KR810001604B1 - Olefine polymerization catalyst and polymerization process - Google Patents

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Description

[Name of invention]

Production of olefin polymerization or copolymerization catalyst

Detailed description of the invention

The present invention provides a method for preparing a polymerization or copolymerization catalyst of an olefin having three or more carbon atoms which can produce a high-stereoregular polymer or copolymer in high yield while suppressing formation of unnecessary extremely fine polymer particles. It is about.

Catalyst systems composed of solid titanium halides and organoaluminum compounds have been used for a long time for the preparation of high-stereoregular polymers of x-olefins. Polymerization using these catalysts produces high-stereoregular polymers, but yields are still low for the polymer relative to the unit amount of titanium catalyst component, and an additional process is required to remove catalyst residues from the final polymer. In recent years, the drawbacks of the known techniques are to solve several kinds of methods, such as Japanese Unexamined Patent Publication Nos. 48-16986, 48-16987, and 48-16988 (German Federal Republic Publication Nos. 2,230,728, 2,230,752 and 2,230,672) have been developed.

These methods employ a high-stereoregular polymer by polymerizing α-olefins such as propylene using a catalyst consisting of a solid component obtained by simultaneously grinding a complex formed between titanium halide and a constant electron donor with anhydrous magnesium halide and a constant electron donor. Attempting to obtain (α-olefin). However, the stereoregularity of the final polymer is still insufficient for this method, and the yield of the polymer for the unit titanium atoms is still insufficient. In addition, these methods have low yields of polymers for unit chlorine atoms in the catalyst, and the polymerization reaction has to be carried out with low concentration slurry because of the low apparent density of the final polymer and thus is economically disadvantageous and the polymerization activity of the catalyst is lost in a short time. There is a grievance as a fault.

The specification of Bulsan Seok-ku Publication No. 2,113,313 (May 29, 1972) describes a method for selectively preparing atactic polymers as main products or stereoregular polymers as main products. This patent publication discloses a Ti catalyst component obtained by contacting a titanium compound with an active magnesium halide carrier and an anhydrous compound of Groups I to IV of the periodic table, such as Si, on the carrier in the above-described manner. Subsequently, when used in the form transformed with an electron donor, it demonstrates that a stereoregular polymer is obtained as a heavy product. However, this publication describes only SiO ₂ as an anhydrous compound of Si. Furthermore, this patent publication states that ethers, thioethers, amines and phosphines, ketones and esters can be used as electron donors, but does not exemplify any specific compound belonging to esters. Since the isotacticity of the polymer represented by its boiling n-heptane extraction residue is about 70% in all the examples of this patent publication, the method of this patent is far from producing satisfactory high-stereoregular polymers. far. On the other hand, the only electron donors used in this patent to prepare isotactic polymers are N, N ', N'',N'''-tetramethylethyleneamine. Furthermore, in this patent, only anhydrous lithium chloride and SiO ₂ are clearly used as the anhydrous compound of the elements of Groups I to IV of the periodic table.

Many proposals have been made to use magnesium-containing solid titanium catalyst components obtained by reacting a reaction product formed between an organic magnesium compound such as Grignard reagent and an organic phosphorus siloxane such as hydropolysiloxane or polysiloxane with a halogen compound of titanium or vanadium ( Japanese Laid-Open Patent Publication Nos. 49-11975, 49-133488 and 49-58189), and these proposals do not describe the catalyst components obtained by further reacting the above-mentioned catalyst components with organic acid esters. Moreover, the use of the catalyst components described above imposes polymerization limitations on methylene and copolymers with ethylene and other α-olefins, such as propylene, butene-1 or hexene-1, which are less than about 10%. These known patent publications give polymers or limitations of α-olefins having three or more carbon atoms. These known patent publications do not deal with any given stereoregularity of polymers or copolymers of α-olefins having three or more carbon atoms. These specifications also do not mention the use of organic acid esters essential in the present invention to form titanium catalyst components. Comparative Example 1, later described herein, indicates that the polyethylene attempted to polymerize propylene using this titanium catalyst component produced in the organic acid ester member could not achieve the improvement attempted by the present invention.

In an attempt to overcome the above-mentioned deficiencies with respect to Blanche Publication No. 2,113,313, the same co-inventors as the present inventors

(i) magnesium halides such as magnesium chloride, magnesium bromide or magnesium iodide, (ii) certain Si compounds, preferably organic Si compounds, particularly preferably organic polysiloxanes, (iii) organic carboxylic esters and (iv) specific It has already been explained that the titanium-containing catalyst component composed of the Ti compound becomes a special catalyst for preparing high-stereoregular polyolefins (German Patent Publication No. 2,504,036) when mixed with the organoaluminum compound. In this patent publication, inorganic magnesium compounds, in particular magnesium, are described for the use of halides, and these magnesium compounds are dehydrated or pulverized under reduced pressure before use, and classified into flat particle sizes of 1 to 50 microns. This patent makes no reference to the use of organo magnesium compounds that do not require such manipulation or treatment. There is also no mention that the use of organo magnesium compounds will further contribute to the technology involving those types of catalysts.

The present inventors have selected (i) an organosilicon selected from the group consisting of an organosilicon compound containing a magnesium bonded directly to one or more carbon atoms and an organosilanol and an organopolysiloxane containing at least one hydroxyl group directly bonded to silitine. Reaction products with the containing compounds, (ii) organic acid esters, and (iii) magnesium-containing solid titanium catalyst components formed by contacting titanium compounds are excellent catalysts for the polymerization or copolymerization of α-olefins containing three or more carbon atoms, or It has been found to be useful for providing excellent catalysts for the copolymerization of these olefins with up to 10 mole% of ethylene and / or diolefins. In addition, the magnesium-containing solid titanium catalyst component has the advantage that it does not require the operation or treatment carried out when using magnesium halide as the moon body, and the fact that it easily provides a catalyst with good reproducibility of catalytic activity and three or more carbon atoms It has been found that it is useful for obtaining high-stereoregular polymers or copolymers of olefins having a high yield.

The halogen content of the polymers or copolymers produced by the present catalyst can be reduced and the designated magnesium containing solid titanium catalyst components can further contribute to the preparation techniques of the high stereoregular olefin polymers or copolymers having three or more carbon atoms. It was confirmed that there is. In addition, the inventors of the present invention are particularly useful for the simple preparation of polymers or copolymers of olefins containing apparent three or more carbon atoms of high density and reduced content of micropowdery polymers or copolymers which are disadvantageous in handling.

It is therefore an object of the present invention to provide a process for preparing high-stereoregular polyolefins with the above-described improved effects.

Another object of the present invention is to provide a catalyst for use in the process of the present invention.

Other objects and advantages of the present invention will become more apparent from the following description.

Polymerization or copolymerization of α-olefins having at least 3 carbon atoms as referred to herein is homogeneous polymerization of α-olefins having at least 3 carbon atoms, up to 10% with α-olefins having 3 or more carbon atoms Copolymerization with ethylene and / or diolefins.

Examples of α-olefins are propylene, 1-butene, 4-methyl-1-pentene and 3-methyl-1-butene, and examples of diolefins include conjugated diolefins such as butadiene, dicyclopentadiene and ethylidenenor And non-conjugated dienes such as bornen and 1,5-hexadiene.

The catalyst used in this invention consists of (A) the magnesium containing solid titanium catalyst mentioned above, and (B) the organometallic compound of the Group I-III metal of the periodic table.

As already explained, component (A)

(i) between a magnesium-containing free magnesium compound bonded directly to one or more carbon atoms, and a silicon-containing compound selected from the group consisting of organic silanols and organic polysiloxanes containing at least one hydroxyl group directly bonded to silicon; And an organic complex derived from or reacted with the reaction product from (ii) an organic acid ester and (iii) a titanium compound.

The organo magnesium compound is, for example, a compound of the following structural formula.

R'-Mg-R ''

Wherein R 'is a member of the group consisting of an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, and an aryl group having 6 to 12 carbon atoms, and R' 'represents a halogen atom, 1 to 10 carbon atoms, One of the group consisting of an alkyl group, a cycloalkyl group having 3 to 10 carbon atoms, and an aryl group having 6 to 12 carbon atoms). Such an organic magnesium compound is an organic magnesium compound which is widely referred to as a Grignard reagent. These compounds may also be used in the form of adducts with ethers such as tetrahydrofuran. They do not have to be in the form of ether adducts, they may be in the form of the Journal of Chemical Society (Grignard reagents synthesized in a conventional inert solvent solution in 1961 by the method described on page 1175).

Specific examples of these organo magnesium compounds include

CH ₃ MgCl, CH ₃ MgBr, CH ₃ MgI: C ₂ H ₅ MgCl, C ₂ H ₅ MgBr, C ₂ H ₅ MgI: C ₃ H ₇ MgCl, C ₈ H ₇ MgBr, C ₃ H ₇ MgI: C ₄ H ₉ MgCl, C ₄ H ₉ MgBr, C ₄ H ₉ MgI: C ₅ H ₁₁ MgCl, N ₅ HMgI, C ₅ H ₁₁ MgI: C ₆ H ₁₃ MgCl, C ₆ H ₁₃ MgBr, C ₆ H ₁₃ MgI: C ₇ H ₁₅ MgBr, C ₇ H ₁₅ MgI: C ₈ H ₁₇ MgCl, C ₈ H ₁₇ MgBr, C ₈ H ₁₇ MgI: C ₉ H ₁₉ MgCl, C ₉ H ₁₉ MgBr, C ₉ H ₁₉ MgI: C ₁₀ H ₂₁ MgCl: C ₆ H ₅ MgCl, C ₆ H ₅ MgBr, C ₆ H ₅ MgI: CH ₃ (C ₆ H ₄ ) MgCl, CH ₃ (C ₆ H ₄ ) MgBr, CH ₃ (C ₅ H ₄ ) Halogen-containing organic magnesium compounds such as Mgl, Mg (CH ₃ ) ₂ , Mg (C ₂ H ₅ ) ₂ , Mg (C ₃ H ₇ ) ₂ , Mg (C ₄ H ₉ ) ₂ , Mg ( ₅ H ₁₁ ) ₂ , Mg (C ₆ H ₁₃ ) ₂ , Mg (C ₇ H ₁₅ ) ₂ , Mg (CH ₃ ) (C ₂ H ₅ ), Mg (C ₂ H ₅ ) (C ₃ H ₇ ), Mg (CH ₃ ) (C ₄ H ₉ ), Mg (C ₂ H ₅ ) (C ₄ H ₉ ), Mg (C ₆ H ₅ ) ₂ , Mg [CH ₃ (C ₆ H ₄ )] ₂ , Mg (C ₂ H ₅ ) (C ₆ H ₅ ), and Mg (C ₂ H ₅ ) CH ₃ (C ₆ H ₄ )]. Halogen-free magnesium compounds such as these.

The organo magnesium compound may contain other metals such as Al, Zn and B. These compounds can be synthesized by the methods shown in the Journal of Organometallic Chemistry (1975), Vol. 93, page 1. The organosilicon containing compound to be reacted with the organo magnesium compound is, for example,

(a) an organic silanol of the general formula

B '''ιSiOH ₄ -ι

Wherein R '' is a member of the group consisting of hydrogen, vinyl C ₁ -C ₄ alkyl and lower alkyl or optionally halogen containing phenyl, silver 1,2 or 3, and at least one R '''is optionally alkyl Or phenyl with halogen.

(b) an organic aliphatic polysiloxane of the general formula

Q (Q ₂ SiO) nSiO ₃

Wherein Q is hydrogen, —OH, C ₁ -C ₄ alkyl C ₃ -C ₈ cycloalkyl, C ₆ -C ₈ aryl, C ₁ -C ₁₂ alkoxy and phenoxy, n is an integer from 1 to 1000 , And not all Q can be hydrogen atoms at the same time)

(c) organic cyclopolysiloxanes of the general formula

(Q ₂ SiO) n

Wherein Q and n are as described above.

Specific examples of the organic silanol compound (a) include (CH ₃ ) ₃ SiOH, (CH ₃ ) ₂ (C ₂ H ₅ ) SiOH), (CH ₃ ) ₂ (C ₅ H ₅ ) SiOH, (C ₂ H ₅ ) SiOH, (C ₆ H ₅ ) ₃ SiOH, (C ₂ H ₅ ) ₂ Silanols with one hydroxyl group, such as HSiOH, (CH ₃ ) ₂ Si (OH ₃ ), (CH ₂ ) C ₆ H ₅ ) Si (OH) ₂ , (C ₂ H ₅ ) ₂ Si (OH) ₂ , (C ₂ H ₅ ) (C ₆ H ₅ ) Si (OH) ₂ , (C ₆ H ₅ ) ₂ Si (OH ) ₂ and _{(CH 3) (CH 2 〓CH} ) Si (OH) silanol having two hydroxyl groups such as ₂ nolryu and Cl2C ₆ H ₃ Si (OH) sila nolryu with three hydroxyl groups such as ₃ to be.

Specific examples of the organoaliphatic polysiloxane (b) include hexanemethyldisiloxane, decamethyltetrasiloxane, tetracosamethylundecsiloxane, 3-hydrheptamethylsiloxane, 3,5-dihydrooctamethylsiloxane, 3,5,7 Trihydrononmethylmethylpentasiloxane, tetramethyl-1,3-diphenyldisiloxane, pentamethyl-1,3,5-triphenyltrisiloxane, heptaphenyldisiloxane, octaphenyltrisiloxane, methylpolysiloxane and phenylmethylpolysiloxane There is this. Examples of the organic cyclopolysiloxane (c) include 2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, hexamethylcyclotrisiloxane, oxmethylcyclotetrasiloxane, decamethylcyclopenta Siloxane, triphenyl-1,3,5-trimethylcyclotrisiloxanehexa, phenylcyclotrisiloxane and octaphenylcyclotetrasiloxane.

If Q represents an organic group in the above formula, it may be a substituent such as hydrogen or a hydroxyl group.

The reaction product (i) used to produce the magnesium-containing solid titanium catalyst component (a) in the present invention is a reaction product produced between the organic magnesium compound and the organic silicon-containing compound exemplified above. The molar ratio of the organic magnesium compound to the organic silicon-containing compound of Mg / Si is preferably about 0.1 to about 10.

Examples of the organic acid ester (ii) which is another component used to produce the magnesium-containing solid titanium catalyst component (A) are organoaliphatic acid esters, organoalicyclic acid esters and organoaromatic acid esters. Preferred examples of the organic acid ester (ii) include (a) C ₁ -C ₁₈ optionally substituted by halogen, preferably C ₁ -C ₈ , more preferably C ₁ -C ₄ saturated or unsaturated aliphatic carboxylic acids; C ₁ -C ₁₈ , more preferably C ₁ -C ₄ saturated or unsaturated aliphatic primary alcohols, C ₁ -C ₈ , preferably C ₅ -C ₆ saturated or unsaturated alicyclic alcohols, C ₆ -C ₁₀ , Esters formed between alcohols selected from C ₆ -C ₈ phenols and C ₁ -C ₄ saturated or unsaturated aliphatic alcohols bound to C ₃ -C ₁₀ aliphatic or aromatic rings, (b) C ₃ -C ₁₀ aliphatic lacs Tones, (c) carboxylic acid esters (d) C ₆ -C ₁₂ , preferably C ₆ -C ₈ alicyclic carboxylic acids and C ₁ -C ₈ , preferably C ₁ -C ₄ saturated or unsaturated aliphatic 1 Esthetes formed between tertiary alcohols, (e) C ₇ -C ₁₈ , preferably C ₇ -C ₁₂ , aromatic carboxylic acids and C ₁ -C ₁₈ preferably C ₁ -C ₈ More preferably C ₆ -C ₄ saturated or unsaturated aliphatic primary alcohol, C ₃ -C ₈ preferably C ₆ -C ₈ saturated or unsaturated alicyclic alcohol, C ₆ -C ₁₀ preferably C ₆ -C Esthetes formed between ₈ phenols and C ₁ -C ₄ saturated or unsaturated aliphatic primary alcohols bound to C ₃ -C ₁₀ aliphatic or aromatic rings (f) C ₈ -C ₁₂ aromatic lactones and (g) There is a mixture of these esters.

Specific examples of the organic acid esters include primary alkyl esters of saturated fatty acids such as methyl formate, ethyl acetate, n-amyl acetate, 2-ethylhexyl acetate, n-butyl formate, ethyl butyrate and ethyl valerate, vinyl acetate and acetic acid. Alkenyl esters of saturated fatty acids such as altyl, primary alkyl esters of unsaturated fatty acids such as methyl acrylate, methyl methacrylate and n-butyl crotonate, and halogenated aliphatic monocarboxyls such as methyl chloroacetate and ethyl dicyclolo acetate Acid esters, propiolactone, lactones such as γ-butyloyl lactone and δ-valetolactone, carboxylic acid esters such as ethylene carboxylate, methyl cyclohexanecarboxylic acid, ethyl cyclohexanecarboxylic acid, Alicyclic acid esters such as methyl methyl cyclohexanecarboxylic acid and ethyl methylcyclohexanecarboxylic acid.

Specific examples of aromatic acid esters which are the most preferred organic acid esters in the present invention include (a) methyl benzoate, ethyl benzoate, n- or i-propyl, benzoic acid n-, i-, sec-, or tert-butyl, benzoic acid n- or i-amyl, benzoic acid n-hexyl, n-benzoic acid, n-octyl, 2-ethylhexyl benzoic acid, vinyl benzoate and benzoyl benzoate, wherein the alkyl group is usually from 1 to 8 carbon atoms, preferably Is a saturated or unsaturated hydrocarbon group containing 1 to 4 carbon atoms), preferably methyl benzoate and ethyl. (b) cycloalkyl benzoates such as benzoic acid cyclopentin and cyclohexyl carbonate, wherein the cycloalkyl group is a non-aromatic cyclic hydrocarbon group containing usually 3 to 8 carbon atoms, preferably 5 or 6 carbon atoms) c) aryl benzoates such as phenyl benzoate, benzoic acid 2-chlorophenyl and benzoic acid 4-chlorobenzyl, wherein the aryl group is a hydrocarbon group containing 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, the aromatic An alkyl group containing a halogen and / or usually 1 to 4 carbon atoms may be bonded to the ring (d) An aromatic monocarboxylic acid ester in which an electron donating substituent such as an alkoxy or alkyl group is bonded to an aromatic ring. Methyl aniseate, ethyl aniseate, i-propyl anise, i-butyl aniseate, phenyl anisate, benzyl-o-methoxybenzoate, ethyl p-ethoxy Alkoxy, such as methyl phosphate, n-butyl p-ethoxybenzoate, ethyl p-alioxybenzoate, phenyl p-ethoxybenzoate, methyl methyl o-ethoxybenzoate, ethyl verarate, and ethyl asymmetric guamicol carboxylate Benzoic acid esters, wherein the alkyl group constituting the alkoxy group is usually an alkyl group containing 1 to 4 carbon atoms, preferably a methyl or ethyl group, and the alkyl and attyl groups of this ester are as defined above, and (f) p- Methyl toluate, p-tolueneethyl, p-toluene, i-propyl, toluic acid n- or i-aryl, p-toluic acid altyl, p-toluic acid phenyl, p-toluic acid 2-tolyl, 0-toluic acid Ethyl, ethyl m-toluate, methyl p-ethyl benzoate, p-ethyl benzoate sec-butyl, 0-ethyl benzoic acid i-propyl, m-ethyl benzoic acid n-butyl, 3,5-xylene carboxyethyl and p-styrene Alkyl benzoic acid esters, such as ethyl carboxylate (here, in the aromatic ring of benzoic acid The combined alkyl group is usually a saturated or unsaturated hydrocarbon group containing 1 to 8 carbon atoms and the alkyl and atyl groups of this ester are as defined above.) (G) amino such as methyl p-aminobenzoate and ethyl p-aminobenzoate Containing benzoic acid esters (h) naphthoic acid esters such as methyl naphthoate, ethyl naphthoate, propyl naphthoic acid and butyl naphthoate (i) aromatic lactones such as coumarin and phthalide.

Of these, benzoic acid, alkyl benzoic acid and alkoxybenzoic acid esters are preferred. Preference is given to C1-C4 alkylesters of benzoic acid, 0- or p-toluic acid or p-anisic acid, in particular methyl or ethyl esters.

Preferred titanium compounds for use in the formation reaction of the catalyst component (A) are tetravalent titanium compounds of the following general formula.

Ti (OR) g ^X 4-g

g

4이다.Wherein R is a C ₁ -C ₆ alkyl group or a C ₆ -C ₁₂ allyl group, X is a halogen atom such as Cl, Br or I, 0

g

4

Specific examples of such titanium compounds include titanium tetrahalides such as TiCl 4, TiBr ₄ , and TiI ₄ . Ti (OCH ₃ (Cl ₃ , Ti (OCH ₅ ) Cl ₃ , Ti (On-C ₄ H ₉ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃ and Ti (Oiso-C ₄ -H ₉ ) Br) Such as titanium trihalide alkoxy, Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (O nC ₄ H ₉ ) ₂ Cl and Ti (OC ₂ H ₅ ) ₂ Br; Monohalogenated trialkoxy such as titanium halide, Ti (OCH ₃ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Cl, Ti (O n -C ₄ H ₉ ) ₃ Cl and Ti (OC ₂ H ₅ ) ₃ Br Titanium tetraalkoxytitanium such as Ti (OC H ₃ ) ₄ Ti (OC ₂ H ₅ ) Ti (OnC ₄ H ₉ ) ₄ Titanium tetrahalogenated is preferred, with titanium tetrachloride being the best.

The solid titanium catalyst component (A) of the present invention is a reaction product obtained by contacting (i) an organic magnesium compound with an organic silicon-containing compound, (ii) an organic acid ester, and (iii) a titanium compound.

Various contacting methods for preparing component (A) can be used. Preferably, reaction product (i) is first reacted with organic acid ester (ii), and then the reaction product is reacted with reaction titanium compound (iii).

The reaction product (i) is carried out in several ways. The reaction may be carried out in an inert organic solvent such as ether or heptane, nucleic acid or kerosene. The organo magnesium compound may be synthesized before use. Alternatively, the compound may be produced by presenting the original metal magnesium, silicon-containing compound and (alkyl halide compound in the production reaction system of the reaction product (i). The reaction temperature is, for example, from room temperature to about 300 ° C., preferably from about 30 minutes to The molar ratio of the organo magnesium compound to the organosilicon-containing compound varies depending on the type of these compounds, preferably with 0.1 to 10 atoms of silicon per atom of magnesium. The reaction product can be maintained in the solvent during or after the reaction to obtain the final product.

The compound structure of the reaction product (i) of the organomagnesium compound and the organosilicon-containing compound is not known in detail. The infrared absorption spectrum of reaction product (i) shows that the absorption bands for Si—O—Si bonds of OH and polysiloxane in silanol are virtually lost and new absorption bands appear between 800 and 1000 cm ⁻¹ . This is indicated when the organo magnesium compound is reacted with an organosilicon containing compound such as silanol or polysiloxane. The emergence of new absorbent bands is probably due to the production of Si-O-Mg in the reaction product.

Preferred reaction products (i) have a ratio of organic magnesium to organic silicon-containing compounds represented by Ms / Si of about 0.1 to about 10, and Mg-C bonds observed in the organic magnesium compounds in their absorption spectra are substantially lost. Compounds. These reaction products may include other magnesium compounds. For example, they may contain small amounts of reaction products generated between the organic magnesium compound and the electron donor or magnesium halide.

In the production of the solid titanium catalyst component (A) in the present invention, the contact of the reaction product (i) with the organic acid ester (ii) is preferably carried out by mechanical co-pulverization. At this time, the mechanical co-pulverization may be carried out in the presence of a co-existence of an inorganic or organic filler or a grinding aid. Examples of such adjuvants include LiCl, CaCl, SrCl ₂ , BaCl ₂ , NaSO ₄ , Na ₂ CO ₃ , TiO ₂ , NaB ₄ O ₇ , Ca ₃ (PO ₃ ) ₂ , CaSO ₄ , BaCO ₃ , Al ₂ (SO ₄ ) ₃ , B ₂ O ₃ , SiO ₂ , polyethylene, polypropylene and polystyrene.

The co-pulverization treatment is carried out in the substantial absence of oxygen or water using a bowl and a device such as a rocking mill or impact mill. The ratio between the reaction product (i) and the organic acid ester (ii) is such that the amount of the organic acid ester (ii) is preferably from about 0.001 to about 10 molar times, more preferably from about 0.01 to about 1 mole, relative to 1 atom of magnesium in the reaction product (i). To be molested. The grinding conditions may be appropriately selected depending on the kind of the reaction product (i) and the organic acid ester (ii) or the grinding device, for example. Usually the grinding time is from about 1 hour to about 10 days, the grinding temperature is at or near room temperature, and there is no need to specifically cool or heat the grinding apparatus. For example, a stainless steel (SUS 32) bowl 2.5gg with a diameter of 15 mm is contained in a stainless steel bowl mill cylinder with an internal diameter of 100 ml and an internal diameter of 100 mm, and a rocking mill with a grinding force of 7 g impacts in the case of a rocking mill containing 20 to 40 g of crushed material. At acceleration, a grinding time of at least about 6 hours, preferably at least about 24 hours, is carried out to a significant extent.

In order to react the titanium compound (iii) of another component for forming the solid titanium catalyst component (A) in the present invention, various operating methods can be used. For example, the reaction product (i) and the organic acid ester (ii) may be mechanically ground in the presence of the titanium compound (iii) to contact these three components under mechanical grinding conditions, or the powdered product obtained by the above-described method may further be added to the titanium compound. Or the titanium compound (iii) is contacted with the mechanically pulverized product of the reaction product (i) and the organic acid ester (ii) in the mechanically pulverized member.

When the contact with the titanium compound is carried out under grinding conditions, it is possible to use a titanium compound in the form of a complex with an organic acid. When used under grinding conditions, the amount of the titanium compound in the form of a complex with an organic acid is preferably 0.01 to about 10 molecules, more preferably about 0.01 to about 1 atom, per atom of magnesium.

This powdered product can be washed or washed so that lene can be used as the solid catalyst component (A). In the final stage of catalyst preparation, it preferably reacts with the liquid titanium compound in the mechanically pulverized member.

In specifying the titanium compound in the liquid phase in the mechanical powdering member, the powder product produced from (i) and (ii), or the powder product produced from (i), (ii) and (iii), such as titanium tetrachloride It is preferable to suspend in a liquid titanium compound or a solution of a titanium compound in an inert organic solvent such as hexane, heptane or kerosene. According to this method, a small amount of impurities generated during the grinding step does not adversely affect and the ratio of the raw materials can be varied widely.

The titanium compound is preferably used in an amount of about 0.0011 to about 1000 atoms, particularly about 0.05 atoms or more, per atom of magnesium in the amount of titanium atoms, but the amount may depend on the amount of the organic acid ester. There is no particular limitation at the temperature at which the liquid titanium compound reacts in the absence of mechanical grinding conditions. However, it is usually preferable to carry out the contact reaction at a temperature of about 20 to about 200 캜 for at least about 0.5 hours.

When contacting under mechanical grinding conditions, the resulting catalyst component (A) is separated, for example, by filtration and thoroughly washed with an inert organic solvent of the kind previously envisaged, which is then used for synthesis.

The contact of the magnesium and silicon containing reaction product (i) with the organic acid ester (ii) is also carried out in an inert solvent such as hexane, heptane or kerosene in the absence of mechanical grinding conditions.

When materials (i) and (ii) are contacted without mechanical grinding, the amount of organic acid ester (ii) is preferably from about 0.01 mole to about 1 mole per mole of magnesium in the reaction product (i). The reaction is then sufficient if it is carried out at a reaction temperature of room temperature to about 200 ° C. for about 5 minutes to about 2 hours.

After the reaction, the reaction product is separated or washed with evaporation and inert solvent to separate the final desired product. The reaction of the reaction product with the titanium compound can be substantially carried out according to the reaction method between the milled product and the above-described desired titanium compound.

The solid titanium component (A) obtained by the present invention has a representative composition consisting of about 1.0 to 6.0 wt% titanium, 10.0 to 20.0 wt% magnesium, 40 to 70 wt% halogen and 5.0 to 15.0 wt% organic acid ester. . This composition does not change substantially even upon hexane washing at room temperature.

The surface area of component (A) is usually 10 m ² / g or more, preferably 50 m ² / g or more.

m

3의 수이다)의 화합물, 예컨대 알킬알루미늄화합물, 알킬알루미늄알록시드, 알킬알루미늄 수화물, 알킬알루미늄할로겐화물, 디알킬아연 및 디알킬마그네슘이 있다. 유기 알루미늄 화합물의 예로는 Al(C₂H₅)₃, Al(CH₃)₃, Al(C₃H₇)₃Al(C₄H₉)₃, Al(₁₂H₂₅)₃(C₂H₅)₂AOAl(C₂H₅)₂와 같은 트리알킬 또는 트리알케닐알루미늄, (C₄H₉)₂AlOAl(C₂H₅)₂(C₄H₉)₂Al OAl(C₄C₉)₂또는 (C₂H₅)₂AlNAl(C₂H₅)₂와 같이 복수개의 Al원자가 원소 또는 산소 또는 질소 원자를 C₆H₅경유하여 결합하고 있는 알킬 알루미늄 화합물(C₂H₅)₂ALH 및 (C₄H₉)₂AlCl와 같은 디알킬알루미늄 수소화물 및 (C₂H₅)₂Al(OC₂H₅) 및 (C₂H₅)₂Al(OC₆H₅)와 같은 디알킬알루미늄알콕시드가 있다.The organometallic compound of the Group I to Group III metal of the periodic table used as the catalyst component (B) contains a hydrocarbon group bonded directly to the metal, and an organoaluminum compound is preferably used. Examples of such organometallic compounds are of the general formula R'mAl (OR ') _3-m , where R' is an alkyl group, preferably a C ₁ -C ₄ straight or branched chain alkyl group, wherein at least two R 'groups are the same or different , m is 1.5

m

3), such as alkylaluminum compounds, alkylaluminum alkoxides, alkylaluminum hydrates, alkylaluminum halides, dialkylzinc and dialkylmagnesium. Examples of organoaluminum compounds include Al (C ₂ H ₅ ) ₃ , Al (CH ₃ ) ₃ , Al (C ₃ H ₇ ) ₃ Al (C ₄ H ₉ ) ₃ , Al ( ₁₂ H ₂₅ ) ₃ (C ₂ H ₅ ) Trialkyl or trialkenylaluminum such as ₂ AOAl (C ₂ H ₅ ) ₂ , (C ₄ H ₉ ) ₂ AlOAl (C ₂ H ₅ ) ₂ (C ₄ H ₉ ) ₂ Al OAl (C ₄ C ₉ ) ₂ or _{(C 2 H 5) 2 AlNAl} (C 2 H 5) a plurality of Al atom element, or oxygen, or an alkyl bonded to the nitrogen atom via C ₆ H ₅ aluminum compounds, such as ₂ (C ₂ H _{5) 2} Dialkylaluminum hydrides, such as ALH and (C ₄ H ₉ ) ₂ AlCl and di, such as (C ₂ H ₅ ) ₂ Al (OC ₂ H ₅ ) and (C ₂ H ₅ ) ₂ Al (OC ₆ H ₅ ) Alkyl aluminum alkoxides.

Of these, trialkylaluminum is most preferred.

According to the present invention, olefins having three or more carbon atoms are mutually up to 10 mol% in the presence of a catalyst composed of (A) a magnesium-containing solid titanium catalyst component and (B) an organometallic compound of Groups I to III metals of the periodic table. May be polymerized or copolymerized with ethylene and / or diolefin. It is preferred to use a reaction temperature between room temperature and about 200 ° C., more preferably between about 50 ° and about 180 ° C., and between atmospheric pressure and about 50 gg / cm ² , more preferably between about 2 and about 20 gg / cm ² . This polymerization reaction or copolymerization reaction can be carried out in the presence or absence of an inert liquid medium. Examples of liquid media are pentane, hexane, heptane, iso-octane and kerosene.

The polymerization can be carried out batchwise, semicontinuously or continuously. It is also possible to polymerize in two or more stages with different reaction conditions.

The concentration of the catalyst to be supplied to the polymerization reaction system can be changed as desired. For example, in liquid phase polymerization, the solid catalyst component (A) is usually used at a concentration of 0.001 to 0.5 mmol liters of the liquid medium in terms of titanium atoms, and the catalyst component (B) is usually used in the liquid medium in terms of metal atoms. It is used at a concentration of 0.5 to 50 millimoles / liter. The ratio of Al or other metal atoms to Ti atoms is preferably 1: 1 to 100: 1, preferably 1: 1 to 30: 1. In vapor phase polymerization, the solid catalyst component (A) per ml of volume of the reaction zone is at a concentration of 0.001 to 50 mmol (in terms of titanium atoms), and the catalyst component (B) is converted to 0.01 to 5 mmol aluminum or other metal atoms. Can be used in

Hydrogen may also be the cause (which increases the melt index of the polymer) to decrease the molecular weight of the polymer produced and present in the polymerization reaction system.

To control the stereoregularity of α-olefins, ethers, ethylene glycol derivatives, amines, amides, sulfur-containing compounds, nitriles, esters, carboxylic acids, acid amide oxy acids, keto acids, acid anhydrides, acid halides, amino acids, etc. May be present in the polymerization reactor system. Of these, all of the aforementioned aromatic carboxylic acid esters which are organic acid esters are preferred. Such aromatic acid esters may be selected from those previously cited for the preparation of the solid catalyst component (A). Particularly preferred esters are benzoic acid esters and nearly plastid benzoic acid esters such as toluene salts, tiphthalate salts, diterephthalate salts, hydroxyancin salts and amino benzoate salts. Most preferred are methyl p-toluate and ethyl p-toluate.

These stereoregulatory modifiers may be used in the form of adducts with the organometallic compound (B). The effective amount of the stereoregularity regulator is usually from about 0.01 to about 2 moles, particularly preferably from about 0.1 to about 1 mole, per mole of the organometallic compound (B).

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

Example 1

A commercially available Greenite Reagent C ₂ H ₅ MgCl (2 mol / liter, 50 ml in terahydrofuran) was suspended in 300 ml of refined kerosene and TOSHIBA Execcon TSF-451 (methylpolysiloxane, 20 cetistrooke) 14.8 g was added and the reaction mixture was heated to 200 ° C. and reacted for 30 minutes to obtain a white solid. The solid was filtered off, washed with hexane and dried, and then 15 g of this compound was dried with 21 ml of ethyl benzoate under a nitrogen atmosphere. The cylinder was charged into a wheat cylinder and contacted at 125 ppm for 100 hours.

The solid product thus treated was suspended in 300 ml of titanium tetrachloride, and the suspension was stirred at 80 ° C. for 2 hours. After completion of the reaction, the solid part was filtered and washed sufficiently with nucleic acid to obtain a titanium-containing solid catalyst component, the composition of which was 2.5% by weight titanium, 56% by weight chlorine, 8.5% by weight magnesium and 8.2% by weight ethyl benzoate.

Into a 2-liter autoclave, 750 ml of hexane sufficiently freed of oxygen and water were introduced, and 5.0 mmol of triethyl aluminum and 1.59 mmol of methyl p-toluate were introduced under a propylene atmosphere at 40 ° C. After 5 minutes, the titanium-containing solid catalyst component was introduced with 0.03 Mali mol based on titanium atoms into the autoclave, the polymerization system was heated to 60 ° C. and the total pressure was raised to 7.0 gg / cm ² by propylene. Subsequently, 400 ml of hydrogen was introduced to polymerize propylene for 4 hours.

After the completion of the polymerization, the solid was filtered to obtain 125 g of white powdered polypropylene. This product had a boiling n-heptane extraction residue of 95.8% m, a bulk density of 0.38, a melt index of 6.0, and 90% of the particle size of the powder was 74 microns or more. It was made of particles.

The liquid phase was concentrated to give 8.3 g of a solvent soluble polymer.

Example 2-5

The procedure of Example 1 was repeated in the preparation of catalysts using the respective polysiloxanes listed in Table 1 instead of TOSHIBA silicone TSF-451.

The result was the same as the first table.

TABLE 1

Example 6

Diphenylsilanediol (22.4 g) synthesized by hydrolysis of diphenylclosilane was suspended in 200 ml of toluene, and 104 ml of a 2M / 1 tetrahydrofuran solution of ethyl magnesium chloride was added dropwise thereto, and severe exotherm at the time of addition. As this occurred the mixture was ice cooled and kept at room temperature. After completion of the addition, a reflux condenser was attached to the reactor and the reaction was carried out at 65 ° C for 1 hour. After completion of the reaction, the solvent was distilled off to obtain a white solid.

16.6 g of the solid was suspended in 200 ml of kerosene, and 2 ml of ethyl benzoate was added and reacted at 80 ° C. for 2 hours. The solid obtained was filtered, washed with nucleic acid, dried, and then suspended in titanium tetrachloride 200 again. The reaction was stirred at 80 ° C. for 2 hours. After the completion of the reaction, the bridged beak was filtered and thoroughly washed with hexane to obtain a titanium solid catalyst component, the composition of which was 3.6% by weight titanium, 58% by weight chlorine, 17% by weight magnesium, and 6.5% methyl benzoate.

Propylene was polymerized in the same manner as in Example 1 except that the titanium-containing solid catalyst component was used at 0.03 millimoles on a titanium atom basis, and 133 g of powdered propylene was obtained. The polymer had a boiling n-heptane extraction residue of 94.2%, a volume density of 0.37 and a melt index of 5.3 and a particle size distribution of 88% of the particle size was 74 microns or more. The liquid phase was concentrated to give 9.5 g of solvent soluble polymer.

Example 7

20 g of Toray Silicone SH-6018 (hydroxyl oxane containing molecular weight 1600 and hydroxyl content of 6.0% by weight) was suspended with 100 ml of hexane, and the suspension was heated to 60 DEG C and n-butylmagnesium chloride 2M / 1 tetrahydro was added thereto. 23 ml of furan solution was added dropwise over 30 minutes and allowed to react at isothermal temperature for 1 hour. After completion | finish of reaction, the solid part was filtered out at room temperature, the obtained solid was suspended in 300 ml of kerosene, 3 ml of benzoic ethyl was added, and it was made to react at 0 degreeC for 1 hour. The reaction product was filtered, washed with hexane, dried and suspended in 150 ml of titanium tetrachloride, and then reacted with titanium tetrachloride at 120 ° C. for 2 hours. The obtained solid was filtered off and washed with hexane to obtain a titanium solid catalyst component. The composition was 5.0 wt% titanium, 56 wt% chlorine, 12 wt% magnesium, and 4.4 wt% ethyl benzoate.

Except for using the titanium-containing solid catalyst component in an amount of 0.03 mmol on the basis of titanium atoms propylene was synthesized according to the same procedure as in Example 1 to give 127 g of a white powdery polypropylene. The polymer had a boiling n-heptane extraction residue of 95.3%, a volume density of 0.36, a melt index of 5.7, and a particle size distribution or 91% of the powders having a particle size of 74 microns or more.

The liquid phase was concentrated to give 7.9% of the solvent soluble polymer.

Example 8-11

In the catalyst preparation, a tita-containing solid catalyst component was synthesized in the same manner as in Example 1 except that instead of ethyl benzoate, each of the organic esters listed in Table 2 was used to polymerize propylene. This result was the same as in the second table.

TABLE 2

Example 12

To 100 mmol of trimethylhydroxysilane was added dropwise 50 ml of a tetrahydrofuran solution of n-butyl chloride 2M / 1 synthesized from metal magnesium and n-butyl chloride, and the reaction mixture was kept at room temperature during this addition period. After completion of the addition, the reaction mixture was allowed to react for 1 hour under reflux to the boiling point of tetrahydrofuran. After the reaction was completed, tetrahydrofuran was maintained and the residue was dried to obtain a white powder.

The rotary beam was contacted in a mill in the same manner as in Example 1 with 10 g of the obtained white solid together with 1.5 ml of methyl benzoate. The solid product thus treated was suspended in 200 ml of titanium tetrachloride and reacted at 80 ° C. for 2 hours with stirring. After the reaction was completed, the solid part was filtered and thoroughly washed with hexane to obtain a titanium solid catalyst component, the composition of which was 2.1 weight% titanium and 995 weight% chlorine.

Propylene was polymerized in the same manner as in Example 1 except that 0.03 mmol of the obtained titanium-containing solid catalyst component was used on a titanium atom basis to obtain 120 g of a white powdery polypropylene. The polymer had a boiling n-heptane extraction residue of 93.8%, a volume density of 0.36, and a melt index of 7.6. The particle size distribution of the powder was a solid having a particle size of 74 microns or more.

Concentration of the liquid phase gave 8.9% of a solvent-soluble polymer.

Example 13

A white solid was synthesized in the same manner as in Example 6 except that 52 mmol of 2 Mg (nC ₄ H ₉ ) was used instead of magnesium chloride.

A titanium-containing solid catalyst component was produced in the same rotary contact manner as in Example 1 except that 15 g of the obtained white solid and 2 ml of ethyl benzoate were used. The catalyst component contained 2.9% by weight of titanium and 57% by weight of chlorine.

Propylene was polymerized in the same manner as in Example 1 except that this titanium solid catalyst component was used in an amount of 0.03 mmol on the basis of titanium atoms to obtain 98 g of a polypropylene of white powder. The polymer had a boiling n-heptane extraction residue of 94.7%, a volume density of 0.35, and a melt index of 6.2. The particle size distribution of the powder contained 87% of the particles having a particle size of 74 microns or more.

6.4 g of solvent-soluble polymer was obtained by concentrating a liquid part.

Comparative Example

The white solid obtained in Example 1 (reaction product of ethylmagnesium chloride with Toshiba silicon TSF-451 (15 was suspended in 300 ml of titanium tetrachloride without reacting with an organic acid ester and reacted at 130 ° C. for 2 hours). The solids were filtered off during the hot and washed thoroughly with purified hexane to obtain a titanium-containing solid catalyst component, which contained 3.9% by weight titanium and 59% by weight chlorine.

Into a 2-liter autoclave, 750 ml of hexane sufficiently kept oxygen and moisture were charged, and 0.03 mmol of the titanium-containing solid catalyst component obtained above and 0.03 mmol of the titanium-containing solid catalyst component was added at 40 ° C. under a propylene atmosphere. Introduced. The polymerization system was heated to 60 ° C. and propylene was used to raise the total pressure to 60 gg / cm ² , followed by introduction of 300 ml of hydrogen to polymerize propylene for 2 hours.

After the polymerization was completed, the solid material could not be collected because the entire polymerization mixture became rubbery polypropylene. Methanol was precipitated to obtain 38.1 g of doped polypropylene. This product had a steep n-heptane extraction residue of 40,1%, which showed remarkably low stereoregularity.

Claims (1)

(i) the reaction of an organic silicon-containing compound selected from the group consisting of magnesium-containing organic magnesium compounds bonded directly to at least one carbon atom and organic silanol containing at least one hydroxyl group directly bonded to silicon and organic polysiloxanes; A product comprising (ii) an organic acid ester and (ii) a magnesium-containing solid titanium catalyst component (A) formed by contacting a titanium compound with an organometallic compound (B) of Groups I to III metals of the periodic table, at least three Method for producing a polymerization or copolymerization catalyst of olefins having carbon atoms with up to 10 mol% of ethylene or diolefin