CS236763B2 - Catalyst for processing of alpha-olefine polymere - Google Patents

Abstract

A catalyst component, solid (II), is prepared by reacting a trivalent metal halide with a hydroxide, oxide or carbonate of a divalent metal, a double compound containing any such compound, or a hydrate of a divalent metal compound thereby to form a solid product (I); and reacting the solid product (I) with an electron donor comprising one or more electron donor compounds, and with an electron acceptor comprising titanium tetrachloride and optionally one or more other electron acceptor compounds, thereby to form a solid product (II), the electron donor and/or the electron acceptor being reacted with the solid product (I) in at least two separate portions. Reaction of the catalyst component with an organoaluminium compound gives an alpha -olefin homo- or co- polymerization catalyst.

Description

The present invention relates to a catalyst for the production of α-olefin polymers by polymerizing α-olefins, in particular propylene polymers, consisting of a solid product II obtainable by reaction of aluminum or ferric chloride with a magnesium, oxide or magnesium carbonate or a double compound containing any of these compounds or with a magnesium hydrate compound to form solid product I, followed by reacting the solid product I with at least one electron donor from the group comprising, for example, esters, and with at least one electron acceptor from the group comprising titanium tetrachloride to form solid product II, and (b) an organoaluminum compound.

To date, many inventions using electron donors as one of the components of the α-olefin polymerization catalyst have been proposed.

For example, catalysts - containing magnesium chloride (anhydrous), Mg-Cl-bonded solids, magnesium carbonate, oxides or hydroxides of Group II or Group VIII elements of the Periodic System - elements etc. and as one of the electron donor components have been described .

On the other hand, the present inventors have previously developed catalysts for the polymerization of ethylene or α-olefins prepared by reacting a trivalent metal halide with a divalent metal compound to form a solid product (I) with a transition metal compound deposited in various ways on solid product (I). For example

1) a process in which a solid product catalyst obtained by reacting said solid product (I) with a polysiloxane or an electron donor and then reacting the obtained material with a transition metal compound (Japanese Laid-Open Publication No. 13 827/1977) is used as a catalyst No. 50,994 (1974) (corresponding to U.S. Patent No. 3,987,233), and Japanese Patent Application No. 127,750 (1977);

2) a process using catalyst components of a product obtained by simultaneous addition to said product (Ij of a polysiloxane or electron donor and a transition metal compound, or by adding a polysiloxane complex with a transition metal compound prepared beforehand (Japanese Patent Application Nos. 21,246 / 1978, 21). 247/1978 and 32 031/1978 etc.,) U.S. patent application filed on Feb. 21, 1979 corresponding in part to the foregoing;

3) a process in which the product obtained by reacting the solid product (I) with a transition metal compound and then reacting the obtained material with a trivalent metal alcoholate and then reacting the obtained material again with a transition metal compound [Japanese Laid-Open Patent Publication No. 19,790 (1977 (Patent Application No. 96 427 / (1975, corresponding to U.S. Patent No. 4,076,922))] etc. have already been filed for patenting.

The present inventors have carried out various studies to improve these earlier inventions and as a result find that the efficiency of the catalyst is highly dependent on the manner in which said solid product (I) is reacted with an electron donor and an electron acceptor. The authors have carried out further studies in this regard and have the result that good yields can be obtained by reacting said electron donor and said electron acceptor in at least two separate doses.

The invention is an improved catalyst for the production of α-olefin polymers by polymerizing α-olefins, in particular propylene polymers, consisting of (a) a solid product II obtainable by reacting aluminum or ferric chloride with a hydroxide, -oxide or magnesium carbonate or a double compound containing any or a hydrate of a magnesium compound to form a solid product I and then reacting the solid product I with at least one electron donor from the group comprising, for example, esters, and at least one electron acceptor - from the group comprising titanium tetrachloride and silicon, to and (b) an organoaluminum compound.

The catalyst according to the invention is characterized in that the catalyst as solid product II comprises a product obtainable by reacting the above solid product I with electron donors and / or electron acceptors in two separate doses and using titanium tetrachloride as at least one electron acceptor.

The process for producing the catalyst used in the polymerization process of the invention will be described in detail.

First, a trivalent metal halide is reacted to obtain a solid product (I).

The trivalent metal halide used is, for example, aluminum chloride (anhydrous), aluminum bromide (anhydrous), ferric chloride (anhydrous), etc. As the divalent metal compounds, for example, hydroxides such as magnesium hydroxide, e.g. calcium hydroxide, zinc hydroxide, manganese hydroxide etc., oxides such as magnesium oxide, calcium oxide, zinc oxide, manganese oxide etc., double oxides containing a bivalent metal such as MgAl ₂ O ₄ , Mg ₂ SiO ₄ , Mg ₆ MnO ₈ etc. , carbonates or double carbonates, for example magnesium carbonate, manganese carbonate, MgCO ₃ . CaCO ₃ etc., halide hydrates such as stannous chloride dihydrate, magnesium chloride polyhydrate (η - 1 - 6), nickel chloride hexahydrate, manganese chloride tetrahydrate, potassium magnesium chloride hexahydrate etc., halide and hydroxide containing hydrates such as MgCl 2. nMg (OH) 2. mH 2 O (n == 1 ~ 3, m = 1-6), etc., double oxide hydrates, e.g. 3 MgO. 2 SiO _2; . 2 H 2 O, etc., hydrates of a carbonate-hydroxide double compound, for example 3 MgCO ₂ . Mg (OH) ₂ . . 3 H ₂ O, etc., hydrates of a double hydroxide and carbonate compound containing a divalent metal, for example MgAl ₂ (OH) 1 ₆ CO 3. 4 H ₂ O, etc., and the like.

The solid product (I) is prepared as follows:

It is preferred to grind the trivalent metal halide together with the divalent metal compound in a ball mill for 5 to 50 hours or in a vibratory mill for 1 to 10 hours to mix sufficiently. With respect to the mixing ratio, 0.1 to 20 moles per mole of trivalent metal halide is usually sufficient. A particularly preferred range is 1 to 10 moles. The reaction temperature is usually in the range of room temperature (20 ° C) to 500 ° C, preferably 50 ° C to 300 ° C. The reaction time is suitably in the range from 30 minutes to 50 hours. At lower reaction temperatures, the reaction is carried out for a long time to allow the reaction to proceed sufficiently so that unreacted trivalent metal cannot be left. The solid product so obtained is referred to as the solid product (I), which is then reacted with an electron donor (abbreviated ED) and an electron acceptor ¹ (abbreviated EA).

ED used in this reaction refers to organic compounds containing at least one oxygen, nitrogen, sulfur and phosphorus atom, such as alcohols, ethers, esters, aldehydes, carboxylic acids, ketones, nitriles, isocyanates, azo compounds, phosphines, phosphites, phosphinites, thioethers , thioalcohols, polysiloxanes, etc.

For specific examples, alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, phenol, cresol, xylenol, ethylphenol, naphthol, cumyl alcohol, etc., ethers such as diethyl ether, di-n-propyl ether , di-n-butyl ether, diisoamyl ether, di-n-pentyl ether, di-n-hexyl ether, di-n-octyl ether, diisooctyl ether, ethylene glycol monomethyl ether, diphenyl ether, tetrahydrofuran etc., esters such as ethyl acetate, butyl formate, amyl acetate, vinyl butyrate, vinyl acetate, benzoic acid methyl ester, benzoic acid ethyl ester, benzoic acid propyl ester, benzoic acid butyl ester, benzoic acid octyl ester, benzoic acid 2-ethylhexyl ester, toluylic acid methyl ester, toluylic acid ethyl ester, toluylic acid 2-ethylhexyl ester, ethyl ester of anisic acid, propyl ester of anisic acid, ethyl ester of cinnamic acid, methyl ester of naphthoic acid, et naphthoic acid ester, naphthoic acid propyl ester, naphthoic acid butyl ester, naphthoic acid 2-ethylhexyl ester, phenylacetic acid ethyl ester etc., aldehydes such as acetaldehyde, benzaldehyde etc., carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid , oxalic acid, succinic acid, acrylic acid, maleic acid, benzoic acid, etc., ketones such as methylethylketone, methylisobutylketone, benzophenone etc., nitriles such as acetonitrile etc., amines such as methylamine, diethylamine, tributylamine, triethanolamine, pyridine , aniline, etc., isocyanates such as phenyl isocyanate, toluyl isocyanate etc., azo compounds such as azobenzene etc. phosphines such as ethylphosphine, triethylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, triphenylphosphine etc., phosphites such as dimethylphosphite, di- n-octylphosphite, tri-n-butylphosphite, triphenylphosphite etc., phosphinites such as ethyldi ethylphosphinite etc., thioethers such as diethylthioether, diphenylthioether, methylphenylthioether, ethylene sulfide, propylene sulfide etc., thioalcohols such as ethylthioalcohol, n-propylthioalcohol, thiophenol and the like.

Further, as far as the polysiloxanes are concerned, siloxane polymers with a chain or ring form represented by the general formula (in which R 1 and R 2 denote the same or different kinds of substituents and denote an integer), and especially those in which R ₁ and R 2 denote one or a plurality of hydrogen atoms, a hydrocarbon group such as alkyl, aryl, etc., halogens, alkoxy, aryloxy, and carboxylic acid groups, said two or more groups being spaced and combined in the molecule in different proportions.

With respect to specific examples, which are generally preferably used, lower polymers such as octamethyltrisolloxane, octaethylcyclotetrasiloxane, etc., alkylsiloxane polymers, such as dimethylpolysiloxane, ethylpolysiloxane, methylethylpolysiloxane, etc., polymers of arylsiloxiloxane, etc. polymers of alkylarylsiloxanes, for example diphenyloctamethyltetrasiloxane, methylphenylpolysiloxane, and the like.

It is also possible to use these different kinds of polysiloxanes in a mixture. Furthermore, it is essential that these polysiloxanes be in the liquid phase during the reaction, and it is therefore desirable that the polysiloxanes be selected in the form of a liquid phase (HBB). §G) and such • <pp ^^. Ý: ^^ ljnř ^ <aD _! ^ I / _F) M jW4 áIOOT & NWI ^ TA píHf®W 2gjsCó $ oyýtfCiP -lQh ⁵ oaží2 -угШй щ ^ Jj Jy ^{2 1} 1> γ dobiavned .bydebla ../uJanovti·•výše. Eqi jp. qmošvAí.> RfppJvvfti.il j i νβ) ρ® MR potilivě, ípípfi-vefipeijěŘRůž síuíwy? (j .aníoekin _P Pale j-Di-lkud .spiitkíh-EA lUžvacíbo, MW01 tQjtvypáíkgSBU MS в! ^ ЙМ®йй9 Mqt 8 $ ШйеВ -)) С 1 t ^groups? F Híi jpž / rVro аетЮЙЙМ tables.!, B ^ Q4 ^ ul: j ^ ig..rj: .lK ^ _f (<WMWi |> ýhιd ^ ΐ! pJ'í ^ йQϊnic: ítý ^ č.r.Ч: ž {tΦ ^ ijd pínaríýíj .β Ι ι ι <<ρ <<<<<<<<<»<» ,. ШоШ and eighth k.EWMHÝ) aM.Qrii .íftqsfQgitgvftlQlp ^ ^ io ^ ^ y ^ fofoBflfiSilĎííiRft T гцй _(уапад | _1Ш;; le ^ lPFďdbPpíiijQiwiič Π ^ t ^ ili ^ i ^ E ^ N ^^ th, , rμ ЙlQriftLj ^] ¢ ižaíýíýíL _{^^%) £} fl! ^ j) φ (^ w ^ f

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-eelyHíerv .ovoonoHe yvileevd 'leieoiyriíe .ev упШегуЯ' udeelyflk-) .evoiBn угШегуЯ Ί91 in which

R and R‘ are individually hydrocarbon radicals, for example alkyl, aryl, alkaryl, cycloalkyl, etc., or alkoxy,

X represents a halogen atom, for example chlorine, bromine and iodine, and n and n ‘are individually any number, provided that 0 <n + n‘ · 3.

For specific examples, mention may be made of trialkyl aluminum, for example trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, tri-n-butyl aluminum, triisobutylaluminum, tri-n-hexyl aluminum, triisohexyl aluminum, tri-2-methylpentyl aluminum, trl-n-octyl n-decyl aluminum etc., diethyl aluminum monohalides, such as diethyl aluminum monochloride, di-n-propyl aluminum monochloride, diisobutyl aluminum monochloride, diethyl aluminum monofluoride, diethyl aluminum monobromide, diethylaluminum monohydride, alkyl aluminum hydride, alkyl hydrides, alkyl hydrides, alkyl hydrides ethyl aluminum, ethyl aluminum dichloride, isobutyl aluminum, etc., in addition, alkoxyalkyl aluminum, for example monoethoxydiethyl aluminum, diethoxy monoethyl aluminum, etc. may also be used.

The ratio of the amount of such organoaluminum to be combined with the solid product (II) is in the range of 50-5000 g of the organoaluminum compound, based on 100 solid product (II), and by simply mixing together one can obtain a catalyst with an activity suitable for. α-olefin polymerization useful as in the case of the Ziegler-Natta catalyst.

The polymerization reaction can be carried out in a hydrocarbon solvent such as n-hexane, n-heptane, n-octane, benzene, toluene and the like, and it is also possible to carry out the reaction without using any solvent but in a liquefied α-olefin monomer such as in liquefied propylene, liquefied 1-butene and the like.

The polymerization is carried out at a polymerization temperature of room temperature [20 ° C] up to 200 ° C at a polymerization pressure of atmospheric pressure (0.1013 MPa) up to 5.0 MPa, usually for 5 minutes to 10 hours. In the polymerization, the necessary amount of hydrogen can be added to control the molecular weight as in the conventional polymerization process.

With respect to α-olefins used in the present invention, straight chain monoolefins such as ethylene, propylene, 1-butene, 1-hexene, 1-o-ktene, 1-decene, etc., branched monoolefins are exemplified. 4-methyl-1-pentene, 2-methyl-1-pentene, 3-methyl-4-butene, etc., diolefins, such as butadiene, isoprene, chloroprene, styrene, etc. α-olefins, but also copolymerization by combining different α-olefins, such as propylene with ethylene, 1-betene with ethylene, propylene with 1-butene, etc.

A first effect achieved by the polymerization process according to the invention is that highly crystalline polyolefins are obtained. For example, according to the above inventions of the inventors, the content of crystalline n-heptane insoluble polypropylene was 75 to 96%, while according to the invention it increased to about 92 to 97%.

A second effect of the present invention is that propylene polymers are particularly improved. According to the above methods in the inventions made by the inventors of the present invention, the ethylene polymer particles have a good form and have a bulk density (BD) of up to 0.45, but the propylene polymer particles have a bad form and have a BD of only 0.08 to 0. 18 and the particles were not yet uniform. In the case of the present invention, the BD propylene polymers were up to 0.35 and also the particle shape was improved to almost spherical form.

A third effect of the present invention is that the yield of α-olefin polymers relative to the solid product (II) is sufficiently high and, in particular in the case of propylene polymerization under conventional polymerization conditions, is up to 5 x 10 3 - 2 x 10 · g (polymer) / g (solid product (II), even if the removal of the catalyst remaining in the obtained polymer, i.e., ash removal, polymers are not discolored and no adverse effect such as degradation of the physical properties of the polymers, mold rust during molding) polymers, etc.

A fourth effect of the present invention is that transition metals are used very efficiently and, in the case of conventional propylene polymerization, the polymer yield is up to 1 _x 10 &lt; -1 &gt; - 5 _x 10 6 g (polymer) / g (transition metal atom).

The present invention will be illustrated in more detail in the Examples below.

Examples

Example 1

1) Preparation of solid products (I) and (II) g of anhydrous aluminum chloride and 58 grams of magnesium hydroxide are reacted by co-milling on a vibrating mill at 180 ° C for 10 hours, and the reaction proceeds with the evolution of hydrogen chloride gas . After heating, the reaction product obtained was cooled with a stream of nitrogen and a solid product (I) was obtained.

100 g of this solid product (I) and 20 grams of titanium tetrachloride as EA were placed in a vibrating ¹ mill and reacted together at 120 degrees Celsius for 5 hours, after which time unreacted titanium tetrachloride was removed under reduced pressure. followed by cooling the product obtained.

In addition, 12.0 g of titanium tetrachloride-benzoic acid complex were added as' ED (molar ratio - 1: 1, the term "molar ratio" will be omitted further), and the reaction was carried out by milling with a vibratory mill at 40 ° C for 120 hours to give the solid product (II). The titanium atom content in 1 g of solid product (II) was 19.5 mg.

2) Preparation of Polypropylene Polymer

In a 1.5 liter, nitrogen purged stainless steel reactor, a liter of n-hexane, 480 mg of triisobutyl aluminum and 12 mg of the solid product (II) obtained according to paragraph 1 above) were charged and propylene was polymerized with 75 ml of hydrogen. The propylene partial pressure was 1.28 MPa at 60 ° C for 5 hours. After completion of the polymerization, the solvent was removed by evaporation to obtain the polymer. Five grams of this polymer was subjected to extraction with 50 ml of n-heptane using a Soxhlet extractor at the boiling point of n-heptane (98 ° C). The obtained n-heptane-soluble product was converted into atactic polypropylene and the residue was converted into isotactic polypropylene. The isotactic index was expressed as follows:

Isotactic index = amount of isotactic polymer _ total amount of polymer x 100

The obtained polymer had a BD of 0.35 and had a much better form. The results are shown in Table 1 along with the results of the other examples.

Example · 2

A 785 ml ball mill with a diameter of 100 mm (made from SUS 304) containing 80 stainless steel balls of 10 mm diameter was charged with 20 g of solid product (I) obtained in Example 1, 3 g of silica chloride as EAt and 4.0 g of ethyl cinnamate as ED and the reaction was carried out during milling at 40 ° C for 75 hours. After completion of the reaction, the unreacted materials were removed under reduced pressure, and then 80 g of titanium tetrachloride as EA2 was added and the reaction was continued during grinding at 80 ° C for 40 hours. After completion of the reaction, the reaction product was separated by filtration in a nitrogen purged dry box, followed by washing three times with n-hexane in portions of 150150 ml and then drying to obtain a solid product (II).

Using this solid product (II), polypropylene was polymerized as in Example 1. The results are shown in the table

1.

Example 3

The complex obtained by reacting 3 g of aluminum chloride with 1.7 g of dimethylpolysiloxane as ED 1 with stirring was added to a ball mill and 20 g of solid product (I), as in Example 1, were added and the reaction was carried out during grinding. at 30 ° C for 48 hours. Then 8 g of titanium tetrachloride complex such as EA2 with tetrahydrofuran such as ED2 (1: 2) was added, and the reaction was carried out during grinding at 50 ° C for 60 hours to obtain a slurry of solid product (II). The results are shown in Table 1.

Examples g of anhydrous aluminum chloride and 30 grams of magnesium oxide were reacted together during ball milling at 120 ° C for 48 hours to obtain a solid product (I).

g of this solid product (I); and. 5. g of a titanium tetrachloride complex such as EA with ethyl phenylacetic acid ED (1: 1) was reacted together during a milling in a vibratory mill at room temperature (20 ° C) for 30 minutes. The product obtained was suspended in a solution of 180 g of titanium tetrachloride in 50 ml of n-heptane and the reaction was carried out at 100 cq for 4 hours. After completion of the reaction, the reaction product was separated by dry-box filtration, followed by washing three times with 150 ml of n-hexane and then drying to obtain the solid product (II).

Using the solid product (II), polypropylene was polymerized as in Example 1. The results are shown in Example 1.

Example 5 g of the material obtained by heating 60 grams of aluminum chloride (anhydrous) and 20 grams of hydrotalcite [MgtAl ₂ (OH) ₁₆ CO ₃ . . 4Η ₂ · 0] at 100 ° C · 2 hours was · · milled and placed in a reaction using a vibrating · mill at 250 ° C for 1 hour O-, to obtain a solid product (I).

ml of methyl hydrogen polysiloxane such as EDi and 50 g of the above solid; of product (I) was added to 200 ml of n-hexane and reacted at 40 ° C for 1 hour, followed by isolation by filtration, washing with n-hexane and drying. Twenty grams of this dry solid, 3 grams of methyl toluyl ester such as ED ₂ and 6 grams of titanium tetrachloride such as EA were put in a ball mill and ground and reacted at 80 ° C for 20 hours, and unreacted materials were then removed under reduced pressure. pressure at 80 ° C for 2 hours to give a solid product (I).

Using this solid product (II), polypropylene was polymerized as in Example 1. The results are shown in the table

AND.

Example 6 g of ferric chloride (anhydrous) and 70 g of magnesium aluminum oxide (MgAlyO.) Were reacted in a vibratory mill at 320 cc for 5 hours to obtain a solid product (I).

To a suspension of 20 g of this solid product (I) in 180 ml of toluene was added 10 g of ethanol as ED ₁ and the reaction was carried out at 30 ° C for one hour. Then 150 ml of toluene was added and the decanter was repeated twice to obtain a total amount of 180 ml. As ED _2, 8 g of benzophenone was added and the reaction was carried out at 60 cc for 30 minutes, followed by decanting, adding 150 ml of toluene, decanting and obtaining a total amount of 60 ml. Then 100 ml of titanium tetrachloride as EA and 20 ml of n-butyl ether were added. The reaction was carried out at 130 ^° C for one hour, followed by isolation by filtration, washing with n-hexane and drying to give the solid product (II).

Using this solid product (II), propylene was polymerized as in Example 1. The results are shown in Table 1.

EXAMPLE 7 g of aluminum chloride (anhydrous) and 65 g of magnesium chloride (hexahydrate) (MgCl2 · 6H2) were reacted together - under a vibrating mill at 80 ° C for 20 hours to obtain a solid product. (AND).

To 20 g of this solid product (I) was added 3 g of n-butyl ether (EDJ). The reaction was carried out in a vibratory mill at 40 ° C for 30 minutes and then 2 g of benzoic acid (ED ₂ ) was added to the further reaction in a vibrating mill at 60 ^C C for 30 minutes. the reaction product was suspended DO- liquid mixture of 120 g of titanium tetrachloride and 30 ml of n-hexane and the reaction was carried out at 75 degrees Celsius for 3 hours. after - completion of the reaction, unreacted materials were distilled off under reduced pressure to obtain a solid product (II).

Using this solid product (II), propylene was polymerized as in Example 1. The results are shown in Table 1.

Comparative Example 1

Example 1 was repeated except that the solid product (I) was reacted with titanium tetrachloride not in two separate batches as in Example 1, but at once.

100 g of the solid product (I) obtained in Example 1, 20 g of titanium tetrachloride and 12 g of titanium tetrachloride-ethyl benzoate complex (1: 1) were mixed and ground and reacted in a vibratory mill at 120 ° C for 5 hours and further allowed to react under grinding at 40 ° C for 120 hours, followed by removal of unreacted titanium tetrachloride under reduced pressure to give a solid product (II). Using the solid product (II), propylene was polymerized as in Example 1. The results are shown in Table 1. As can be seen from the table, any of the polymer yields, isotactic index and BD were worse compared to Example 1.

Comparative Example 2

Example 6 was repeated with the exception that solid product (I) was added and reacted with three kinds of ED, not in three separate doses as in Example 6, but at one time.

To suppress the same solid product (I) obtained in Example 6 in 180 ml of toluene, 10 g of ethanol, 8 g of benzophenone, 100 ml of titanium tetrachloride and 20 ml of di-n-butyl ether were simultaneously added and the reaction was carried out at 30 ° C. one hour, then at 60 ° C for 30 minutes and then at 130 ° C for one hour; followed by isolation by filtration, washing with n-hexaane and drying to give the solid product (II).

Propylene was polymerized as in Example 6 except this solid product (II) was used. The results are shown in Table 1. As can be seen from the table, the results in this case were also much worse than in Example 6.

Example 8

Using the solid product (II) obtained in Example 1, prepylene-ethylene copolymerization was performed.

mg of this solid product (II) obtained according to Example 1, 420 mg of triethyl aluminum and 20 ml of hydrogen were introduced into the polymerization vessel and the polymerization was carried out at 60 DEG C. for 4 hours with ethylene being added 8 times at 30 minute intervals. minutes, in each case in an amount of 10 g of ethylene and at a partial pressure of propylene

1,08 MPa. After the reaction, the same operations as in Example 1 were performed to obtain a propylene-ethylene copolymer. The polymer yield per 1 g of solid product (II) was 20.800 g (polymer) and the isotactic index was 92.0.

Example 9

Propylene-1-butene copolymerization was carried out as in Example 8, except that ethylene was replaced with 20 g of 1-butene. The yield of polymer per g of solid product (II) was 20,300 g (polymer). The isotactic index was 91.0.

Example 10

Using the solid product (II) obtained according to Example 2, ethylene was polymerized.

Using the 8 mg solid product (II) obtained according to Example 2 and 480 mg triisobutyl aluminum, the polymerization reaction was carried out at 85 ° C for 5 hours under a hydrogen partial pressure of 0.50 MPa and an ethylene partial pressure of 0.50 MPa. After completion of the reaction, the polymer was obtained as in Example 1. Yield of polymer bvl 18,800 g (polymer) / g [solid product (II)].

BD: 0.40, MI: 6.5.

Example 11

Using the solid product (II) obtained according to Example 3, 1-butene was polymerized.

Using 20 g of the solid product (II) obtained according to Example 3 with 380 mg of triethyl aluminum, 480 g of 1-butene were continuously added at 70 ° C for 4 hours and then the reaction was continued for 2 hours. After completion of the reaction, the solvent was distilled off to give 2.73 g of polybutene. The polymer yield was 13 650 g (polymer) / g [solid product (II)].

Example 12

133 g of aluminum chloride (anhydrous) and 40 g of magnesium oxide were milled in a ball mill for 24 hours and then heated at 120 ° C for 2 hours, followed by cooling and further grinding for 10 hours to obtain the solid product (I) g of this solid product (I) and the reaction product obtained by mixing and reacting 12 g of ethyl benzoate (ED) with 4.5 g of silica chloride (EA) at room temperature (20 ° C) were milled And allowed to react in a ball mill at 35 ° C for 48 hours. 20 g of the obtained powder were suspended in 180 g of titanium tetrachloride (EA2) and the reaction was carried out at 80 ° C for 2 hours; followed by removal of the supernatant fluid by decantation, additional addition of 180 g of titanium tetrachloride, reaction at 80 degrees Celsius for 1 hour, and removal of the supernatant fluid by decantation. The addition of 150 ml of n-hexane and removal of decantations was repeated twice, followed by isolation by dry-box filtration and drying to give the solid product (II).

Using this solid product (II), propylene was polymerized as in Example 1. The results are shown in Table 1.

Example 13 g of solid product (I) obtained in the same manner as in Example 12 2 g of cumyl alcohol (ED) and 5 g of ethyl benzoate (ED2) were ground and reacted in a ball mill at 40 ° C for 48 hours, then 9 g · silica (EAJ) was added and ground and the reaction was carried out for 24 hours to obtain a powder. 20 g of this powder was then suspended in 240 g of titanium tetrachloride (EA ₂ ) and 150 ml of n-hexane was added and the supernatant removal was repeated twice, followed by isolation by filtration and drying to obtain a solid product (II).

Using this solid product (II), propylene was polymerized as in Example 1. The results are shown in Table 1.

Example. 14 g of the solid product (I) obtained in the same manner as in Example 12 and 12 g of benzoic acid methyl ester (ED) were milled and reacted in a ball mill at 30 ° C for 24 hours and then 15 g were added. Silica Chloride (EAjJ) was carried out for 48 hours to obtain a powder. Twenty grams of this powder was suspended in 350 g of titanium tetrachloride (EA2) and the reaction was carried out at 80 ° C for 2 hours, followed by Removing the supernatant by decanting, adding 200 ml of tetrachlorethylene and decanting, then adding 200 milliliters of n-hexane and decanting twice more, followed by distillation of the n-hexane under reduced pressure to obtain a solid product (II).

Using the solid product (II), propylene was polymerized as in Example 1. The results are shown in Table 1.

Example 15 g of solid product (I) obtained in the same manner as in example 12 and 16 g of benzoic acid isopropyl ester (ED) were milled and reacted in a ball mill at 45 ° C for 48 hours.

Twenty g of the obtained powder was suspended in 190 g of titanium tetrachloride (EA) and the reaction was then carried out at 70 ° C for 4 hours, followed by isolation by filtration to separate and remove the reaction liquid. The solid obtained was resuspended in 220 g of titanium tetrachloride and the reaction was then carried out at 90 ° C for one hour, followed by removal of the reaction liquid by decantation. 250 ml of n-hexane was added and the decantation was repeated twice, followed by distilling off the n-hexane under reduced pressure to obtain a solid product (II).

Using this solid product (II), propylene was polymerized as in the example

1. The results are shown in Table 1.

Example 16

Twelve g of the solid product (II) obtained according to Example 12 and 480 g of triisobutyl aluminum were suspended in 500 g of liquefied propylene in the absence of solvent and 90 ml of hydrogen were introduced. The polymerization reaction was carried out at a polymerization temperature of 65 ^° C for 3 hours at a pressure of 70 psig. After completion of the polymerization reaction, the remaining propylene was removed to give 158 g of propylene polymer. The polymer yield per g of solid product (II) was 12 170 g and the polymer yield per g of titanium atom was 0.69 x 10 ⁶ g. Isotactic index: 92.0, BD polymer at 0.30 and MFR: 4.8.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7

Comparative Example 1 Comparative Example 2

Example 12

Example 13

Example 14

Example 15

Example 16

Table 1

Content of atoms Polymer yield g Isotaktic- BD MFR titanium in solid product (II) (mg / g) in g of solid product (II) in g titanium atoms index (g / cm ³ ) (2.16 kg) (240 ° C) 19.5 20 300 1.04 x 10 « 96.0 0.35 7.5 20.5 21 400 1.04 x 10 « 96.0 0.33 6.8 35.0 17 300 0.49 x 10 ^G 96.5 0.35 4.9 16.8 17 200 1.02 x 10 « 97.0 0.32 4.2 24.5 14 300 0.58 x ^10G 96.0 0.30 3.8 22.3 11 300 0.50 x 10 ^G 95.8 0.31 3.4 23.4 12 300 0.53 x ^10G 95.2 0.30 4.8 20.2 2 540 0.13 x 10 ⁶ 85.0 0.08 4.1 25.0 1 050 0.04 x 10 ⁶ 75.0 0.06 4,5 19.0 14 500 0.76 x ^10G 92.1 0.31 4.9 22.0 16 200 0.74 x 10 « 93.0 0.32 4.8 16.0 13 300 0.53 x 10 « 93.1 0.30 3.9 18.0 14 100 0.78 x 10 « 92.1 0.30 4.1 19.0 13 170 0.69 x 10 « 92.0 0.30 4.8

OBJECT OF THE INVENTION

Claims (1)

Catalyst for the production of polyolefins by polymerizing polyolefins, in particular propylene polymers, consisting of (a) a solid product II obtainable by reacting aluminum or ferric chloride with magnesium hydroxide, oxide or carbonate, or a double compound containing any of these compounds, or a hydrate of a magnesium compound to form solid product I, followed by reacting the solid product I with at least one electron donor from the group comprising, for example, esters, and with at least one electron acceptor from the group comprising titanium tetrachloride and silica to form solid product II, and (b) an organoaluminium compound characterized in that as solid product II the product is obtainable by reacting solid product I with electron donors and / or electron acceptors in two separate doses and using titanium tetrachloride as at least one electron acceptor.