KR102379126B1 - Ziegler-Natta procatalyst compositions AND OLEFINE polymerization process - Google Patents

Abstract

The present invention provides a Ziegler-Natta procatalyst composition comprising at least one transition metal compound and at least one internal electron donor, wherein the internal electron donor comprises a first internal electron donor and a second internal electron donor, the first internal electron donor and the second internal electron donor relate to a Ziegler-Natta procatalyst composition for olefin polymerization and an olefin polymerization method, characterized in that they have different degrees of polymerization, and according to the present invention, the physical properties of the product can be improved by controlling the molecular weight distribution .

Description

Ziegler-Natta procatalyst compositions AND OLEFINE polymerization process

The present invention relates to a Ziegler-Natta procatalyst composition and an olefin polymerization method, and more particularly, an olefin polymer having a broad molecular weight distribution as well as a high stereoregularity by using two internal electron donor compounds having different degrees of polymerization. To a Ziegler-Natta procatalyst composition capable of producing

Polyolefin polymer is a thermoplastic polymer that can be easily processed, reused and recycled, and is used in various fields such as automobile parts or transparent materials. Polyolefin polymers are obtained from petrochemicals and are formed from hydrocarbons such as ethylene and alpha-olefins, which are available in abundance.

Catalyst systems suitable for the production of polyolefins and their components are well known. One type of such catalyst is a Ziegler-Natta catalyst. By Ziegler-Natta catalyst is meant a catalyst system containing a transition metal-containing solid catalyst compound (main catalyst), an organometallic compound (cocatalyst) and at least one electron donor compound (eg external electron donor).

The Ziegler-Natta catalyst directly affects the properties and properties of the polyolefin produced according to its composition, structure, and manufacturing method. Therefore, in order to change the properties of the polyolefin produced, a change in the composition of the catalyst, change in the support structure, change in the preparation method of the catalyst, etc. should be accompanied during the preparation of the catalyst, and the preparation method of each catalyst or the composition of the composition Studies on the catalyst activity changed due to the difference, the molecular weight of the polymerized polymer, and the stereoregularity should be conducted in parallel.

Molecular weight distribution (MWD) affects the properties of the polyolefin and itself affects the end use of the polymer, and the broad molecular weight distribution generally improves flowability at high shear rates during processing, as in blowing and extrusion techniques. Improves the processability of polyolefins in applications requiring high-speed processing at fairly high die swells.

With respect to the Ziegler-Natta catalyst for olefin polymerization, the Ziegler-Natta catalyst exhibits better performance with higher activity and higher stereoregularity, allowing polyolefins to be obtained in higher yields and having a broader molecular weight distribution. development is required.

WO 2015/091984 A WO 2014/118164 A WO 2011/106494 A KR 2011-0034520 A

The present invention is to solve the problems of the prior art described above, and one object of the present invention is to mix internal electron donors having different degrees of polymerization, to control molecular weight distribution, and to improve product properties, Ziegler-Natta To provide a procatalyst composition.

Another object of the present invention is an improved procatalyst composition for the polymerization of olefins, particularly polypropylene, which allows obtaining polyolefins with a broader molecular weight distribution and higher yield while maintaining good stereoregularity. is to provide

Another object of the present invention is to provide a method for polymerization of olefins by using materials having different degrees of polymerization as internal electron donors, thereby reducing costs and maximizing the efficiency of olefin polymerization.

One aspect of the present invention for achieving the above object is,

at least one transition metal compound and at least one internal electron donor;

A Ziegler-Natta procatalyst composition, wherein the internal electron donor comprises a first internal electron donor and a second internal electron donor, wherein the first internal electron donor and the second internal electron donor have different degrees of polymerization. It relates to a Ziegler-Natta procatalyst composition for polymerization.

The first internal electron donor is a haloalkylate compound and the second internal electron donor is a diether compound.

The haloalkylate compound is bismethyl carbonyloxy iodo benzene, bis ethyl carbonyloxy iodo benzene, bis propyl carbonyloxy iodo benzene, bis isopropyl carbonyloxy iodo benzene, bis butyl carbonyloxy iodo benzene. It may be a compound selected from the group consisting of do benzene, bis n-butyl carbonyloxy iodo benzene, and bis t-butyl carbonyloxy iodo benzene.

Preferred examples of the diether compound include 2,2-diisobutyl-1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2,2-dicyclopentyl- 1,3-dimethoxypropane and 9,9-bis(methoxymethyl)fluorene.

The first internal electron donor may be bis t-butyl carbonyloxy iodo benzene, and the second internal electron donor may be 9,9-bis-methoxymethyl-fluorene.

The Ziegler-Natta procatalyst composition of the present invention may further comprise one or more aluminum-containing cocatalysts.

The Ziegler-Natta procatalyst composition of the present invention may further comprise an external electron donor.

Another aspect of the present invention for achieving the above object is,

A process for the polymerization of olefins, characterized in that under olefin polymerization conditions, one or more olefin monomers are contacted with the Ziegler-Natta procatalyst composition and cocatalyst of the present invention to form a polymer product.

By using the Ziegler-Natta procatalyst composition of various embodiments of the present invention to mix and use internal electron donors having different degrees of polymerization during polymerization of olefins, it is possible to provide an optimal polymer molecular weight distribution than a catalyst based on a single internal electron donor. can

In particular, in the case of the Ziegler-Natta catalyst of the present invention, it exhibits high activity, excellent stereoregularity, and excellent melt index, and due to these characteristics, various polymerization products can be manufactured, and the production cost during the molding and processing of the polymer product. It can provide the effect of lowering

Hereinafter, the present invention will be described in more detail. In the description of the present invention, if a detailed description of a related well-known function or configuration obscures the gist of the present invention, the related description will be omitted.

As used herein, the terms "comprises," or "comprising," are not intended to exclude the presence of any additional component, step or process. That is, all compositions claimed herein using the term "comprising" may include any additional additives, adjuvants or compounds unless stated to the contrary.

The following terms are observed in all aspects of the invention:

As used herein, "Ziegler-Natta catalyst" is a transition metal-containing solid catalyst compound supported on a metal or metalloid compound (eg, a magnesium compound or a silica compound) titanium halide, chromium halide, hafnium halide, zirconium halide and vanadium It means containing a transition metal halide selected from halides.

As used herein, "internal electron donor" means an electron donating compound containing one or more oxygen (O) and/or nitrogen (N) atoms. This internal electron donor is used as a reactant in the preparation of a solid main catalyst.

As used herein, "external electron donor" refers to an electron donor compound used as a reactant in olefin polymerization. The external electron donor is a compound added independently of the main catalyst. It is not added during main catalyst formation. It contains at least one functional group capable of donating at least one electron pair to a metal atom. External electron donors can affect the catalytic properties, including, but not limited to, stereoselectivity of the catalyst system in the polymerization of olefins having three or more carbon atoms, hydrogen sensitivity, ethylene sensitivity, randomness of comonomer incorporation, and Affects catalyst productivity.

In the present invention, the term "procatalyst" refers to a catalyst that can be converted into a catalyst upon activation.

As used herein, "molecular weight distribution" or "MWD" means the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), that is, Mw/Mn, and is used as a measure of the broadness of the molecular weight distribution of a polymer. .

Surprisingly, the present inventors have found that the combination of a haloalkylate compound and a diether compound having different degrees of polymerization as an internal donor makes it possible to produce a polymer having a broad molecular weight distribution, and thus the present invention has been devised. Because of the improved catalytic activity and improved properties, the Ziegler-Natta procatalyst composition for olefin polymerization of the present invention is very suitable for the production of olefinic polymers, especially polypropylene.

One embodiment of the present invention is a Ziegler-Natta procatalyst composition comprising at least one transition metal compound and at least one internal electron donor, wherein the internal electron donor comprises a first internal electron donor and a second internal electron donor, The first internal electron donor and the second internal electron donor relate to a Ziegler-Natta procatalyst composition for polymerization of olefins, characterized in that they have different degrees of polymerization.

The internal electron donor increases the activity of the catalyst in the polyolefin polymerization reaction and improves the stereoregularity of the produced polyolefin, while substantially reducing the catalytic activity within a narrow temperature range when the softening point of the polymer is approached, and thus By reducing the heat generation, it is possible to prevent the formation of agglomerates during the olefin polymerization reaction.

The first internal electron donor may be a haloalkylate compound, and the second internal electron donor may be a diether compound.

The haloalkylate compound is bismethyl carbonyloxy iodo benzene, bis ethyl carbonyloxy iodo benzene, bis propyl carbonyloxy iodo benzene, bis isopropyl carbonyloxy iodo benzene, bis butyl carbonyloxy iodo benzene. A compound selected from the group consisting of do benzene, bis n-butyl carbonyloxy iodo benzene and bis t-butyl carbonyloxy iodo benzene may be used.

Examples of the diether compound include 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-t-butyl-1,3- Dimethoxypropane, 2-cumyl-1,3-dimethoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane, 2-(2-cyclohexylethyl)-1,3-dimethoxypropane , 2- (p-chlorophenyl) -1,3-dimethoxypropane, 2- (diphenylmethyl) -1,3-dimethoxypropane, 2 (1-naphthyl) -1,3-dimethoxypropane, 2 (p-fluorophenyl) -1,3-dimethoxypropane, 2 (1-decahydronaphthyl) -1,3-dimethoxypropane, 2 (pt-butylphenyl (1,3-dimethoxypropane; 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2,2- Dibutyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-diethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-dipropyl-1 ,3-diethoxypropane, 2,2-dibutyl-1,3-diethoxypropane, 2-methyl-2-ethyl 1,3-dimethoxypropane, 2-methyl-2-propyl-1,3-dime Toxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl-2-phenyl 1,3-dimethoxypropane, 2-methyl-2-cyclohexyl-1,3-dimethoxypropane , 2-methyl-2-methylcyclohexyl-1,3-dimethoxypropane, 2,2-bis(p-chlorophenyl)-1,3-dimethoxypropane, 2,2-bis(2-phenylethyl) -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-bis(2-ethylhexyl)-1,3-dimethoxypropane, 2,2-bis(p-methylphenyl)-1 ,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3 -dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclo Pentyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropyl, 2,2-diisobutyl-1,3-diethoxypropane, 2,2-di Isobutyl-1,3-dibutoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2,2-di-sec-butyl-1,3-dimethoxypropane, 2,2 -di-t-butyl-1,3-dimethoxypropane, 2,2-dineopentyl 1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2- Phenyl-2-benzyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 9,9-bis(methoxymethyl)fluorene, 9,9- Bis(methoxymethyl)-2,3,6,7-tetramethylfluorene, 9,9-bis(methoxymethyl)-2,3,4,5,6,7-hexafluorofluorene, 9 ,9-bis(methoxymethyl)-2,3-benzofluorene, 9,9-bis(methoxymethyl)-2,3,6,7-dibenzofluorene, 9,9-bis(methoxy Methyl)-2,7-diisopropylfluorene, 9,9-bis(methoxymethyl)-1,8-dichlorofluorene, 9,9-bis(methoxymethyl)-2,7-dicyclopentyl Fluorene, 9,9-bis(methoxymethyl)-1,8-difluorofluorene, 9,9-bis(methoxymethyl)-1,2,3,4-tetrahydrofluorene, 9, 9-bis(methoxymethyl)-1,2,3,4,5,6,7,8-octahydrofluorene, 9,9-bis(methoxymethyl)-4-t-butylfluorene, etc. Including, one or more of them may be used alone or in combination.

Preferred examples of the diether in the present invention are 9,9-bis(methoxymethyl)fluorene, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3 -diethoxypropane, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclopentyl -1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane.

In a preferred embodiment, the first internal electron donor is t-butyl carbonyloxy iodo benzene and the second internal electron donor is 9,9-bis-methoxymethyl-fluorene.

The first internal electron donor and the second internal electron donor may be present in the composition in a molar ratio of about 10:1 to about 1:10, and the concentration of the internal electron donor may be 0.05-2 moles per mole of the transition metal compound. The internal electron donor serves to increase the activity of the catalyst in the polymerization reaction and to improve the stereoregularity of the synthesized polyolefin. When the content of the internal electron donor is too small compared to the content of the transition metal compound, If the regularity cannot be controlled and the content of the internal electron donor is too large, the activity of the catalyst may be low.

The transition metal compound included in the Ziegler-Natta procatalyst composition of the present invention is meant to include a group IVB, VB, or VIB transition metal or an organic compound containing such a transition metal, and specific examples of the transition metal include Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, and Sg may be mentioned, but are not necessarily limited thereto.

The transition metal compound has the formula T _x X _y , wherein T _x is a transition metal, X is a halogen or a C1-10 hydrocarboxyl or hydrocarbyl group, and x is the group X in the compound in combination with a Group 2 metal compound. is the number of T _x may be a Group 4, 5 or 6 metal. In one embodiment, T _x is a Group 4 metal, such as titanium. X may be chloride, bromide, C1-4 alkoxide or phenoxide or mixtures thereof. In one embodiment, X is chloride.

Non-limiting examples of suitable transition metal compounds that may be used to form the Ziegler-Natta procatalyst composition include TiCl ₄ , ZrCl ₄ , TiBr ₄ , TiCl ₃ , Ti(OC ₂ H ₅ ) ₃ Cl, Zr(OC ₂ H ₅ ) ) ₃ Cl, Ti(OC ₂ H ₅ ) ₃ Br, Ti(OC ₃ H ₇ ) ₂ Cl ₂ , Ti(OC ₆ H ₅ ) ₂ Cl ₂ , Zr(OC ₂ H ₅ ) ₂ Cl ₂ and Ti(OC ₂ H ₅ )Cl ₃ . Mixtures of such transition metal compounds may also be used. There is no limit to the number of transition metal compounds as long as at least one transition metal compound is present.

The Ziegler-Natta procatalyst composition of the present invention may further include an aluminum-containing cocatalyst. Non-limiting examples of suitable aluminum-containing cocatalysts include trialkylaluminum, dialkylaluminum hydride, alkylaluminum dihydride, dialkylaluminum containing 1 to 10, or 1 to 6 carbon atoms in each alkyl- or alkoxide-group. organoaluminum compounds such as alkylaluminum halides, alkylaluminum dihalides, dialkylaluminum alkoxides and alkylaluminum dialkoxide compounds. In one embodiment, the co-catalyst may include a C1-4 trialkylaluminum compound such as triethylaluminum (TEAl).

In addition, the Ziegler-Natta procatalyst composition may further include a cocatalyst. The cocatalyst can reduce the transition metal compound to form an active site, thereby increasing catalytic activity. The cocatalyst is not particularly limited, and any organometallic compound known to be used in the preparation of a general catalyst for polyolefin synthesis may be used without limitation.

Specific examples of the promoter include trimethylaluminum, triethylaluminum, triisobutylaluminum, tributylaluminum, diethylaluminum dichloride, ethylaluminum dichloride, ethylaluminum sescuchloride, tripropylaluminum,

and tributylaluminum, tripentylaluminum, trihexylaluminum, and trioctylaluminum.

In addition, the Ziegler-Natta procatalyst composition may further include an external electron donor. In the Ziegler-Natta procatalyst composition, as the transition metal compound is reduced, a portion of the internal electron donor is removed, and the vacancy may be bonded to the external electron donor to allow polymerization to proceed. Accordingly, the role of the external electron donor in the Ziegler-Natta procatalyst composition is similar to that of the internal electron donor described above. That is, it is possible to more effectively increase the activity of the catalyst in the polyolefin polymerization reaction, and to increase the stereoregularity in the olefin polymerization.

The external electron donor may be used without particular limitation as long as it is an external electron donor commonly used in polyolefin synthesis. Specific examples of the external electron donor include n-propyltrimethoxysilane, dinormalpropyldimethoxysilane, isopropyltrimethoxysilane, diisopropyldimethoxysilane, n-butyltrimethoxysilane, dinormalbutyldimethoxy Silane, isobutyltrimethoxysilane, diisobutyldimethoxysilane, tert-butyltrimethoxysilane, ditertiary butyldimethoxysilane, normalpentyltrimethoxysilane, dinormalpentyldimethoxysilane, cyclopentyltrimethoxy Silane, dicyclopentyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylethyldimethoxysilane, cyclopentylpropyldimethoxysilane, cyclohexyltrimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane , cyclohexylethyldimethoxysilane, cyclohexylpropyldimethoxysilane, cycloheptyltrimethoxysilane, dicycloheptyldimethoxysilane, cycloheptylmethyldimethoxysilane, cycloheptylethyldimethoxysilane, cycloheptylpropyldimethoxysilane, Phenyltrimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, phenylethyldimethoxysilane, phenylpropyldimethoxysilane, normalpropyltriethoxysilane, dinormalpropyldiethoxysilane, isopropyltriethoxysilane , diisopropyl diethoxysilane, normal butyltriethoxysilane, dinormalbutyldiethoxysilane, isobutyltriethoxysilane, diisobutyldiethoxysilane, tert-butyltriethoxysilane, ditertiary butyldiethoxysilane, Normalpentyltriethoxysilane, dinormalpentyldiethoxysilane, cyclopentyltriethoxysilane, dicyclopentyldiethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclopentylpropyldiethoxysilane, cyclo Hexyltriethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldiethoxysilane, cyclohexylpropyldiethoxysilane, cycloheptyltriethoxysilane, dicycloheptyldiethoxysilane, cycloheptyl Methyldiethoxysilane, cycloheptylethyldiethoxysilane, cycloheptylpropyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, phenylmethyldiethoxysilane, phenylethyldiethoxysilane and phenylpropyldiethoxysilane, etc. , one or more of them may be used alone or in combination.

The external electron donor is used together with a co-catalyst during polymerization, and may be selectively used if necessary. The concentrations of the external electron donor and the cocatalyst may each include 0.01 to 10 moles, preferably 0.1 to 10 moles, per 1 mole of the transition metal compound.

In addition, the Ziegler-Natta procatalyst composition may further include a support. In the Ziegler-Natta procatalyst composition, the transition metal compound and the internal electron donor may be fixed or supported on the support. In addition, the order in which the transition metal compound and the internal electron donor are supported on the support is not particularly limited, but the support and the transition metal compound are first reacted to form an active site, and then the internal electron donor is added. The reaction is preferred to increase the catalytic activity.

There is no particular limitation on the support, and a support known to be commonly used in the preparation of a general Ziegler-Natta catalyst can be used without limitation. Preferably, the support includes silica, alumina, zeolite, a magnesium compound, a mixture thereof, or a hybrid support thereof, and more preferably a magnesium compound. The hybrid carrier refers to a state in which two or more of silica, alumina, zeolite, and magnesium compounds react or are combined.

Specific examples of the magnesium compound include magnesium dihalide, dialkoxy magnesium, alkylmagnesium halide, alkoxymagnesium halide, or aryloxymagnesium halide. When magnesium dihalide or dialkoxymagnesium is used as a support, catalyst activity and synthesis The stereoregularity of the polyolefin used can be further improved.

The Ziegler-Natta procatalyst composition of the present invention may include fillers, binders, solvents, polymerization modifiers, and the like as additional components. Sufficient amounts of the procatalyst composition and optional binder should be used to fill any voids between the filler particles to create a relatively dense, hard and break resistant shell on the surface of the procatalyst particles.

Suitable fillers are inert to the other components of the procatalyst composition and also to the active component used in any subsequent polymerization. Suitable compounds may be organic or inorganic and include, but are not limited to, silica, titanium dioxide, zinc oxide, magnesium carbonate, magnesium oxide, carbon and calcium carbonate. In some embodiments, the filler is a hydrophobic fumed silica that imparts a relatively high viscosity to the slurry and good strength to the spray-dried particles. In other embodiments, more than one filler may be used.

The Ziegler-Natta procatalyst composition of the present invention is spray dried to make solid particles, and the spray-dried procatalyst particles are mixed with the cocatalyst to form an active catalyst composition. The spray-dried procatalyst particles can be activated before, simultaneously with or after contact with the monomer or monomers to be polymerized. In a preferred embodiment, the procatalyst is partially or fully activated outside the polymerization reactor by contacting the procatalyst with a portion of the cocatalyst in an inert liquid hydrocarbon. After contacting the procatalyst composition with the cocatalyst, the hydrocarbon solvent may be removed by drying, followed by feeding the catalyst composition to the polymerization reactor, where necessary additional amounts of the same or a different cocatalyst are used to terminate activation make it The partially activated catalyst or unactivated procatalyst composition and the cocatalyst or additional amounts of the cocatalyst are fed into the reactor by the same feed line or by separate feed lines.

Another aspect of the present invention relates to a process for the polymerization of olefins, characterized in that under olefin polymerization conditions, one or more olefin monomers are contacted with a procatalyst composition prepared by the process of the invention, and a cocatalyst to form a polymer product. will be.

Materials having different polymerization degrees are mixed and used as the internal electron donor. Although the catalysts described herein can be used for solution, slurry or gas phase polymerizations, the Ziegler-Natta catalysts prepared from the procatalyst compositions of the present invention have improved productivity when used in gas phase olefin polymerization processes.

One suitable method for carrying out the polymerization process according to the invention comprises carrying out the following steps in any order or in any combination, or in subcombinations of individual steps:

a) feeding a Ziegler-Natta catalyst composition to a polymerization reactor;

b) feeding an aluminum-containing cocatalyst compound to the polymerization reactor;

c) feeding at least one polymerizable monomer to the reactor; and

d) extracting the polymer product from the reactor.

Monomers suitable for polymerization in the present invention include C2-C20 olefins, diolefins, cycloolefins and mixtures thereof. Particularly suitable are ethylene homopolymerization processes and copolymerizations of ethylene with C3 to C8 α-olefins (eg 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene).

Examples of the olefinic monomer include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1- dodecene, 1-tetradecene, 1-hexadecene, 1-aitocene, norbornene, norbornadiene, ethylidene noboden, phenyl noboden, vinyl noboden, dicyclopentadiene, 1,4-butadiene, 1 ,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene.

In a continuous gas phase process, the partially or fully activated procatalyst composition is continuously fed to the reactor along with a separate portion of any additional activator compound necessary to terminate activation. Polymerization is generally carried out in a fluidized bed at a temperature and pressure sufficient to initiate the polymerization reaction in the presence of a catalytically effective amount of a catalyst composition in the absence of moisture, oxygen, CO, CO ₂ or catalytic toxins such as acetylene.

The polymerization reaction can be carried out in gas phase, liquid phase, or solution phase. When carrying out the polymerization reaction in the liquid phase, a hydrocarbon solvent may be used, or olefin itself may be used as the solvent. The polymerization temperature is usually in the range of -50 to 350°C, preferably 20°C. If the polymerization temperature is less than -50 ℃, the activity of the catalyst is not good, and if it exceeds 350 ℃, it is not good because the stereoregularity is lowered.

The polymerization pressure may be carried out at 1 to 100 atmospheres, and it is preferable to proceed under the conditions of 2 to 40 atmospheres. When the polymerization pressure exceeds 100 atm, it is not preferable from an industrial and economic point of view.

The polymerization reaction can be carried out by any of batch, semi-continuous, and continuous methods.

A heat stabilizer, a light stabilizer, a flame retardant, carbon black, a pigment, an antioxidant, etc. which are usually added may be added to the polyolefin prepared using the solid catalyst of an embodiment of the present invention. In addition, the prepared polyolefin may be mixed with low-density polyethylene (LDPE), high-density polyethylene (HDPE), polypropylene, polybutene, ethylene/propylene rubber, and the like.

The polyolefin prepared by using the Ziegler-Natta procatalyst composition of the present invention has a large particle size and uniformity, contains a low fine powder content, and can be usefully used in molding materials such as plates, films, containers and fibers.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are for illustrative purposes only, and are not intended to limit the scope of protection limited by the appended claims.

Example

Example 1

로 유지하면서 사염화티타늄 0.1 mol과 톨루엔 30 ㎖를 투입한다. 1시간 교반 후 반응기의 온도를 110℃로 올려 주면서 비스 t-부틸 카보닐옥시 아이오도 벤젠과 9,9-비스메톡시메틸플루오렌을 주입하였다. 110℃에서 1시간 반응 후 교반을 멈추고 상등액을 제거하고, 톨루엔 80 ㎖와 사염화티타늄 20 ㎖을 투입하여 1시간 반응시킨다. 고체 성분을 톨루엔과 헥산으로 세척하여 고체 촉매를 얻었다.In a high-purity nitrogen atmosphere, 10 g of diethoxymagnesium and 80 ml of toluene were put into a double-jacketed glass reactor with a stirrer, and 15

0.1 mol of titanium tetrachloride and 30 ml of toluene are added while maintaining After stirring for 1 hour, while raising the temperature of the reactor to 110° C., bis t-butyl carbonyloxy iodobenzene and 9,9-bismethoxymethylfluorene were injected. After the reaction at 110° C. for 1 hour, stirring was stopped, the supernatant was removed, and 80 ml of toluene and 20 ml of titanium tetrachloride were added and reacted for 1 hour. The solid component was washed with toluene and hexane to obtain a solid catalyst.

Comparative Example 1

A catalyst was prepared in the same manner as in Example 1, except that only bis-t-butyl carbonyloxy iodobenzene was used as an internal electron donor during the preparation of the procatalyst composition for olefin polymerization.

Comparative Example 2

A catalyst was prepared in the same manner as in Example 1, except that only 9,9-bismethoxymethylfluorene was used as an internal electron donor in preparing the procatalyst composition for olefin polymerization.

Test Example 1: Catalyst Performance Evaluation Experiment

In order to evaluate the performance of the Ziegler-Natta catalyst for olefin polymerization according to the present invention, the following experiment was performed. Polymerization of propylene was performed using a 2-liter polymerization reactor. The process of reducing the pressure in the reactor to a vacuum of 3 Torr or less and filling with high-purity nitrogen was repeated 5 times. After filling the reactor with 500 g of propylene and 750 cc of hydrogen at room temperature, 3 mmol of triethylaluminum, 0.18 mmol of dicyclopentyldimethoxysilane, and 0.0044 mmol of the catalyst prepared in Example 1 and Comparative Examples 1-2 and the reactor temperature was raised to 70° C. and reacted for 1 hour. Propylene was removed from the polymer and a final polymerization product was obtained.

The polymerization activity of the catalysts prepared in Example 1 and Comparative Examples 1 and 2 and the stereoregularity and characteristics of the polymerization product were evaluated by the following method, and the results are shown in Table 1 below.

1) Catalyst activity

It was obtained in units of g-polymer/g-catalyst from the weight of the final polymerization product.

2) Melt Index

It was measured at 230°C and a load of 2.16 kg according to ASTM D1238 conditions.

3) Isotacticity Index of polypropylene

The stereoregularity of polypropylene was obtained by the weight ratio of the polymer extracted and the dissolved polymer while the temperature was lowered after being dissolved in boiling xylene.

4) molecular weight distribution (MWD)

It was obtained as a ratio (Mw/Mn) of a weight average molecular weight (Mw) and a number average molecular weight (Mn) measured using gel permeation chromatography (GPC).

catalyst catalytic activity
(Kg PP/g cat.) Melt Index
(g/10min) molecular weight distribution
(MWD) Stereoregularity (%) Example 1 41.2 11.3 5.6 98.0 Comparative Example 1 28.2 16.3 4.7 95.4 Comparative Example 2 51.6 8.5 3.8 98.8

As can be seen from the results in Table 1, higher activity and stereoregularity than the catalysts of Comparative Examples 1 and 2 by controlling the molecular weight distribution during polypropylene polymerization using the exemplary Ziegler-Natta procatalyst composition of the present invention It was confirmed that the physical properties of the product can be improved by showing .

In the above, the preferred embodiments of the present invention have been described in detail as an example, but these descriptions merely describe and disclose exemplary embodiments of the present invention. Those skilled in the art will readily recognize that various changes, modifications and variations can be made from the foregoing description and accompanying drawings without departing from the scope and spirit of the present invention. Accordingly, such modifications or changes of the present invention should be construed as being included in the claims of the present invention.

Claims (11)

at least one transition metal compound and at least one internal electron donor;
A Ziegler-Natta procatalyst composition, wherein the internal electron donor comprises a first internal electron donor and a second internal electron donor, wherein the first internal electron donor and the second internal electron donor have different degrees of polymerization;
The first internal electron donor is t-butyl carbonyloxy iodo benzene, and the second internal electron donor is 9,9-bis-methoxymethyl-fluorene, Ziegler-Natta procatalyst for olefin polymerization, characterized in that composition. delete delete delete delete The Ziegler-Natta procatalyst composition for olefin polymerization according to claim 1, wherein the first internal electron donor and the second internal electron donor are present in the composition in a molar ratio of 10:1 to 1:10.
The Ziegler-Natta procatalyst composition for olefin polymerization according to claim 1, wherein the concentration of the internal electron donor is 0.05 to 2 moles per 1 mole of the transition metal compound. The Ziegler-Natta procatalyst composition for olefin polymerization according to claim 1, wherein the Ziegler-Natta procatalyst composition further comprises at least one aluminum-containing cocatalyst.
The Ziegler-Natta procatalyst composition for olefin polymerization according to claim 1, wherein the Ziegler-Natta procatalyst composition further comprises an external electron donor.
10. A polyolefin polymer product characterized in that under olefin polymerization conditions, one or more olefin monomers are contacted with the Ziegler-Natta procatalyst composition of any one of claims 1, 6-9, and a cocatalyst. Olefin polymerization method.
11. The method according to claim 10, wherein the polyolefin is polypropylene.