried to obtain a spherical magnesium chloride adduct.
The amount of Mg in the spherical magnesium chloride adduct was measured by compleximetry and the amounts of ethanol, methanol and o-hydroxy-benzoate in the spherical magnesium chloride adduct were respectively measured by liquid chromatography. The results show that the molar ratio of magnesium chloride of ethanol, methanol and o-hydroxy-ethyl benzoate in the spherical magnesium chloride adduct was 1: 2.1: 0, 7: 0.005. As measured using a Mastersizer 2000 laser granulometer (produced by Malvern Instruments Ltd), the average diameter of the spherical magnesium chloride adduct particle was 40 μm. (2) Preparation of the catalyst component for the polymerization of olefins
In a 2000 ml glass reaction bottle, 500 ml of titanium tetrachloride was introduced and cooled to -20 ° C and then 40 g of the magnesium chloride adduct prepared in step (1) of the Example 5 were added and the mixture was then stirred at -20 ° C for 30 minutes. The system was then slowly heated to 110 ° C, during which time 7.5 ml of diisobutyl phthalate was added. After holding at 110 ° C for 30 minutes, the liquid was removed by filtration. The filter cake was washed twice with titanium tetrachloride and was washed five times with hexane and then dried to give a C3 catalyst component for the polymerization of olefins. The amount of Ti element in the catalyst component was measured spectrophotometrically using a grating spectrophotometer; the amount of Mg element in the catalytic component was measured by compleximetry; and the amount of diisobutyl phthalate in the catalyst component was measured by liquid chromatography. The results show that the mass ratio of Ti, Mg, diisobutyl phthalate in the catalyst component was 1: 7.5: 5.2. (3) Polymerization of propylene
In a 5 liter autoclave, after flushing with a stream of N2, 5 ml of a solution of triethylaluminum in hexane (the concentration of triethylaluminum was equal to 0.5 mmol / ml), 1 ml of a solution of cyclohexylmethyldimethoxy-silane (CHMMS) in hexane (the concentration of CHMMS was 0.1 mmol / ml), 10 ml of anhydrous hexane and 8 mg of the C3 catalyst component were introduced into the N2 stream. . After sealing the autoclave, 1.5 liters of hydrogen (standard volume) and 2.3 liters of liquid propylene were added, the mixture was heated to 70 ° C. and allowed to react at this temperature for one o'clock.
Example 6
The preparation of the magnesium chloride adduct and the catalyst component for olefin polymerization and propylene polymerization were carried out according to methods identical to those described in Example 5, except that the amount of hydrogen added during the polymerization of propylene was equal to 5.0 liters.
Comparative Example 3 (1) Preparation of a magnesium chloride adduct
In a 300-liter autoclave, 90 liters of white oil, 90 liters of silicone oil, 9.0 kg of magnesium chloride, 14.5 liters of ethanol and 1.8 liters (14.7 moles) of dimethoxypropane were introduced, heated with stirring to 125 ° C and further stirred at this temperature for 2.5 hours. Then the resulting mixed liquid was transferred after sufficient shear dispersion by means of a high-gravity rotary bed to hexane which had previously been cooled to -30 ° C. After removing the liquid by filtration, the filter cake was washed five times with hexane and dried to obtain a magnesium chloride adduct. (2) Preparation of the catalyst component for the polymerization of olefins
The catalyst component for the polymerization of olefins was prepared using a method identical to that described in Example 5 except that the magnesium chloride adduct prepared in step (1) of Comparative Example 3 was used to obtain a DC2 catalyst component. (3) Polymerization of propylene
The polymerization of propylene was carried out using a method identical to that described in Example 5.
Comparative Example 4
The preparation of the magnesium chloride adduct and the catalyst component for olefin polymerization and propylene polymerization were carried out according to methods identical to those described in Comparative Example 3, except that the amount of hydrogen added during the polymerization of propylene was 5.0 liters.
Comparative Example 5 (1) Preparation of a magnesium chloride adduct
In a 300 liter autoclave, 90 liters of white oil, 90 liters of silicone oil, 9.0 kg of magnesium chloride and 14.5 liters of ethanol were introduced, heated with stirring up to 125 ° C. C and further stirred at this temperature for 2.5 hours. Then the resulting mixed liquid was transferred, after sufficient shear dispersion, by means of a high-gravity rotary bed, to hexane which had previously been cooled to -30 ° C. After removing the liquid by filtration, the filter cake was washed five times with hexane and dried to obtain a magnesium chloride adduct. (2) Preparation of the catalyst component for the polymerization of olefins
The catalyst component for the polymerization of olefins was prepared using a method identical to that described in Example 5 except that the magnesium chloride adduct prepared in step (1) of Comparative Example 4 was used to obtain a catalytic constituent DC3. (3) Polymerization of propylene
The polymerization of propylene was carried out using a method identical to that described in Example 5.
Comparative Example 6
The preparation of the magnesium chloride adduct and the catalyst component for olefin polymerization and propylene polymerization were carried out according to methods identical to those described in Comparative Example 5, except that the amount of hydrogen added during the polymerization of propylene was 5.0 liters.
Test example 4
Using an optical microscope system of the Nikon Eclipse E200-JVC color video camera type, the magnesium chloride adducts and catalytic components prepared in Example 5 and Comparative Example 3 were observed. The optical microphotograph of the magnesium chloride adduct prepared in Example 5 is as shown in Figure 4, and the optical microphotograph of the magnesium chloride adduct prepared in Comparative Example 3 is such that 5. The optical microphotograph of the catalyst component prepared in Example 5 is as shown in Figure 6 and the optical microphotograph of the catalyst component prepared in Comparative Example 3 is as shown in Figure 7.
As can be seen from FIG. 4 and FIG. 5, the particles of the magnesium chloride adduct prepared in Example 5 were characterized by a relatively regular morphology, a substantially spherical shape, a relatively large particle size distribution, and a particle surface that was smooth and substantially free of non-spherical particles, whereas the particles of the magnesium chloride adduct prepared in Comparative Example 3 contained a large amount of non-spherical particles. As can be seen in FIG. 6 and FIG. 7, the particles of the catalyst component prepared in Example 5 were characterized by a uniform particle size distribution and a regular morphology, while the particles of the catalyst component prepared in FIG. Comparative Example 3 included a relatively large amount of broken particles.
Test Example 5 (1) The melt index of the polymer is measured according to the method of ASTM D1238-99. (2) The isotacticity of the polymer is measured by the heptane extraction method carried out as follows: 2 g of a dry polymer sample are extracted with boiling heptane in a continuous extractor 6 hours, then the residual is dried to constant weight and the ratio of the weight of the residual polymer (g) to 2 is considered isotacticity.
The results obtained by the above methods are shown in Table 3 below.
Table 3
As can be seen from the results in Table 3, the catalyst prepared using the magnesium chloride adduct of the present invention as a catalyst support had a relatively good hydrogen sensitivity in the polymerization of propylene. . Specifically, by comparing the polymer melt index prepared by polymerization of propylene using the catalytic component C3 with the melt indices of the polymers prepared by polymerization of propylene using the catalytic constituents DC2 and DC3, it can be seen that the polymer prepared using the catalytic component C3 had a better sensitivity to hydrogen.
The above concrete embodiments are only used for the description of the preferred embodiments of the present invention. However, the present invention is not limited to the concrete details in the above embodiments. Within the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and all such simple modifications belong to the scope of protection of the present invention.
Furthermore, it should be pointed out that the various concrete technical features described in the above concrete embodiments, in the case where they are not contradictory, can be combined in any convenient way. In order to avoid unnecessary repetition, the various possible ways of combining are not described herein.
In addition, the various different embodiments of the present invention may also be arbitrarily combined and also be considered to be the content described in the present invention, provided that they do not conflict with the concept of the present invention.

权利要求:
Claims (45)
[1]
A magnesium halide adduct, characterized in that it comprises a compound represented by the formula MgXY, a compound represented by the formula ROH, methanol and a modifier selected from a DOE and an o-hydroxy- benzoate, and, optionally, water, in the formula MgXY, X represents a halogen atom and Y, being independently selected from X, represents a halogen atom, a C1-C14 alkyl group, a C1-alkoxy group; C14, C6-C14 aryl or C6-C14 aryloxy; in the formula ROH, R is C 2 -C 12 alkyl, C 3 -C 10 cycloalkyl or C 6 -C 10 aryl; DOE is a polyol ester represented by the formula (I)

Wherein R 1 and R 2, which may be the same or different, may independently of one another represent a halogen atom, a substituted or unsubstituted linear or branched C 1 -C 20 alkyl group, cycloalkyl C3 to C20, C6 to C20 aryl, C7 to C20 aralkyl or C2 to C20 alkenyl; R3-R6 and R1-R2k, which may be the same or different, may represent, independently of one another, a hydrogen atom, a halogen atom, a linear or branched C 1 -C 20 alkyl group, substituted or unsubstituted substituted C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl, C 2 -C 20 alkenyl, C 2 -C 20 ester, C 1 -C 20 alkyl containing a heteroatom, C 3 -C 20 cycloalkyl containing a heteroatom, C6-C20 aryl containing a heteroatom, C7-C20 aralkyl containing a heteroatom, C2-C20 alkenyl containing a heteroatom, wherein the heteroatom may be one or more heteroatoms selected from the group consisting of a halogen atom nitrogen, oxygen, sulfur, silicon and phosphorus; or two or more of R3-R.6 and R1-R2k are linked to form a saturated or unsaturated ring structure; the groups between the parentheses "[]" represent k bonded carbon atoms in sequence, and each of the carbon atoms is further bound to two substituents, which means that there are k carbon atoms and 2k substituents R1, R2, R3. . . R2k between parentheses; k represents an integer in the range of 0 to 10; when k = 0, in the polyol ester represented by formula (I), the carbon atom substituted with R3 and R4 is directly bonded to the carbon atom substituted with R5 and R6; the o-hydroxy-benzoate is represented by the following formula (II):

(II) wherein R represents a linear or branched C1-C12 alkyl, C3-C10 cycloalkyl, C6-C10 aryl or C7-C10 arylalkyl group.
[2]
A magnesium halide adduct according to claim 1, characterized in that the formula of the magnesium halide adduct is MgXY-mROH-nCH30H-tM-qH20, wherein MgXY and ROH are as defined in claim 1; M represents a modifier selected from DOE and an o-hydroxy benzoate as defined in claim 1; m is 1 to 2.4, preferably 1.5 to 2.2; n is 0.1 to 1.0, preferably 0.3 to 0.8; a value of from 0.0001 to 0.1, preferably from 0.0002 to 0.01; q has a value of 0 to 0.8, preferably 0 to 0.5.
[3]
A magnesium halide adduct according to claim 2, characterized in that the o-hydroxybenzoate is used as modifier M, and is 0.001 to 0.05, more preferably 0.002 to 0, 04.
[4]
A magnesium halide adduct according to any one of claims 1 to 3, characterized in that the compound represented by the formula MgXY is one or more compounds selected from the group consisting of magnesium dichloride, magnesium dibromide, phenoxy magnesium chloride, isopropoxy magnesium chloride and butoxy magnesium chloride.
[5]
A magnesium halide adduct according to any one of claims 1 to 3, characterized in that the compound represented by the formula ROH consists of one or more compounds selected from the group consisting of ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, isopentanol, n-hexanol, n-octanol and 2-ethylhexanol.
[6]
A magnesium halide adduct according to any one of claims 1 to 3, characterized in that the o-hydroxy benzoate is one or more o-hydroxybenzoates selected from the group consisting of methyl hydroxy-benzoate, ethyl o-hydroxy-benzoate, n-propyl o-hydroxy-benzoate, isopropyl o-hydroxy-benzoate, n-butyl o-hydroxy-benzoate and isobutyl o-hydroxybenzoate
[7]
Magnesium halide adduct according to one of Claims 1 to 3, characterized in that, in the DOE represented by the formula (I), R 1 and R 2 represent independently of each other halogen, C1-C12 alkyl, C3-C12 cycloalkyl, C6-C12 aryl, C7-C12 aralkyl or C2-C12 alkenyl; preferably C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 6 -C 6 aryl or C 7 or C 7 aralkyl; R3-R6 and R1-R2k represent, independently of each other, a hydrogen atom, a halogen atom, a C1-C12 alkyl group, C3-C12 cycloalkyl, C6-C12 aryl, aralkyl C7 to C12, C2 to C12 alkenyl or C2 to C12 ester; preferably, R3-R6, independently of one another, is hydrogen, C1-C6alkyl or C3-C6cycloalkyl, and if-R214, independently of one another, represent a hydrogen atom. hydrogen or a C1-C4 alkyl group.
[8]
Magnesium halide adduct according to any one of claims 1 to 3, characterized in that the DOE is a diol ester represented by the formula (la)

Wherein R 1 and R 2 are as defined by formula (I) and preferably independently of one another are halogen, C 1 -C 12 alkyl, C 3 -C 12 cycloalkyl C6-C12 aryl, C7-C12 aralkyl or C2-C12 alkenyl; more preferably independently of each other are C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 6 -C 6 aryl or C 7 or C 6 aralkyl; R3 '-R61, R7 and Re, which may be the same or different, may independently of one another be a hydrogen atom, a halogen atom, a linear or branched C1-C20 alkyl group, a cycloalkyl group, C3 to C20, C6 to C20 aryl, C7 to C20 aralkyl or C2 to C20 alkenyl, C1 to C20 alkyl containing a heteroatom, C3 to C20 cycloalkyl containing a heteroatom, C6 to C20 aryl containing a heteroatom C7-C20 aralkyl containing a heteroatom, C2-C20 alkenyl containing a heteroatom, wherein the heteroatom may be one or more heteroatoms selected from the group consisting of halogen, nitrogen, oxygen sulfur, silicon and phosphorus; or two or more of R3-R6 'and R7-R8 are linked to form a saturated or unsaturated ring structure, preferably R3'-R6', R7-R8, independently of one another, represent a hydrogen atom, halogen atom, C1-C12 alkyl, C3-C12 cycloalkyl, C6-C12 aryl, C7-C12 aralkyl or C2-C12 alkenyl, more preferably, R3 · and R6; independently of one another are hydrogen, C 1 -C 6 alkyl or C 3 -C 6 cycloalkyl, and R 7 -R 8, which are the same or different, independently of one another, a hydrogen atom or a C1-C4 alkyl group.
[9]
A magnesium halide adduct according to claim 8, characterized in that the diol ester represented by the formula (Ia) consists of one or more diol esters selected from 1,3-propanediol dibenzoate , 2-methyl-1,3-propanediol dibenzoate, 2-ethyl-1,3-propanediol dibenzoate, 2,2-dimethyl-1,3-propanediol dibenzoate, (R) -1 dibenzoate phenyl-1,3-propanediol, 1,3-diphenyl-1,3-propanediol dibenzoate, 1,3-diphenyl-1,3-propanediol di-n-propionate, 1,3-dipropionate diphenyl-2-methyl-1,3-propanediol, 1,3-diphenyl-2-methyl-1,3-propanediol diacetate, 1,3-diphenyl-2,2-dimethyl-1,3-dibenzoate propanediol, 1,3-diphenyl-2,2-dimethyl-1,3-propanediol dipropionate, 1,3-di-tert-butyl-2-ethyl-1,3-propanediol dibenzoate, diacetate of 1 3-diphenyl-1,3-propanediol, 1,3-diisopropyl-1,3-propanediol di- (4-butylbenzoate), 1-phenyl-2-amino-1,3-propanediol dibenzoate, di 1-phenyl-2-methyl-1,3-butanediol benzoate, 1-phenyl-2-methyl-1,3-butanediol neopentanoate, 3-butyl-2,4-pentanediol dibenzoate, 3-dibenzoate 3-dimethyl-2,4-pentanediol, 2,4-pentanediol dibenzoate, 2,4-pentanediol di- (p-chlorobenzoate), 2,4-pentanediol di- (m-chlorobenzoate), 2,4-pentanediol 2,4-pentanediol (p-bromobenzoate), 2,4-pentanediol di- (o-bromobenzoate), 2,4-pentanediol di- (p-methylbenzoate), di- (p-tert-butylbenzoate) 2,4-pentanediol, 2,4-pentanediol di- (p-butylbenzoate), 2-methyl-1,3-pentanediol di- (p-chlorobenzoate), di- (p-methylbenzoate) 2 1-methyl-1,3-pentanediol, 2-butyl-1,3-pentanediol di- (p-methylbenzoate), 2-methyl-1,3-pentanediol di- (p-tert-butylbenzoate), neopentanoate; 2-methyl-1,3-pentanediol, 2-methyl-1,3-pentanediol benzoate-cinnamate, 2,2-dimethyl-1,3-pentanediol dibenzoate, 2,2-dimethyl benzoate-cinnamate -1,3-pentanediol, dibenzoate 2- thyl-1,3-pentanediol, 2-butyl-1,3-pentanediol dibenzoate, 2-allyl-1,3-pentanediol dibenzoate, 2-methyl-1,3-pentanediol dibenzoate, dibenzoate of 2-ethyl-1,3-pentanediol, 2-propyl-1,3-pentanediol dibenzoate, 2-butyl-1,3-pentanediol dibenzoate, 2,2-dimethyl-1,3-pentanediol dibenzoate 1,3-pentanediol di- (p-chlorobenzoate), 1,3-pentanediol di- (m-chlorobenzoate), 1,3-pentanediol di- (p-bromobenzoate) 1,3-pentanediol (o-bromobenzoate), 1,3-pentanediol di- (p-methylbenzoate), 1,3-pentanediol di- (p-tert-butylbenzoate), di- (p-butylbenzoate) ) 1,3-pentanediol, 1,3-pentanediol benzoate-cinnamate, 1,3-pentanediol dicinnamate, 1,3-pentanediol dipropionate, 2-methyl-1,3-benzoate-cinnamate, pentanediol, 2,2-dimethyl-1,3-pentanediol dibenzoate, 2,2-dimethyl-1,3-pentanediol benzoate-cinnamate, 2-ethyl-1,3-pentanediol dibenzoate, 2-butyl-l, 3-pentanediol , 2-allyl-1,3-pentanediol dibenzoate, 2-methyl-1,3-pentanediol benzoate-cinnamate, 2,2,4-trimethyl-1,3-pentanediol diisopropylformate, 1-dibenzoate, trifluoromethyl-3-methyl-2,4-pentanediol, 2,4-pentanediol di-p-fluoromethylbenzoate, 2,4-pentanediol di- (2-furanformate), 2-methyl-6-dibenzoate heptene-2,4-heptanediol, 3-methyl-6-heptene-2,4-heptanediol dibenzoate, 4-methyl-6-heptene-2,4-heptanediol dibenzoate, 5-methyl-6-dibenzoate -heptene-2,4-heptanediol, 6-methyl-6-heptene-2,4-heptanediol dibenzoate, 3-ethyl-6-heptene-2,4-heptanediol dibenzoate, 4-ethyl-6-dibenzoate heptene-2,4-heptanediol, 5-ethyl-6-heptene-2,4-heptanediol dibenzoate, 6-ethyl-6-heptene-2,4-heptanediol dibenzoate, 3-propyl-6-dibenzoate -heptene-2,4-heptanediol, 4-propyl-6-heptene-2,4-heptanediol dibenzoate, 5-propyl-6-heptene-2,4-heptanediol dibenzoate, 6-propyl-dibenzoate 6 -heptene-2,4-heptanediol, 3-butyl-6-heptene-2,4-heptanediol dibenzoate, 4-butyl-6-heptene-2,4-heptanediol dibenzoate, 5-butyl dibenzoate 6-heptene-2,4-heptanediol, 6-butyl-6-heptene-2,4-heptanediol dibenzoate, 3,5-dimethyl-6-heptene-2,4-heptanediol dibenzoate, 3-dibenzoate 5-Diethyl-6-heptene-2,4-heptanediol, 3,5-dipropyl-6-heptene-2,4-heptanediol dibenzoate, 3,5-dibutyl-6-heptene-2,4-dibenzoate -heptanediol, 3,3-dimethyl-6-heptene-2,4-heptanediol dibenzoate, 3,3-diethyl-6-heptene-2,4-heptanediol dibenzoate, 3,3-dipropyl dibenzoate 6-heptene-2,4-heptanediol, 3,3-dibutyl-6-heptene-2,4-heptanediol dibenzoate, 3-ethyl-3,5-heptanediol dibenzoate, 4-ethyl-3 dibenzoate , 5-heptanediol, 5-ethyl-3,5-heptanediol dibenzoate, 3-propyl-3,5-heptanediol dibenzoate, 4-propyl-3,5-heptanediol dibenzoate, 3-butyl dibenzoate -3,5-heptanediol, 2,3-dimethyl-3,5-hepta dibenzoate nediol, 2,4-dimethyl-3,5-heptanediol dibenzoate, 2,5-dimethyl-3,5-heptanediol dibenzoate, 2,6-dimethyl-3,5-heptanediol dibenzoate, dibenzoate 3,3-dimethyl-3,5-heptanediol, 4,4-dimethyl-3,5-heptane-diol dibenzoate, 4,5-dimethyl-3,5-heptanediol dibenzoate, 4,6-dimethyl dibenzoate -3,5-heptanediol, 4,4-dimethyl-3,5-heptanediol dibenzoate, 2,6-dimethyl-3,5-heptanediol dibenzoate, 2-methyl-3-ethyl-3,5-dibenzoate heptanediol, 2-methyl-4-ethyl-3,5-heptanediol dibenzoate, 2-methyl-5-ethyl-3,5-heptanediol dibenzoate, 3-methyl-3-ethyl-3,5-dibenzoate -heptane-diol, 3-methyl-5-ethyl-3,5-heptanediol dibenzoate, 4-methyl-3-ethyl-3,5-heptanediol dibenzoate, 4-methyl-4-ethyl dibenzoate 3,5-heptanediol, 9,9-bis- (benzoyloxymethyl) -fluorene, 9,9-bis- ((m-methoxy-benzoyloxy) methyl) -fluorene, 9,9-bis- ((m- chloro-benzoyloxy) methyl) -fluorene, 9,9-bis - ((p-chloro-benzoylox y) methyl) -fluorene, 9,9-bis (cinnamoyloxy-methyl) -fluorene, 9- (benzoyloxymethyl) -9- (propylcarboxymethyl) -fluorene, 9,9-bis (propylcarboxymethyl) fluorene, 9,9-bis (acryloxymethyl) -fluorene and 9,9-bis (neopentylcarboxymethyl) -fluorene.
[10]
10. Magnesium halide adduct according to one guelcongue of claims 1 to 3, characterized in that it is spherical particles, and the spherical particles have an average particle diameter of 10 to 100 pm.
[11]
11. Catalytic constituent for the polymerization of olefins, characterized in that it comprises a product obtained by reaction of the spherical magnesium halide adduct according to any one of claims 1 to 10, with a compound of titanium and an internal electron donor compound.
[12]
Catalyst component according to Claim 11, characterized in that the titanium compound is a compound represented by the general formula Ti (OR ') 3-aZa and / or Ti (OR') 4-bZb, in which R 'represents a C 1 -C 20 alkyl group, Z represents a halogen atom, a represents an integer of 1 to 3 and b represents an integer of 1 to 4.
[13]
Catalyst component according to Claim 12, characterized in that the titanium compound is one or more compounds selected from titanium trichloride, titanium tetrafluoride, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrachloride, titanium tetrachloride, titanium tetrachloride, titanium tetrachloride, titanium tetra tributoxytitanium chloride, dibutoxy titanium dichloride, butoxytitanium trichloride, triethoxytitanium chloride, diethoxytitanium dichloride and ethoxytitanium trichloride, more preferably titanium tetrachloride and / or titanium tetrabromide.
[14]
14. Catalyst component according to any one of claims 11 to 13, characterized in that the internal electron donor compound is one or more compounds selected from carboxylates, esters of alcohols, ethers, ketones, amines and silanes, preferably one or more compounds selected from monohydroxylic or polyhydroxyl aliphatic carboxylates, mono- or polyhydroxy aromatic carboxylates, esters of dihydric alcohols and diethers.
[15]
15. Catalytic component according to any one of claims 11 to 13, characterized in that, in the catalytic component for the polymerization of olefins, the weight ratio of the titanium element, the magnesium element and the donor compound. internal electrons is 1: 5-15: 2-15, preferably 1: 6-13: 3-12.
[16]
A process for the preparation of the magnesium halide adduct according to any one of claims 1 to 10 which comprises the following steps: (1) mixing a compound represented by the formula MgXY and a compound represented by the formula ROH and, optionally, an inert liquid medium, and heating the resulting mixture with agitation to obtain a melt of magnesium halide adduct; (2) adding the melt of magnesium halide adduct, after shear dispersion, to a cooling medium, to form spherical solid particles; (3) allowing the spherical solid particles and dimethoxypropane to perform a contact reaction in an inert dispersion medium; and (4) allowing the product obtained by the contact reaction of step (3) and the modifying agent selected from a DOE and an o-hydroxy-benzoate to perform a contact reaction in an inert dispersion medium.
[17]
17. A process according to claim 16, characterized in that, in step (1), the heating temperature is from 100 to 140 ° C and the heating time is from 1 to 5 hours.
[18]
18. Process according to any one of claims 1 to 17, characterized in that, in step (1), the molar ratio of the added amount of the compound represented by the formula MgXY to the added amount of the compound represented by the ROH formula is equal to 1: 1-8.
[19]
19. Process according to any one of claims 16 to 18, characterized in that, in step (1), the inert liquid medium is used in an amount of 0.8 to 10 liters with respect to one mole of MgXY measured in magnesium element, and the inert liquid medium is an organic silicon compound and / or an aliphatic hydrocarbon compound.
[20]
20. Process according to any one of claims 16 to 19, characterized in that, in step (2) the cooling medium is an inert hydrocarbon solvent, preferably one or more selected from the group consisting of pentane, hexane, heptane, gasoline and petroleum ether.
[21]
21. Process according to any one of claims 16 to 20, characterized in that in step (2) the temperature of the cooling medium is -40 ° C to 0 ° C, preferably -30 ° C at -10 ° C.
[22]
22. Process according to any one of claims 16 to 21, characterized in that, in step (3), the conditions of the contact reaction comprise: a reaction temperature of 40 to 65 ° C and a reaction time from 1 to 5 hours.
[23]
23. A method according to any one of claims 16 to 22, characterized in that, in step (3), relative to one mole of the compound represented by the formula MgXY measured in magnesium element, the amount of dimethoxypropane added goes from 0.1 to 1.5 moles, preferably from 0.2 to 1.0 moles.
[24]
24. A process according to any one of claims 16 to 23, characterized in that, in step (4), the conditions of the contact reaction comprise: a reaction temperature of 40 to 65 ° C and a reaction time from 1 to 5 hours.
[25]
25. A process according to any one of claims 16 to 24, characterized in that, in step (4), with respect to one mole of the compound represented by the formula MgXY measured in magnesium element, the amount of DOE added goes from 0.01 to 0.5 mole, preferably from 0.02 to 0.2 mole.
[26]
26. Process according to any one of claims 16 to 24, characterized in that, in step (4), relative to one mole of the compound represented by the formula MgXY measured in magnesium element, the amount of o-hydroxy benzoate added ranges from 0.001 to 0.05 mole, preferably from 0.002 to 0.04 mole.
[27]
A process for the preparation of the catalyst component according to any one of claims 11 to 15, which comprises the following steps: (1) mixing a compound represented by the formula MgXY and a compound represented by the formula ROH and optionally, an inert liquid medium, and heating the resulting mixture with agitation to obtain a melt of magnesium halide adduct; (2) adding the magnesium halide adduct melt, after shear dispersion to a cooling medium, to form spherical solid particles; (3) allowing the spherical solid particles and dimethoxypropane to perform a contact reaction in an inert dispersion medium; (4) allowing the product obtained by the contact reaction of step (3) and a modifier selected from a DOE and an o-hydroxy-benzoate to perform a contact reaction in an inert dispersion medium to obtain a product of addition of spherical magnesium halide; and (5) reacting the spherical magnesium halide adduct with a titanium compound, and adding an internal electron donor compound in one or more periods of time before, during, and after the reaction of the product of addition of spherical magnesium halide with a titanium compound.
[28]
28. A method according to claim 27, characterized in that, in step (1), the heating temperature is from 100 to 140 ° C and the heating time is from 1 to 5 hours.
[29]
29. Process according to any one of claims 27 and 28, characterized in that, in step (1), the molar ratio of the amount of the compound represented by the formula MgXY to the amount of the compound represented by formula ROH is equal to 1: 1-8.
[30]
30. Process according to any one of claims 27 to 29, characterized in that, in step (1), the inert liquid medium is used in an amount of 0.8 to 10 liters with respect to one mole of MgXY measured in magnesium element, and the inert liquid medium is an organic silicon compound and / or an aliphatic hydrocarbon compound.
[31]
31. Process according to any one of claims 27 to 30, characterized in that, in step (2), the cooling medium is an inert hydrocarbon solvent, preferably one or more selected from the group consisting of pentane , hexane, heptane, gasoline and petroleum ether.
[32]
32. Process according to any one of claims 27 to 31, characterized in that, in step (2), the temperature of the cooling medium ranges from -40 ° C. to 0 ° C., preferably from -30 ° C. C at -10 ° C.
[33]
33. Process according to any one of claims 27 to 32, characterized in that, in step (3), the conditions of the contact reaction comprise: a reaction temperature of 40 to 65 ° C and a reaction time from 1 to 5 hours.
[34]
34. Process according to any one of claims 27 to 33, characterized in that, in step (3), relative to one mole of the compound represented by the formula MgXY measured in magnesium element, the amount of dimethoxypropane ranges from 0.1 to 1.5 moles, preferably 0.2 to 1.0 moles.
[35]
35. Process according to any one of claims 27 to 34, characterized in that, in step (4), the conditions of the contact reaction comprise: a reaction temperature of 40 to 65 ° C and a reaction time from 1 to 5 hours.
[36]
36. Process according to any one of claims 27 to 35, characterized in that, in step (4), relative to one mole of the compound represented by the formula MgXY measured in magnesium element, the amount of DOE goes from 0.01 to 0.5 mole, preferably 0.02 to 0.2 mole.
[37]
37. Process according to any one of claims 27 to 35, characterized in that, in step (4), relative to one mole of the compound represented by the formula MgXY measured in magnesium element, the amount of o-hydroxy benzoate ranges from 0.001 to 0.05 moles, preferably from 0.002 to 0.04 moles.
[38]
38. Process according to any one of claims 27 to 37, characterized in that, in step (5), the molar ratio of the amount of the spherical magnesium halide adduct measured as magnesium element, the amount of the titanium compound measured in titanium element and the amount of the internal electron donor compound may be 1: 20-150: 0.005-1, preferably 1: 30-120: 0.010.6.
[39]
39. Catalyst component for the polymerization of olefins, as prepared by the process according to any one of claims 27 to 38.
[40]
40. Use of the magnesium halide adduct according to any one of claims 1 to 10 in a catalyst component for the polymerization of olefins.
[41]
41. Use of the magnesium halide adduct according to any one of claims 1 to 10 as a catalyst support.
[42]
42. Use of the catalyst component for the polymerization of olefins according to any one of claims 11 to 15 and 39 in a catalyst for the polymerization of olefins.
[43]
43. Catalyst for olefin polymerization, characterized in that it comprises: (1) the catalyst component for the polymerization of olefins according to any one of claims 11 to 15 and 39; (2) an alkylaluminum compound; and (3) optionally, an external electron donor compound.
[44]
44. Use of the catalyst for the polymerization of olefins according to claim 43 in a polymerization of olefins.
[45]
A process for the polymerization of olefins comprising, under olefin polymerization conditions, contacting one or more olefins with a catalyst, characterized in that the catalyst is the catalyst for the following olefin polymerization. claim 43.

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