FI59107C - FOERFARANDE FOER FRAMSTAELLNING AV SYNNERLIGEN STEREOREGULJAERA POLYOLEFINER OCH VID FOERFARANDE ANVAEND CATALYSATOR - Google Patents

Description

\ uär * \ [B] (11) ANNOUNCEMENT CQ <(\ n

I lJ U 'UTLÄGGNI NGSSKRIFT

C Patent nySnnotty 10 06 1931

Patent eeddolat y (S1) Kv.ik? /Int.ci.3 C 08 F V6 ^ ·, 10/00 SUOMI-FINLAND (21) Ptt * nttlh * k «muf - P * t« ntan * 6knlng 762176 (22 ) H * k * ml * pllvt - Ansäknlnpdtg 30. 07.75 (23) AlkupUvt - Giltl | h «tsdag 30.07.75 (41) Tullut | utkiMk * l - Bllvlt offentllg ^ Q2 yg

National Board of Patents .......

_ * (44) Date of issue | -

Patent and registration authorities' Antem utiijd och utl. «Krift« o pubitund 27.02.81

(32) (33) (31) Requested • tuolkwt — Bejtrd prlorlMt 10.08.7U

Japan-Japan (JP) 9HÖ1 / 7U

(71) Mitsui Petrochemical Industries, Ltd., 2-5, 3-chome, Kasumigaseki, Chiyoda-ku, Tokyo, Japan-Japan (JP) (72) Akinori Toyota, Iwakuni-shi, Yamaguchi-ken, Syuji Minami, Ohtake -shi, Hiroshima-ken, Norio Kashiwa, Iwakuni-shi, Yamaguchi-ken,

The present invention relates to a process for the preparation of highly stereoregular polyolefin polyolefins and to a catalyst for the preparation of highly stereoregular polyolefinic polyolefins.

Catalyst systems consisting of a solid titanium halide and an organoaluminum compound have previously been used in the preparation of highly stereoregular o <-olefin polymers. The use of these catalyst systems yields strongly stereoregular polymers, but the polymer uptake per unit amount of titanium catalyst moiety is low and further treatment is required to remove catalyst residues from the polymer formed. Recently, some methods have been proposed, for example in DE-A-2 230 672, 2 230 728 and 2 230 752, to overcome the disadvantages of previous methods. These processes aim to prepare strongly stereoregular poly (X-olefins) by polymerizing O-olefins such as propylene using a catalyst containing a solid component obtained by copolymerizing a complex between a titanium halide and a specific electron donor and a magnesium halide. However, the stereoregularity of the polymer formed in these processes is not sufficient and the yield of polymer per titanium atom is unsatisfactory 2,5107 In addition, the yield of polymer per chlorine atom in the catalyst is low due to the low titanium content of the powdered product. must be carried out due to the low apparent density of the polymer formed with a low sludge content, so that the process is economically disadvantageous, especially when the polymerization activity of the catalyst disappears in a short time.

French Public Patent Application FR 2 113 313 (May 29, 1972) discloses a process for the selective preparation of either a main product atactic polymer or a main product stereoregular polymer. This patent states that if a Ti catalyst component prepared by contacting a titanium compound with a mixture of an active magnesium halide support and an anhydrous compound of Groups I-IV, e.g. silicon, is preferably used in the above process as a supported and then modified electron donor. However, only SiO 2 is mentioned in this publication as an anhydrous silicon compound. This publication further mentions that ethers, thioethers, amines, phosphines, ketones and esters can be used as electron donors, but does not mention by way of example any particular ester compound. The isotacticity of the polymer (the extraction residue obtained by boiling in n-heptane in all the examples of the above-mentioned patent is at most about 70 and the process according to this patent is therefore not very satisfactory for the preparation of highly stereoregular polymers. as an electron donor in the preparation of isotactic polymers.In addition, only anhydrous lithium chloride and silica are used in this patent as an anhydrous compound of Group I-IV elements.

Studies to overcome the disadvantages of conventional methods have found that a titanium-containing catalyst component consisting of an organic complex derived from (i) magnesium halide, (ii) organopolysiloxane, (iii) an organic carboxylic acid ester, and (iv) a certain stereo compound . Studies have shown that strongly stereoregular (X-olefin polymers and copolymers can be prepared in high yields using this catalyst while the catalyst remains functional for long periods of time and with a high halogen content due to the catalyst or copolymers of the polymer or copolymer formed and the copolymers formed.

The process according to the invention is characterized in that O (olefins having at least 3 C atoms are polymerized or copolymerized in the presence of a catalyst comprising 3510107 (A) a titanium-containing solid catalyst component consisting of an organic complex derived from (i) magnesium dichloride, (ii) an organopolysiloxane of the formula Q (C 1 -C 6 O 2 SiO 2 (formula 1) in which the Q groups are the same or different, and Q may be a hydrogen atom, a C 1 -C 4 alkyl, a C 1 -C 6 cycloalkyl or a C 8 -C 8 cycloalkyl group). aryl provided that not all Q groups are simultaneously hydrogen atoms, and n is 1-1000, of an organopolysiloxane of formula (Q 2 SiO) n (formula 2) wherein Q and n are as defined above, or XtCl 2 SiO 2 SiQ 9 ( an organopolysiloxane of formula 3) wherein Q and n are as defined above and X is a halogen atom, (iii) an organic carboxylic acid ester having an acid moiety of a C 1 -C 6 saturated or unsaturated aliphatic carboxylate. an acylic acid which is optionally halogen-substituted and whose alcohol moiety consists of a C 1 -C 6 saturated or unsaturated aliphatic primary alcohol, a C 1 -C 6 saturated or unsaturated alicyclic alcohol or a saturated or unsaturated aliphatic primary alcohol substituted with a C gene atoms, an organic carboxylic acid ester having an acid moiety of an aromatic carboxylic acid and an alcohol moiety of a C1-C8 saturated or unsaturated aliphatic primary alcohol, a C1-C8 saturated or unsaturated alicyclic alcohol or a saturated or unsaturated aliphatic aliphatic alcohol groups or halogen atoms, or an alicyclic carboxylic acid ester, namely methyl cyclopentanecarboxylate, methyl hexahydrobenzoate, ethyl hexahydrobenzoate, methyl hexahydrotoluate or ethyl hexahydrotoluate, and (iv) ka Of a titanium compound of the formula wherein X is alkyl, X is the same as defined above, and p is 0 or an integer from 1 to 1, and (B) an organoaluminum catalyst component of the formula wherein the groups are the same or different alkyl groups, and m is a positive number 1.5 ~ 3, wherein in the case of liquid phase polymerization the amount of catalyst is such that the amount of titanium-containing solid catalyst component (A) calculated as Ti atoms is 0.0001-1.0 mmol / polymerization system the volume of the liquid phase in liters, and in the case of vapor phase polymerization, the amount of the titanium-containing solid catalyst component (A) calculated as Ti atoms is 0.001 to 0.5 mmol / liter of the reaction zone, and the organoaluminum catalyst component (A) and the titanium-containing catalyst the atomic ratio is at least 1: 1.

The polymerization or copolymerization of β-olefins having at least 3 carbon atoms comprises the homopolymerization of β-olefins having at least 3 carbon atoms, the copolymerization of at least two β-olefins having at least 3 carbon atoms with each other and the copolymerization of ol -dimerization with ethylene and / or diolefins, preferably in an amount of up to 30 mol / l.

Examples of X-olefins include propylene, 1-butene, 4-methyl-1-pentene, and 3-methyl-1-butene, and examples of diolefins include conjugated diolefins such as butadiene and unconjugated dienes such as dicyclopentadiene, ethylene norbornene, ~ hexadiene.

The organic carboxylic acid ester (iii) may be included in the catalyst in part or in whole as ester-treated products or adducts of compounds (i), (ii) and (iv) prepared by contacting it with compounds (i), (ii) and (iv).

Magnesium chloride (i) as a component of the titanium-containing solid catalyst component (A) is preferably as anhydrous as possible, allowing only an amount of moisture that does not substantially affect the efficiency of the catalyst.

MgCl 2 can be dehydrated before use by heating under reduced pressure at 100-400 ° C. For convenience, the magnesium chloride is preferably used in powder form, with an average particle diameter of 1 to 50 μm. However, if it is ground in the preparation of the catalyst during the contact treatment, then powders with a larger particle size can also be used. An average particle diameter of 1 to 50 μm means that 80% of the total weight of the particles consists of particles with a diameter of 1 to 50 μm.

Examples of polysiloxanes (ii) of the formula QiQ -diphenyldiisiloxane, pentamethyl-1,3,5 ′ triphenyltrisiloxane, heptaphenyldisiloxane and octaphenyltrisiloxane.

Examples of cyclopolysiloxanes of formula (Q 1 SiO 2) (ii) are 2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclo-pentamethylcyclo trimethylcyclotrisiloxane, hexaphenylcyclotrisiloxane and octaphenylcyclotetrasiloxane.

Of the organic polysiloxanes, linear alkyl polysiloxanes are preferred. Methylpolysiloxane and ethylpolysiloxane having a viscosity of up to 200 at 25 ° C are particularly preferred.

Examples of organic carboxylic acid esters of the titanium-containing solid catalyst component (A) include primary alkyl esters of monovalent saturated fatty acids such as methyl formate, ethyl acetate, n-amyl acetate, 2-ethylhexyl acetate, n-butyl 10-acetate, n-butyl formate, ethyl bensyyliasetaatti; allyl acetate; primary alkyl esters of haloaliphatic carboxylic acids such as ethyl chloroacetate, n-propyl dichloroacetate and ethyl chlorobutyrate; primary alkyl esters of unsaturated fatty acids such as methyl acrylate, methyl methacrylate or isobutyl crotonate; primary alkyl esters of benzoic acid such as methyl benzoate, ethyl benzoate, n-propyl benzoate, n- and isobutyl benzoate, n- and isoamyl benzoates, n-hexyl benzoate, n-octyl benzoate and 2-ethylhexyl benzoate; primary alkyl esters of toluic acid such as methyl toluate, ethyl toluate, n-propyl toluate, n- and isobutyl toluate, n- and isoamyl toluate or 2-ethylhexyl toluate; primary alkyl esters of ethyl benzoic acid such as methylethyl benzoate, ethyl ethyl benzoate, n-propylethyl benzoate and n- and isobutyl benzoate; primary alkyl esters of xylylenecarboxylic acid such as methyl 3,3-xylene-1-carboxylate, ethyl 3,5-xylene-1-carboxylate and n-propyl 2,1'-xylene-1-carboxylate; primary alkyl esters of anisic acid such as methyl anisate, ethyl anisate, n-propyl anisate, and n-isobutyl anisates, and primary alkyl esters of naphthalic acid such as methyl naphthoate, ethyl naphthoate, n-propyl, phthalate, and n- and isobutyl.

Of these primary alkyl esters of aromatic carboxylic acids, primary C 1 -C 4 alkyl esters are preferred. Methyl benzoate and ethyl benzoates are particularly preferred.

As already mentioned, some or all of the organic carboxylic acid ester (iii) can be used as ester-treated products or adducts of compounds (i), (ii) and (iv) by contacting them with these compounds (i), (ii) and (iv) .

Examples of the titanium compound of the formula Ti (OR) X (component p p - (iv)) include titanium tetrahalides such as titanium tetrachloride, titanium tetrabromide or titanium tetraiodide; alkoxytitanium trihalide such as methoxytitanium chloride, ethoxytitanium trichloride, n-butoxytitanium trichloride, ethoxytitanium tribromide or isobutoxytitanium tribromide; dialkoxytitanium dihalides such as dimethoxytitanium dichloride, diethoxytitanium dichloride, di-n-butoxytitanium dichloride or diethoxytitanium dibromide; trialkoxytitanium monohalides such as trimethoxytitanium chloride, triethoxytitanium chloride, tri-n-butoxytitanium chloride and triethoxytitanium bromide; and tetraalkoxytitanium such as tetramethoxytitanium, tetraethoxytitanium and tetra-n-butoxytitanium. Of these, titanium tetrahalides, especially titanium tetrachloride, are preferred.

If magnesium chloride (i) treated with an organic carboxylic acid ester (iii) is used to form the titanium-containing solid catalyst component (A) according to the present invention, it is preferable to use mechanical grinding to bring both into contact with each other. Due to the effect of this grinding contact, the organic acid ester has an effective effect on magnesium chloride over a wide concentration range. A sufficient treatment effect can be obtained, although the proportion of the former is small compared to the latter (in a molar ratio of about 1: 1 to 1:20).

If the Si component (ii) is treated with an organic carboxylic acid ester (iii), the treatment is carried out, for example, by adding the organic carboxylic acid ester at room temperature to a silicon compound or its solution in a suitable inert solvent such as pentane, hexane, heptane or kerosene. in an inert solvent and adding a silicon compound to this solution. Of course, the treatment can be carried out in a short time at elevated temperatures, but if desired, the treatment can also be carried out under cooling.

The adduct of the titanium compound (iv) and the organic carboxylic acid ester (iii) can be prepared by adding the organic carboxylic acid ester (iii) in an equimolar amount or excess to the titanium compound itself (if liquid) or a solution thereof in the above inert solvent and removing the precipitate formed. When the titanium compound is a liquid, it can be used in the adduct-forming reaction as a solution in the above-mentioned inert solvent. The washing of the formed precipitate (removal of unreacted titanium compound and organic carboxylic acid ester) can be carried out as the above-mentioned solvent.

The ratio of starting materials anhydrous magnesium chloride (i) // Si component (ii) / organic carboxylic acid ester (iii) / titanium compound (iv) for the catalyst component (A) is not very limited; it is usually 1 / 1000-0.01 / 10-0.005 / 100-0.001, preferably 1/10-0.01 / 1-0.01 / 30-0.01.

The titanium-containing solid catalyst component (A) is prepared by preferably contacting the components (i), (ii), (iii) and (iv) with each other by grinding them together. The order of addition of the ingredients, the addition procedure, and the contact procedure may vary. Some examples are given below.

(1) Anhydrous magnesium chloride (i), organic polysiloxane (ii), organic carboxylic acid ester (iii) and titanium compound (iv) are effectively contacted with each other using a mechanical grinding means (called grinding contact), and the formed titanium-containing solid is preferably treated with solution in an inert solvent.

(2) Magnesium chloride (i), organic polysiloxane (ii) and organic carboxylic acid ester are brought into contact with each other by grinding. The solid formed is treated by suspending it in the titanium compound (iv) or a solution thereof in an inert solvent; or the solid component and the titanium compound (iv) are ground in contact with each other in a substantially dry state, and the mixture is preferably suspended in the titanium compound (iv) or a solution thereof in an inert solvent.

(3) Anhydrous magnesium chloride (i) and an organic carboxylic acid ester (iii) 7 59107 are contacted by grinding, and the mixture is then contacted by grinding with an organic polysiloxane (ii) to form a solid component; or magnesium chloride (i) and the Si component (ii) are first ground together and then with the organic carboxylic acid ester (iii) to form a solid component. Both of these solids are suspended in the titanium compound (iv) or a solution thereof in an inert solvent; or the solid component is contacted by grinding with the titanium compound (iv) in a substantially dry state and then preferably suspended in the titanium compound (iv) or an inert solution thereof.

(H) Anhydrous magnesium chloride (i), an organic polysiloxane (ii), and an adduct of a titanium compound (iv) and an organic carboxylic acid ester (iii) are ground in contact with each other, and the formed titanium-containing solid is preferably suspended in a titanium compound (iv) or its solution in an inert solvent.

(5) The anhydrous magnesium chloride (i) and the orgasmic polysiloxane (ii) are ground in contact with each other, and the grinding is then continued together with the titanium compound (iv) and the organic carboxylic acid ester (iii) adduct. The titanium-containing solid formed is preferably suspended in the titanium compound (iv) or a solution thereof in an inert solvent.

(6) In the procedures according to (1) and (3) above, the titanium compound (iv) is used as an adduct of it and the organic carboxylic acid ester (iii).

(7) Anhydrous magnesium chloride (i), an organic polysiloxane (ii), a titanium compound (iv) and an organic carboxylic acid ester (iii) are ground in contact with each other, and the formed titanium-containing solid is preferably slurried in a titanium compound (iv) or a solution thereof in an inert solvent.

(8) In the procedure according to (7) above, the organic carboxylic acid ester (iii) is also added to the grinding contact system.

In the production of the titanium-containing solid titanium component (A), the grinding contact can be performed, for example, using a rotary ball mill, a vibrating ball mill or an impact mill. As a result of contact, the organic carboxylic acid ester (iii), the organic polysiloxane (ii) and the titanium compound (iv) immediately act on the active surfaces formed during the grinding of magnesium chloride (i) to form an organic complex whose chemical structure has not yet been elucidated. This can be seen from the fact that the diffraction pattern of magnesium chloride powder changes.

The treatment conditions used in the grinding contact of the two or more starting materials for the preparation of the catalyst component (A) using different mills can be selected as follows: For example, using a stainless steel ball mill with 100 balls (^ 15 mm) in a mill cylindrical vessel with a capacity of β 59107 800 ml and an inner diameter of 100 mm, the grinding treatment of 20-1 + 0 g usually takes at least 1 * 8 hours, preferably at least 72 hours at a speed of 125 rpm. The grinding treatment is usually carried out at about room temperature. If the mixture heats up on grinding contact, the system is cooled.

The treatment of the solid obtained in the grinding contact of the starting materials with the titanium compound (iv) can be conveniently carried out by stirring the mixture, usually at a temperature between 1 + 0 ° C, to the boiling point of the mixture to be treated for at least one hour. Alternatively, the solid treatment is carried out by contact grinding in a ball mill under the above grinding conditions for at least 100 hours.

If the titanium compounds are used in two different steps in the above treatment, then the compounds may be the same or different.

The titanium-containing solid catalyst component (A) is formed by separating the organic solid complex prepared as described above from the suspension. It is preferably washed thoroughly with hexane or another inert liquid until the free titanium compound (iv) is no longer detected in the washing liquid.

In the present invention, the catalyst component (B) to be combined with the catalyst component (A) is an organoaluminum compound of the general formula R 'Al (OR * K), wherein R' represents an alkyl group, preferably a straight-chain or branched C 1 -C 4 alkyl group, of two or more R 'groups are the same or different and m is a number in the range 1.5 = m = 3.

Examples of organoaluminum compounds are as follows: (1) If m is 3, the compound is trialkylaluminum. Examples are trimethylaluminum, triethylaluminum, tri-n- and isopropylaluminum, tri-n- and isopropylaluminum and trihexylaluminum. Triethylaluminum and trihutylaluminum are preferred. Combinations of two or more may also be used.

If desired, the trialkylaluminum can be reacted with an organic carboxylic acid ester before use. This reaction can be carried out in a polymerization system before starting the polymerization; or it may be carried out separately and the reaction product is then added to the polymerization system. The reaction proceeds sufficiently by contacting the trialkylaluminum with an organic carboxylic acid ester (or one of them may be in solution in an inert solvent).

The ratio of the amounts of these materials is such that the proportion of trialkylaluminum is usually 2 to 100 moles (calculated as Al atoms) per gram equivalent of the ester group of the organic carboxylic acid ester. The organic carboxylic acid ester may be selected from the group (iii) of various organic carboxylic acid esters used in the preparation of the catalyst component (A). Usually it is the same acid ester used to form the catalyst component (A).

(2) m is at least 1.5 but less than 3 (1.5 to m <3), so the above-mentioned aluminum compound is a partially alkoxylated alkylaluminum. Such 95,5107 alkylaluminum is prepared, for example, by adding a calculated amount of alcohol to trialkylaluminum or dialkylaluminum hydride. To control the reaction, at least one of them is preferably used as a solution in an inert solvent.

When polymerizing or copolymerizing ε-olefins having at least 3 carbon atoms using a catalyst consisting of a titanium-containing solid catalyst component (A) and an organoaluminum catalyst component (r), the polymerization conditions can be selected as those known for polymerization or copolymerization. Usually the polymerization temperature is from room temperature to about 200 ° C and the pressure from normal pressure to about 50 kp / cm 2 The polymerization or copolymerization can be carried out either in the presence or absence of an inert liquid medium Examples of liquid media include pentane, hexane, heptane, heptane, octane and kerosene If the polymerization or copolymerization is carried out without a liquid medium, it may be carried out in the presence of a liquid olefin monomer, or it may be carried out in the gas phase, for example, using a fluidized-bed catalyst.

The concentration of the catalyst charged to the polymerization system for polymerization can be varied if desired. For example, in solid phase polymerization, the titanium-containing solid catalyst component (A) is usually used in concentrations of 0.001 to 1.0 mmol / liter based on titanium, and the catalyst component (B) is usually used in a ratio of 1/1 to 100/1, preferably 1/1 to 30/1 aluminum atom / titanium atom. according to the ratio. In the gas phase polymerization, the titanium-containing solid catalyst component (A) can be used in concentrations of 0.001 to 0.5 mmol (based on the titanium atom) and the catalyst component (B) in amounts of 0.01 to 5 mmol (based on the aluminum atom) per liter of the volume of the reaction zone.

To reduce the molecular weight of the polymer formed (to increase the melt index of the polymer), hydrogen may be present in the polymerization system.

The following examples and comparative examples illustrate the invention in more detail.

Example 1

Preparation of catalyst component (A):

A 800 ml stainless steel (SUS 32) ball mill with an inner diameter of 100 mm, which could hold 100 stainless steel balls (SUS 32), each 15 mm in diameter, was charged with 20 g of anhydrous magnesium chloride, 6.0 ml of ethyl benzoate and 3.0 ml of dimethylpolysiloxane (formula 1, n = 10.1, viscosity 20 cP at 25 ° C) for one hour at a speed of 125 rpm. The solid product formed was slurried in 150 ml of titanium tetrachloride, and the suspension was stirred at 80 ° C for 2 hours. The solid was collected by filtration and washed with purified hexane until no more free titanium tetrachloride was observed. The resulting component- 10 5 91 0 7 ti contained 1 +, 1 wt. # Ti and 58.2 wt. # Cl.

Polymerization: A 2-liter autoclave was charged with 0.05 mL (0.375 mmol) of triethylaluminum, 1 + 3.8 mg (0.0375 mmol, calculated as Ti atoms) of the titanium-containing solid component (A) obtained above, and 750 mL of kerosene (purified kerosene) which was sufficiently free of oxygen and moisture. The polymerization system was heated, and when the temperature reached 70 ° C, propylene was added. The polymerization of propylene started at a total pressure of 7.0 kp / cm 2. The polymerization was continued at 70 ° C for 3 hours, after which the propylene feed was stopped. The contents of the autoclave were cooled to room temperature and the catalyst was decomposed by the addition of methanol. The solid was collected by filtration, washed with methanol and dried to give 1 + 10.3 g of polypropylene as a white powder. The residue extracted from boiling n-heptane of the powder was 9 * +, 5 #, and had an apparent density of 0.30 g / ml.

On the other hand, concentration of the liquid phase gave 15.1 g of a solvent-soluble polymer.

The average polymerization activity of the catalyst per titanium atom above was 51 + 0 g / Ti-mol.h'atm.

Comparative Example 1

Preparation of titanium-containing catalyst component:

A ball mill of the same type as in Example 1 was charged with 20 g of anhydrous magnesium chloride and 17.8 g of an adduct having an average composition of the formula TiCl 2 · CgH 2 COOC 2 H 2 O and contacted by grinding for 100 hours under the same conditions as in Example 1 at 125 rpm. The solid titanium catalyst component formed (corresponding to component (A) in Example 1) agglomerated in a ball mill and was difficult to obtain in powder form. A portion of the solid was washed with 1 liter of purified hexane to the purity shown in Example 1 and dried to form the titanium catalyst component. The titanium catalyst component contained 1 +, 2 wt. # Ti and 6.30 wt. # Cl.

Polymerization:

Propylene was polymerized under the same conditions as in Example 1 using III + mg of the titanium catalyst component obtained above. Only 8.8 g of polypropylene as a white powder and 1.7 g of solvent-soluble polymer were obtained.

Examples 2, 3 and U

In Examples 2-1 +, the titanium catalyst component (A) was prepared in the same manner as in Example 1 except that the polysiloxane mentioned in Table 1 was used in each case. Propylene was polymerized under the same conditions as in Example 1 using the titanium catalyst component formed in the amount shown in Table 1. The results are also shown in Table 1.

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rt X! S rt fC <^ m r-, rt r-l: u: E <___: * rt 1 • • o 'r4 β O U - CV C.

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4-J Xa r-H CO Ή + · * Ί V

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rt ti> ι-l «« ί G n »Pi ia (ti · Η il >> XI> rt v; X, * rj;> rt rt: n, i >> o n) ro rt cti rV E. cti,

Il CO:. · X Π cd Xr! rt (ti .rt + 'cti 1 rt «£ 1 <u · η M <0 rt Xj 1" 1 xi o en vr ^ w— K m' - f <N rl ^ • ii lvl I XI CM fCc h rt ro oo H 6 tl, _ »_ 12 5 91 0 7

Examples 5 ~ 7

In Examples 5 to T, the catalyst component (A) was prepared under the same conditions as in Example 1 except that each of the substituted benzoic acid esters shown in Table 2 was used in the amount shown in Table 2. Propylene was polymerized in the same manner as in Example 1 using catalyst component (A) in the amounts shown in Table 2. The results are shown in Table 2.

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Example 8

Preparation of catalyst component (A):

The solid component was prepared by treating anhydrous magnesium chloride, ethyl benzoate and methyl hydropolysiloxane in a ball mill as described in Example 1. The solid formed was slurried in 100 ml of kerosene containing 50 ml of titanium tetrachloride and the suspension was stirred for 2 hours at 100 ° C. The solid was collected by filtration and washed with purified hexane until no more free titanium tetrachloride was detected. The resulting catalyst component (A) contained 3.0 wt.% And 6l, 2 wt.%.

Polymerization: 750 ml of purified kerosene, 0.092 ml (9.375 mmol) of triisobutylaluminum and 59.5 ml (0.0375 mmol of Ti) of catalyst component (A) were charged to a 2-liter autoclave. The polymerization system was heated and when the temperature reached 70 ° C, the propylene feed was started. The polymerization of propylene started at a total pressure of 7.0 kp / cm 2. The polymerization was continued with stirring at 70 ° C for 5 hours, after which the propylene feed was stopped. The contents of the autoclave were cooled to room temperature, and the solid was collected by filtration, washed with methanol and dried to give 390.1+ g of polypropylene as a white powder and 12.1 g of a solvent-soluble polymer. Upon extraction, n-heptane had a powdery polymer residue of 96.1+% and an apparent density of 0.31 g / ml. The average polymerization activity of the catalyst was 306 g polypropylene / Ti-mmol.h.atm.

Examples 9-13

In Examples 9-13, the catalyst component (A) was prepared under the same conditions as in Example 1 except that the polysiloxane shown in Table 3 was used instead of methylpolysiloxane. Propylene was polymerized as in Example 1 using catalyst component (A) in the amounts shown in Table 3. The results are shown in Table 3.

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Examples lU-17

Preparation of catalyst component A:

In a ball mill, the magnesium compound (i), the silicon compound (ii), the organic carboxylic acid ester (iii) and the titanium compound (iv) were ground together under the ratios and conditions shown in Table. 10 g of the obtained comminuted product and titanium tetrachloride were heated together at 60 ° C for 2 hours. The solid was then filtered off and washed with purified hexane until the wash was Ti-free.

Polymerization: A 2-liter autoclave was charged with the amounts of the organoaluminum compound shown in Table 1 and 0.0375 mmol (as Ti atoms) of the solid Ti-containing component (A) prepared above, as well as sufficiently oxygen-free and water-free purified kerosene. The polymerization system was heated to 60 ° C, at which point propylene was introduced. The polymerization of propylene started at a total pressure of 8.0 kp / cm 2. The polymerization was continued at 60 ° C for 3 hours, then the propylene feed was stopped. The contents of the autoclave were cooled to room temperature and the catalyst was decomposed by the addition of methanol. The solid was filtered, washed with methanol and dried. The results are shown in Table k.

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A ball mill (described in Example 1) was charged with 20 g of anhydrous magnesium chloride, 6.0 ml of ethyl benzoate and 3.0 ml of diraethyl polysiloxane (Formula 1, n = 10.1, viscosity at 25 ° C, 20 CP) under a nitrogen atmosphere, and the mixture was ground for 100 hours. at a speed of 125 rpm. The obtained solid product was suspended in 150 ml of titanium tetrachloride, and the suspension was stirred at 80 ° C for 2 hours. The solid component was filtered and washed with purified hexane until no more titanium tetrachloride was detected in the washings. The obtained component (A) contained U, 1 wt.

Ti and 58.2 weight- # Cl.

Polymerization: A 1 liter glass vessel equipped with a stirrer was charged with 0.5 L of purified kerosene, and the vessel was thoroughly purged with nitrogen gas. Kerosene was heated to 60 ° C and 1.0 mmol of triethylaluminum was added. Then, 0.2 mmol (calculated as Ti atoms) of the Ti-containing catalyst component (A) prepared above was added, and 1-hexene was introduced into the mixture at 10 g / min for 20 minutes, followed by stirring for another 3 hours. The contents of the vessel were poured into a large amount of methanol to give a white polymer. It was filtered, washed with hexane and dried. Yield 125 g.

Example 19 (Preparation of propylene / ethylene / ethylidene norbornene / butadiene copolymer) A 1 liter glass vessel equipped with a stirrer was charged with 1 liter of purified kerosene, and the vessel was thoroughly purged with nitrogen gas.

At 60 ° C, a propylene / ethylene mixture containing 1+ mol / ethylene was introduced into the vessel, then 2 ml of ethylidene norbornene and 0.05 ml of butadiene were added, and finally 2 mmol of triethylaluminum and 0.2 mmol (calculated as Ti atoms) in the examples. lit-17 prepared Ti-containing catalyst component (A), and the mixture was polymerized at 50 ° C for one hour.

Upon completion of the polymerization, the white powdery polymer was filtered, yield 66 g. Differential thermal analysis of its m.p. was lUU ° C. 6.5 g of polymer dissolved in the solvent ·

Example 20 (Preparation of propylene / 1-dodecene / 1-tetradecene copolymer) A 1 liter glass vessel equipped with a stirrer was charged with 0.5 L of purified kerosene, and the vessel was thoroughly rinsed with propylene. 1 mmol of triethylaluminum and 0.2 mmol of the catalyst component (A) prepared in Example 18 were added, 23.6 g of a mixture of 1-dodecene (56.6 mol- #) and 1-tetra-decene (h3.1 * mol- #) were added to the mixture. while conducting propylene at 50 ° C. The reaction was allowed to proceed for one hour. The resulting white powder was filtered and dried. Yield 120.5 g.

The polymer m.p. (differential thermal analysis) was 150 ° C and the crystallization temperature was 8 ° C. The solvent-soluble polymer was 3.1 g.

i 20 59107

These comparative tests

Experiment 1 (present invention)

Preparation of catalyst component (A):

A 800 ml stainless steel (SUS 32) ball mill with an inner diameter of 100 mm, which could hold 100 stainless steel balls (SUS32), each 15 mm in diameter, was charged with 20 g of anhydrous magnesium chloride, 3.98 g ethyl benzoate, 3.0 ml of dimethylpolysiloxane (having a viscosity of 20 cP at 25 ° C) and 2.65 g of titanium tetrachloride under a nitrogen atmosphere and contacted by grinding with each other for 100 hours at 125 rpm. The solid product formed was slurried in 150 ml of titanium tetrachloride, and the suspension was stirred at 80 ° C for 2 hours. The solid was then collected by filtration and washed with purified hexane until free titanium tetrachloride was no longer detected. The component formed contained 2.8% by weight of Ti and 63.0% by weight of # Cl.

Polymerization: A 2-liter autoclave was charged with 0.05 mL (0.375 mmol) of triethylaluminum, 43.8 mg (0.0375 mmol) of the titanium-containing solid component (A) obtained above, and 750 mL of kerosene that was sufficiently oxygen and moisture free. The polymerization system was heated and when the temperature reached 70 ° C propylene was added. The polymerization of propylene started at a total pressure of 7.0 kg / cm. The polymerization was continued at 70 ° C for 3 hours, after which the propylene feed was stopped. The contents of the autoclave were cooled to room temperature, and the catalyst was decomposed by adding methanol. The solid was collected by filtration, washed with methanol and dried to give 280.4 g of polypropylene as a white powder. The residue (II) extracted with boiling n-heptane of the powder was 93.3% and had an apparent density of 0.34 g / ml.

On the other hand, concentration of the liquid phase resulted in 16.2 g of a solvent-soluble polymer.

The average specific polymerization activity of the catalyst per titanium atom was 377 g / Ti mol.h.atm.

Comparative test 2

Catalyst component (A) was prepared in the same manner as in Experiment 1 except that methylpolysiloxane was not used. Using the catalyst component thus formed, the polymerization of propylene was carried out in the same manner as in Experiment 1 except that 0.005 ml of methylpolysiloxane was fed to the autoclave together with the titanium catalyst component and triethylaluminum. The polymerization results are shown in Table A together with the results of Experiment 1.

Comparative test 3

Catalyst component (A) was prepared in the same manner as in Experiment 1 except that neither ethyl benzoate nor methylpolysiloxane was used. Using the catalyst component thus formed 2i 59107, the polymerization of propylene was carried out in the same manner as in Experiment 1 except that 0.071 mmol of ethyl benzoate and 0.05 ml of methylpolysiloxane were fed to the autoclave together with the catalyst component (A) and triethylaluminum.

The polymerization results are shown in Table 5 · \.

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Claims (4)

2k 59107 Process for the preparation of highly stereoregular polyolefins, characterized in that β-olefins having at least 3 carbon atoms are polymerized or copolymerized in the presence of a catalyst comprising (A) a titanium-containing solid catalyst component consisting of an organic complex derived from (i) magnesium dichloride, ( ii) an organopolysiloxane of the formula Q (QgSiO 2 SiQg (formula 1) in which the Q groups are the same or different, and Q may be a hydrogen atom, C 1 -C 4 alkyl, C 8 -C 8 cycloalkyl or C 8 -C 8 aryl provided that not all Q groups are simultaneously hydrogen atoms, and n is 1-1000, of an organopolysiloxane of formula (QJ310) (Formula 2) dn, wherein Q and n are as defined above, or of the formula X (QgSiO) SiQgX (Formula 3) ), wherein Q and n are as defined above, and X is a halogen atom, (iii) an organic carboxylic acid ester having an acid moiety of C 1 -C 6 "saturated now or an unsaturated aliphatic carboxylic acid, optionally halogen-substituted, and the alcohol moiety of which is a C 1 -C 6 saturated or unsaturated aliphatic primary alcohol, a C 1 -C 6 saturated or unsaturated alicyclic alcohol, or a saturated or unsaturated C with an organic carboxylic acid ester, the acid moiety of which is a C 1 -C 6 aromatic carboxylic acid and the alcohol moiety of a C 1 -C 8 saturated or unsaturated aliphatic primary alcohol, a C 1 -C 6 saturated or unsaturated aliphatic aliphatic alcohol, substituted by C8-C18 aromatic groups or halogen atoms, or by an alicyclic carboxylic acid ester, namely methyl cyclo opentanecarboxylate, methyl hexahydrobenzoate, ethyl hexahydrobenzoate, methyl hexahydrotoluate or from a hexane hydrotoluate, and (iv) a titanium compound of the formula Ti (OR) pX1_p wherein R is alkyl, X is as defined above, and p is 0 or an integer from 1 to 1, and (B) R'mAl (OR ') is ) g_m, wherein the R 'groups are the same or different alkyl groups, and m is a positive number from 1.5 to 3, wherein in the case of liquid phase polymerization the amount of catalyst is such that the amount of titanium-containing solid catalyst component (A) calculated as Ti 0.0001 to 1.0 mmol / liter of the liquid phase of the polymerization system, and in the case of vapor phase polymerization, the amount of the titanium-containing solid catalyst component (A) calculated as Ti atoms is 0.001 to 0.5 mmol / liter of the reaction zone volume, and the organoaluminum catalyst the ratio of the catalyst component (A) calculated as the Al atom / Ti atom ratio is at least 1: 1. 25 59107 Catalyst used in the process according to claim 1, characterized in that it comprises (A) a titanium-containing solid catalyst component consisting of an organic complex derived from (i) magnesium chloride, (ii) an organopolysiloxane of the formula QiQgSiOj ^ SiQ ^ (formula I), wherein Q is the same or different and Q may be a hydrogen atom, C 1 -C 6 alkyl, C 8 -C 8 cycloalkyl or C 6 -C 8 aryl, provided that not all Q groups are simultaneously hydrogen atoms, and n is 1-1000, of an organopolysiloxane of the formula (Q 2 SiO) ^ (formula 2) in which Q and n are as defined above, or of an organopolysiloxane of the formula X (Q 2 SiO) nSiQ 2 X (of formula 3) in which Q and n are the same as above, and X is a halogen atom, (iii) an organic carboxylic acid ester having an acid moiety consisting of a C 1 -C 6 saturated or unsaturated aliphatic carboxylic acid, optionally halogen-substituted, and an alcohol moiety m uodostaa. A C 1 -C 6 saturated or unsaturated aliphatic primary alcohol, a C 1 -C 6 saturated or unsaturated alicyclic alcohol or a saturated or unsaturated aliphatic primary alcohol substituted by C 1 -C 6 aromatic groups or halo-esters of an organic carboxylic acid, an organic carboxyl atom, an organic carboxyl atom The C 1 -C 6 aromatic carboxylic acid and the alcohol moiety are a C 1 -C 6 saturated or unsaturated aliphatic primary alcohol, a C 8 -C 8 saturated or unsaturated alicyclic alcohol or a saturated or unsaturated aliphatic primary alcohol substituted with a C gene atoms, or an alicyclic carboxylic acid ester, namely methyl cyclopentanecarboxylate, methyl hexahydrobenzoate, ethyl hexahydrobenzoate, methyl hexahydrotoluate or ethyl hexane in the form of R ee is the same as above, and p is 0 or an integer from 1 to U, and (B) an organoaluminum catalyst component of the formula R 'Al (OR') ^ wherein m 3 ~ m in the formula R 'groups are the same or different alkyl groups, and m is a positive number of 1.5 to 3, and the ratio of the organoaluminum catalyst component (B) to the titanium-containing catalyst component (A), calculated as the Al atom / Ti atom ratio, is at least 1: 1. \ 59107 26 A process for the preparation of a synergistic polyolefin with a stereoregulation, with the aid of a polymer, or a copolymer-serum t-olefin having at least 3 cholaters in a catalyst, in which the Haller (A) is a fast titanium catalyst organically complexed with (i) raagnesium dichloride, (ii) that organopolysiloxane with the formula QiQ ^ SiO ^ SiQg (formula l), the color of the Q group is lychee or olika, och Q can be enriched, C - ^ - C ^ - alkyl, C8-C8-Cyclo-alkyl or C8-C8-aryl under the reaction, in which the Q-group is sampled with an internal atom, and from 1 to 1000, that the organopolysiloxane with the formula (Q2 SiO4 (formula 2)) , the color Q and a branch of this form, or an organopolysiloxane of the formula XtQ ^ SiO ^ SiQ ^ X (Form. 3), the color Q and a branch of this form, and X is a halogen atom, (iii) an organic carboxylic acid ester, color syrupelen bestär av en C ^ -Cg mättad eller omättad aliphatisk carboxylsyra, somhuhuu är halogensubitituera d, och color alcohol is preferred for C 1-4 carbon atoms or aliphatic primary alcohols, and C 8 -C 8 is substituted by alicyclic alcohols or alcohol or aliphatic aliphatic primary alcohols, which are substituted with C 8 -C 8 aromatic groups or halogen atoms, organic carboxylic acid ester, color syrupy preferred or aromatic carboxylic acid and alcoholic alcohol or C3-C8 acid or aliphatic primary alcohol, en Cg-Cg carbonate or alicyclic alcohol or alcohol free or aliphatic primary alcohol, which is substituted by C C8 aromatic groups or halogen atoms, or alicyclic carboxylic acid esters, such as methylcyclopentanecarboxylates, methylhexahydrobenzoates, ethylhexahydrobenzoates, methylhexane hydrolysates with ethyl or hexahydrotoluates, and (iv) en, these are selected from the group consisting of 0 or 1 or U, and (B) and an organoaluminum catalyst component having the formula R 'Al (0R') _, color The m 3 — m R * group is l or an alkyl group, and is positively or 1.5 ~ 3, the colors are separated from the polymerization and the pure phase, the catalyst is not precipitated, and the titanium halide is used as the catalyst catalyst component ( A) in which the Ti atom is 0.0001 -1.0 mmol / liter of polymerization systems with a high volume, and in which case the polymerization in the solid phase, with the addition of titanium halide catalyst catalyst components (A) in which the Ti atom is 0.001 - 0.5 mmol / liter \ '/