DE2822301A1 - PROCESS FOR THE POLYMERIZATION OF ALPHA-OLEFINS HAVING AT LEAST 3 CARBON ATOMS AND A CATALYST FOR USE IN THIS PROCESS - Google Patents

Description

Process for the polymerization of α-olefins with at least 3 carbon atoms and catalyst for use in this process

description

The invention relates to a process for the preparation of a polymer or copolymer from an olefin having at least 3 carbon atoms by polymerizing an olefin containing at least 3 carbon atoms or by copolymerizing olefins containing at least 3 carbon atoms with one another or with not more than 10 mol -% ethylene or a diolefin. In particular, it relates to an improved process for the production of a polymer or copolymer from an olefin having at least 3 carbon atoms, which has an improved bulk density, in particular polypropylene with high stereoregularity, in high yield, with a further extended active service life of the catalyst being achieved. It further relates to a method and a catalyst for use in the method, in which a polymer having a high bulk density and high stereoregularity, even at a polymerization at a high temperature, such as 80 to 90 ⁰ C, is obtained.

There has already been described a process for the preparation of a polymer or copolymer from an olefin having at least 3 carbon atoms, in which an olefin having at least 3 carbon atoms and containing 0 to 10 mol% of ethylene or a diolefin is polymerized or copolymerized in the presence of a catalyst which contains (i) an organoaluminum compound, (ii) an electron donor, and (iii) a solid titanium composition.

8 0 9 P 4 7/1 0 4 2

An example of a catalyst suggested for use in such a process includes the reaction product, which is produced by treating the following starting materials:

(i) an organoaluminum compound that is free of halogen atoms bonded directly to the aluminum atom;

(ii) an electron donating compound (such as a base) in an amount such that 15 to 100% of the organoaluminum compound (i) combined with the electron donating compound; and

(iii) a solid component which, at least on the surface, is the reaction product of a halogenated magnesium compound with a tetravalent titanium compound and an electron donor compound, the molar ratio of electron donor to titanium atom in the product is over 0.2 and the molar ratio of halogen atoms to titanium atom is over 4; and component (iii) is further characterized in that at least 80% by weight of the tetravalent Titanium compound contained in it are insoluble in boiling n-heptane that at least 50% by weight of the

Titanium compound, which is insoluble in n-heptane, are in ^ at 80 ⁰ C, and that the surface of the _{part insoluble in TiCl 4} at 8O and the surface of component (iii) itself is greater than 40 m ² / g (JA- OS 151 691/77, open gel on December 16, 1977).

There is no suggestion of the use of an organoaluminum compound in this Japanese patent publication with halogen atoms bonded directly to the aluminum atom as indicated in (i) above, and the description this publication is limited to an organoaluminum compound, which is free of halogen atoms which are directly bonded to the aluminum atom, e.g. trialkyl aluminum, Dialkyl aluminum hydride, dialkyl aluminum alkoxide and alkyl aluminum sesquialkylate.

In all examples of this publication, the isotacticity obtained (material insoluble in boiling n-heptane) of polypropylene is at most 9 ^, 5%. The bulk density of the polypropylene in these examples is 0.5 (kg / l) at the most and 0.4 (kg / l) at the lowest. According to the measuring method of JIS K-6721 used in the present application, these values are about 0.40 g / ml at the most and about 0.25 g / ml at the lowest. As can be seen from the comparative examples, these are considerably low bulk weights.

The applicant has carried out extensive research in order to overcome the disadvantages of low stereo regularity and low bulk density in the method proposed above. Surprisingly, it has been found that a good quality polymer or copolymer can be prepared from an olefin having at least 3 carbon atoms, which has a high isotacticity and bulk density, determined according to the JIS K-6721 method, of at least about 0.35, if an organoaluminum compound composition is used which contains: an organoaluminum compound having halogen atoms which are bonded directly to the aluminum atom (the use of which is avoided in the known method described above) and an organoaluminum compound which is free of hydrogen atoms which are directly bonded to the aluminum atom and in which the ratio (X / Al) of halogen atoms (X) to aluminum atom (Al) is 0 <X / Al <1.

It has also been found that the above improvement with the attendant benefit of a prolonged Life of the catalyst and a high yield of product can be obtained. It was surprising that one High bulk density polymer with high stereo regularity can be obtained even when the polymerization occurs «A temperature is carried out as high as 80 to

90 ⁰ C is.

809847/1042

The present invention is therefore based on the object of providing an improved process for the production of a polymer or copolymer from an olefin having at least 3 carbon atoms with from 0 to 10 mol% of ethylene or a diolefin with an improved bulk density and high stereo regularity in high yield, at the same time an extended catalyst service life is obtained.

According to the invention, a catalyst is also to be made available which is used in this process can be.

The invention relates to a process for preparing a polymer or copolymer from an olefin having at least 3 carbon atoms, which is characterized in that an olefin having at least 3 carbon atoms and containing from 0 to 10 mol% of ethylene or a diolefin in the presence of a catalyst polymerized or copolymerized, which contains: an organoaluminum compound component, an electron donor and a solid titanium component, which is characterized in that the "catalyst contains:

(1) an organoaluminum compound composition containing;

(a) an organoaluminum compound which is devoid of a halogen atom directly bonded to the Al atom, expressed by the following formula

in the

R is a group from the class hydrogen atoms, alkyl

groups with 1 to 2 carbon atoms, cycloalkyl groups with 5 to 12 carbon atoms, aryl groups with 6 to 12 carbon atoms, alkoxy groups with 1 to 12 carbon atoms, Cycloalkoxy groups of 5 to 12 carbon atoms and aryl signifies oxy groups having 6 to 12 carbon atoms, where

1 the three R groups can be the same or different,

809847/1042

(b) an organoaluminum compound containing halogen atoms, which are directly bonded to the aluminum atom, expressed by the formula

3-n-m in the

R has the meaning given above, ρ

R is a group from the class hydrogen atoms, alkoxy groups having 1 to 12 carbon atoms and aryloxy groups with 6 to 12 carbon atoms means

X denotes a halogen atom, 0 <n <3, 0 <m <3 and 0 <n + m = 3,

where the ratio (X / Al) of the halogen atoms (X) to the aluminum atom (Al) is O <X / A1 <1,

(2) an electron donor and

(3) a halogen-containing solid titanium component which is the reaction product of a magnesium compound, an electron donor and a tetravalent titanium compound, wherein the ratio of electron donor (mol) / titanium atom is not less than 0.2 and the ratio of halogen atoms / titanium atom is not less than is 4; Component (3) is further characterized in that at least 80% by weight of the tetravalent titanium compound it contains are insoluble in boiling n-heptane, that at least 50% by weight of the tetravalent titanium compound ^{are insoluble in TiCl ^ at 80 °} C. and that the surface of the product, which ^{is insoluble in TiCl ^ at 80 0} C, and the surface of component (3) as such are greater than 40 m / g.

The invention also relates to a catalyst for the polymerization or copolymerization of an olefin with at least 3 carbon atoms and containing 0 to 10 mol% of ethylene or a · diolefin, the catalyst contains:

809847/1042

(1) containing an organoaluminum compound composition

(a) an organoaluminum compound free from halogen atoms expressed by the following formula

R ¹ 3 Al in the

R is a group selected from the class of hydrogen atoms, alkyl groups having 1 to 12 carbon atoms, cycloalkyl groups having 5 to 12 carbon atoms, aryl groups having 6 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, Cyc Ioalkoxygruppen having 5 to 12 carbon atoms, and aryloxy groups having 6 to Means 12 carbon atoms, where the three R groups can be the same or different, and

(b) an organoaluminum compound having halogen atoms directly bonded to the aluminum atom by the formula

in the

R has the meaning given above,

2 R is a group from the class hydrogen atoms,

Denotes alkoxy groups with 1 to 12 carbon atoms and aryloxy groups with 6 to 12 carbon atoms, X denotes a halogen atom, 0 <n <3, 0 <m <3 and 0 <n + m = 3,

where the ratio (X / Al) of the halogen atoms (X) to the aluminum atom (Al) is 0 <X / Al <1,

(2) an electron donor and

(3) a halogen-containing solid titanium compound which is the reaction product of a magnesium compound, a Electron donor and a tetravalent titanium compound, the ratio of electron donor (mol) / titanium atom is not less than 0.2 and the ratio of halogen atoms / titanium atom is not less than 4; and component (3) continues characterized in that at least 80% by weight of the in

809847/1042

their tetravalent titanium compound contained are insoluble in boiling n-heptane, that at least 50% by weight of the tetravalent titanium compound ^{are insoluble in TiCl ^ at 80 0} C, and that the surface of the ^{product insoluble in TiCl ^ at 80 0} C and the surface of the component (3) as such are greater than 40 m / g.

In the polymerization or copolymerization of olefins having at least 3 carbon atoms, the order is the addition of the catalyst components (a), (b), (2) and (3) as desired. For example, the four components (a), (b), (2) and (3) are mixed at the same time. Or the components (a), (b) and (2) are first mixed at the same time and then the ingredient (3) is mixed. Or ingredients (a) and (b) are mixed first, then the component (2) is mixed in and finally the component (3) is mixed in. Or the components (a) and (2) are mixed first, then the component (b) is mixed and finally the component (3) is mixed Or the components (a) and (2) are mixed first, then the component (3) is mixed in and Finally, component (b) is added.

Examples of organoaluminum compounds (a) which are free from halogen atoms directly attached to the aluminum atom are bound, and represented by the formula R -zAl are triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, Trihexyl aluminum, triisoprenyl aluminum, trioctyl aluminum, diethyl aluminum ethylate, dibutyl aluminum butylate, Ethyl aluminum sesquibutylate, butyl aluminum sesquibutylate, Diethylcyclopentylaluminum, diethylcyclohexylaluminum, Dimethylcyclohexylaluminum, diethylphenylaluminum, diethyl-p-ethylphenylaluminum, dibutylphenylaluminum, diethylaluminum hydride, Dibuty aluminum hydride and dioctyl aluminum hydride.

809847/1042

The compound R, Al can before use with water, ammonia, alcohol or a primary amine according to a process known per se.

Examples of the organoaluminum compound (b) having halogen atoms, which are bound directly to the aluminum atom,

1 2

represented by the formula R _{1 n} AlX 3-nm R ^represents be Sestellt, alkylaluminum halides such as diethylaluminum chloride, di-n-butyläluminiumchlorid, diisobutylaluminum chloride, Didecenylaluminiumchlorid, Diäthylaluminiumfluorid, Diäthylaluminiumbromid, Diäthylaluminiuinjodid, Diäthylaluminiumsesquichlorid, Diisobutylaluminiumsesquichlorid and Äthylaluminiumdifluorid include; Alkylaluminum alkoxyhalides such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, octylaluminum octoxychloride, ethylaluminum decenoxychloride, ethylaluminum-4-butyl-2,6-dimethylphenoxychloride; and aryl aluminum halides such as diphenyl aluminum chloride or p-ethylphenyl aluminum dichloride.

The alkyl aluminum halide can be mixed with water, ammonia, alcohol, or a primary amine prior to use a process known per se. "

A mixture of a halogen-containing aluminum compound and an organometallic compound of one Metal of groups I or II of the periodic table, such as a Grignard reagent; a mixture of an organoaluminum compound and a halogen compound of silicon or tin; and a mixture of an organoaluminum compound and an alkyl halide, an alkenyl halide, a halide of a metal of group I or II of the periodic table or a hydrogen halide can also be used as organoaluminum

12 nium compound (b) of the formula R _n AlX _1n R 3_ _n _ _m can be used. They are examples of organoaluminum compounds having a halogen atom directly bonded to the aluminum atom, which are prepared by the following methods.

809847/1042

_ ₁₄ _

(a) BHeZ + Κ ' _η Α1Χ · ₃ _ _η - » ^R V- ^1Xn 3-m ^{+ R} '

(b) RSnX ₊ R ' ₃ A1 ) R ¹¹ AlX + R ¹¹¹ SnX

(c) RSiX + R ' ₃ A1

(d) ZrCl ₂ + R ₃ Al } R ₂ AlCl +

(e) SX + R 'Al

(£) HX + R ₂ AlR '- ^ R ₂ AlX + R ¹ H

In the above formula, R, R ', R "and R ¹ "

Ί has the same meaning as given above for R; X owns

the meaning given above for X, η and m have the same meaning as described above, and O <p <2.

In the organoaluminum compound composition (1), containing the organoaluminum compounds (a) and (b), the ratio (X / Al) of the halogen atom (X) to that is Aluminum atom (Al) O <X / A1 <1.

The electron donor used in the present invention (2) includes e.g. amines, amides, ethers, ketones, nitriles, phosphines, stibines, arsines, phosphoramides, esters, Thioethers, thiesters, acid halides, aldehydes, alcoholates, organic carboxylic acid anhydrides, organic carboxylic acids and Amides and salts of metals of groups I to IV of the periodic table. The salts can be used in situ in the implementation of the organic carboxylic acids are produced with component (a) or (b).

Preferred electron donors (2) are selected from organic carboxylic acids with 1 to 22 carbon atoms, organic carboxylic acid anhydrides with 2 to 22 carbon atoms, organic esters with 2 to 18 carbon atoms, organic acid halides with 2 to 15 carbon atoms,

809847/1042

Ether with 2 to 20 carbon atoms, ketones with 3 to 15 carbon atoms, aldehydes with 2 to 15 carbon atoms, organic acid amides with 2 to 8 carbon atoms, Amines and nitriles. Of these, organic carboxylic acid anhydrides, organic carboxylic acids, esters, organic acid halides and esters are particularly preferred. They can be used either alone or as mixtures. Or they can in the form of coordination compounds with compounds of metals such as aluminum or silicon.

Specific examples of organic carboxylic acid anhydrides having 2 to 22 carbon atoms (i-a) include aliphatic ^ Monocarboxylic anhydrides with 2 to 18 carbon atoms, such as acetic anhydride, propionic anhydride, n-butyric anhydride, Isobutyric anhydride, monochloroacetic anhydride, trifluoroacetic anhydride, caproic anhydride, lauric anhydride and stearic anhydride; (i-b) aliphatic polycarboxylic acid anhydrides with 4 to 22 carbon atoms, such as succinic anhydride, maleic anhydride, glutaric anhydride, Citraconic anhydride, itaconic anhydride, methylsuccinic anhydride, dimethylsuccinic anhydride, ethylsuccinic anhydride, Butylsuccinic anhydride, octylsuccinic anhydride, Stearic succinic anhydride and methylglutaric anhydride; (i-c) alicyclic carboxylic acid anhydrides with 8 to 10 carbon atoms, such as BieyeIo [2.2.1] -heptene-2,3-dicarboxylic anhydride or methylbicyclo [2.2] hepten-2,3-dicarboxylic anhydride; and (i-d) anhydrides of aromatic carboxylic acids having 9 to 15 carbon atoms, such as Acetobenzoic anhydride, benzoic anhydride, p-toluic anhydride, Phthalic anhydride and trimellitic anhydride.

Of these, the aromatic carboxylic acid anhydrides are preferred. The aliphatic monocarboxylic anhydrides are most preferred, although they have a somewhat lower polymerization activity exhibit.

809847/1042

Examples of organic carboxylic acids as electron donors (2) and the carboxylic acids such as those listed above in connection with the kit for organic carboxylic acid anhydrides. Particularly preferred carboxylic acids are aliphatic carboxylic acids, such as formic acid, acetic acid, isobutyric acid, caprylic acid, oxalic acid, lactic acid, acrylic acid, chloroacetic acid, stearic acid, behenic acid; and aromatic carboxylic acids such as benzoic acid, p-hydroxybenzoic acid, anisic acid, t-butylbenzoic acid, terephthalic acid, acetoxyacetic acid and toluic acid.

Examples of organic acid esters having 2 to 18 carbon atoms include aliphatic acid esters (iia), alicycligche Acid esters (ii-b) and aromatic acid esters (ii-c).

Examples of aliphatic esters (iia) are esters consisting of carboxylic acids or halogen substitution products. the group of saturated or unsaturated aliphatic carboxylic acids with 1 to 18 carbon atoms, preferably 1 to § carbon atoms, more preferably 1 to 4 carbon atoms, and their halogen substitution products and alcohols or phenols from the group of saturated or unsaturated aliphatic primary alcohols with 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, saturated or unsaturated alicyclic alcohols with 3 to 8 carbon atoms, preferably 5 to € carbon atoms, phenols with 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, and C ₁ -C ^ saturated or unsaturated aliphatic primary alcohols bonded to the ring carbon atom of a C 1 -C ₁₀ aliphatic or aromatic ring; and lactones having 3 to 10 carbon atoms are formed.

Specific examples of aliphatic esters (iia) include primary alkyl esters of saturated fatty acids such as methyl formate, ethyl acetate, n-amyl acetate, 2-ethylhexyl acetate,

809847/1042

_ ₁₇ _ 282230t

n-butyl formate, ethyl butyrate, ethyl valerate, methyl acetylacetate , ethylacetoacetate , propylacetoacetate, butylacetoacetate and octylacetoacetate; Alkenyl esters of saturated fatty acids such as vinyl acetate and allyl acetate; primary alkyl esters of unsaturated fatty acids, such as methyl acrylate, methyl line thacrylate or n-butyl crotonate; Alkyl esters of halogenated aliphatic monocarboxylic acids such as methyl chloroacetate or ethyl dichloroacetate; and lactones such as propiolactone, γ-butyrolactone or 6- valerolactone.

Examples of alicyclic esters (ii-b) are esters that are between alicyclic carboxylic acids with 6 to 12 carbon atoms, preferably 6 to 8 carbon atoms, and saturated or unsaturated aliphatic primary alcohols with 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, are formed. Specific examples include methyl cyclohexane carboxylate, Ethyl cyclohexane carboxylate, methyl methyl cyclohexane carboxylate and ethyl methyl cyclohexane carboxylate.

Examples of aromatic esters (ii-c) are esters between aromatic carboxylic acids with 7 to 18 carbon atoms, preferably 7 to 12 carbon atoms, and alcohols and phenols, selected from the group of saturated or unsaturated aliphatic primary alcohols with 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, saturated or unsaturated alicyclic alcohols with 3 to 8 carbon atoms, preferably 3 to 6 carbon atoms, phenol with 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, and C.-C ^ saturated or unsaturated aliphatic primary alcohols which are bonded to the ring carbon atom of a C ₃ -C ₁₀ aliphatic or aromatic ring, and aromatic lactones having 8 to 10 carbon atoms are formed.

Specific examples of aromatic esters (ii-c) are alkyl or alkenyl esters, preferably C ₁ -Cg-, more preferably C ₁ -C ^ -alkyl esters or C ₂ -Cq-, more preferably C ₂ -C ^ -alkenyl-

809847/1042

esters, of benzoic acid, such as methyl benzoate, ethyl benzoate, n- and isopropyl benzoate, n-, iso-, sec- and tert-butyl benzoates, n- and iso-amyl benzoates, n-hexyl benzoate, n-octyl benzoate, 2-ethylhexyl benzoate, vinyl benzoate and allyl benzoate; Cycloalkyl or cycloalkenyl esters of benzoic acid, preferably C - ^ - Co - J, more preferably C ^ -Cg -cycloalkyl or cycloalkenyl esters of benzoic acid, such as cyclopentyl benzoate, cyclohexyl benzoate or cyclohexenyl benzoate; Aryl or aralkyl, preferably C ^ -C ₁₀ -, more preferably Cg-Co aryl or aralkyl, which may contain a substituent, such as a Halogenatorn or a C, -C · -low alkyl group 'of benzoic acid, phenyl benzoate , 4-tolyl benzoate, benzyl benzoate, styryl benzoate, 2-chlorophenyl benzoate or 4-chlorobenzyl benzoate; and aromatic monocarboxylic acid esters in which an electron donating substituent such as a hydroxyl, alkoxy, alkyl or amino group is attached to the aromatic ring. Examples of aromatic monocarboxylic acid esters which contain an electron donating substituent include esters of hydroxybenzoic acid, preferably C. -Cg-, more preferably C ^ -C ^ -alkyl esters, preferably Cp-Cg- »more preferably C ₂ -C ^ -alkenyl esters, preferably C, -C _Q -, more preferably Cc-Cg-cycloalkyl or cycloalkenyl esters, and preferably Cg-C ₁₀ -, more preferably Cg-C _1Q -aryl or aralkyl esters of hydroxybenzoic acid; typical examples thereof are: methyl salicylate, ethyl salicylate, isobutyl salicylate, isoamyl salicylate, allyl salicylate, methyl p-hydroxybenzoate, n-propyl p-hydroxybenzoate, sec. -Butyl-p-hydroxybenzoate, 2-ethylhexyl-p-hydroxybenzoate, cyclohexyl-p-hydroxybenzoate, phylsalicylate, 2-tolylsalicylate , benzyl salicylate, phenyl-p-hydroxybenzoate, 3-tolyl-phydroxybenzoate, benzyl-p-hydroxybenzoate -α-resorcylate; Esters of alkoxybenzoic acids, preferably esters of lower alkoxybenzoic acids with 1 to 4 carbon atoms, which are preferably a C «. -Cp-alkoxy group, and preferably C ₁ -Cg, more preferably C ^ C ^ -alkyl esters, or preferably Cg-C ₁₀ , more preferably Cg-C ₁ Q-aryl or aralkyl esters of lower alkoxybenzoic acids , such as methyl anisate, Ethyl anisate, isopropyl anisate, isobutyl anisate, phenyl anisate, benzyl anisate, ethyl

809847/1042

o-methoxybenzoate, methyl-p-ethoxybenzoate, ethyl-p-ethoxybenzoate, n-butyl-p-ethoxybenzoate, ethyl-p-allyloxybenzoate, phenyl-p-ethoxybenzoate, methyl-o-ethoxybenzoate, ethyl vera entered and gua - colocarboxylate; Esters of alkyl or alkenylbenzoic acids, preferably alkyl or alkenylbenzoic acids, which preferably contain a C ₁ -C 6, more preferably C -C alkyl group or a Cp -C, more preferably Cp -C alkenyl group, and preferably contain C.-Cg-, more preferably Cj-C.-alkyl esters and preferably Cg-C ^ ₀ -, more preferably Cg-C ₁₀ aryl or aralkyl esters of alkyl or alkenyl benzoic acid, such as methyl p-toluate, ethyl -p-toluate, isopropyl-p-toluate, n- and iso-amyl toluate, allyl-p-toluate, phenyl-p-toluate, 2-tolyl-p-toluate, ethyl-o-toluate, ethyl-m-toluate, methyl-p- ethyl benzoate, ethyl p-ethyl benzoate, sec-butyl pethyl benzoate, isopropyl o-ethyl benzoate, n-butyl m-ethyl benzoate, ethyl 3 »5-xylene carboxylate and ethyl p-styrene carboxylate; and aminobenzoic acid esters, preferably C ^ -C ^ -alkyl esters of aminobenzoic acid, such as methyl p-aminobenzoate and ethyl p-amino benzoate. Other examples of aromatic esters (ii-c) include naphthoic acid esters, preferably C 1 -C 4 -alkyl esters thereof, such as methyl naphthoate, ethyl naphthoate, propyl naphthoate or butyl naphthoate, and aromatic lactones such as coumarin and phthalide.

Of the aromatic esters (ii-c) listed above, the esters of benzoic acid, alkyl- or alkenylbenzoic acids and alkoxybenzoic acids are preferred. Particularly preferred species are C ₁ -C 4 -alkyl esters, for example methyl or ethyl esters, or benzoic acid, o- or p-toluic acid and p-anisic acid.

Examples of organic acid halides having 1 to 15 carbon atoms as the electron donor (2) are halides of Carboxylic acid, as mentioned above in connection with the organic carboxylic acid anhydrides having 2 to 22 carbon atoms, for example. Specific examples of acid halides are acetyl chloride, benzyl chloride, toluoyl chloride, anisoyl chloride, stearoyl chloride, isobutyryl chloride, n-caproyl chloride and benzoyl chloride.

809847/1042

Examples of ethers having 2 to 20 carbon atoms include alkyl ethers containing 2 to 20 carbon atoms, preferably 6 to 20 carbon atoms, such as methyl ether, ethyl ether, isopropyl ether, butyl ether, isoamyl ether, octyl ether, ethylene glycol butyl ether and anisole; cyclic ethers containing 2 to 10 carbon atoms such as tetrahydrofuran and tetrahydropyran; and aromatic ethers containing 7 to 18 carbon atoms such as diphenyl ether.

Examples of ketones having 3 to 15 carbon atoms are acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, Benzophenone, cyclohexanone and benzoquinone.

Examples of aldehydes having 2 to 15 carbon atoms include acetaldehyde, propioaldehyde, octylaldehyde, benzaldehyde, hydroxybenzaldehyde, tolualdehyde and naphthaldehyde.

Examples of organic acid amides having 2 to 8 carbon atoms are acetamide, benzamide and toluamide.

Examples of amines are tributylamine, Ν, Ν'-dimethylpiperazine, tribenzylamine, aniline, pyridine, picoline and tetramethylethylenediamine.

Examples of nitriles are acetonitrile, benzonitrile and tolunitrile.

The proportion of electron donor (2) used is preferably about 0.01 to about 1 mol, particularly preferably about 0.1 to about 0.5 mol per aluminum atom of the organoaluminum compound composition (1) containing the organoaluminum compounds (a) and (b). The ratio between components (a) and (b) is arbitrary. For example, will the component (b) is used in an amount of 0.1 to 5 mol / mol of the component (a). Depending on the types of components (a) and (b) (each of which has at least one compound

809847/1042

may contain), the proportions of (a) and (b) be determined so that the ratio X / Al) of the halogen atom

(X) is also aluminum atom (Al) O <X / A1 <1.

The halogen-containing solid titanium catalyst component which is used together with the ingredients (a), (b) and (2) is a complex essentially containing magnesium, halogen, tetravalent titanium and an electron donor, and which is preferably in the form a reaction product of magnesium dihalide, tetravalent titanium halide and electron donor is present. The ratio of magnesium (MoI) / titanium atom is preferably about 3 to about 40, preferably about 10 to about 30. The ratio of halogen atom / titanium atom is at least 4, preferably about 10 to about 90, more preferably about 20 to about 80 The ratio of electron donor (mol) / titanium atom is at least 0.2, preferably about 0.4 to about 6, more preferably about 0.4 to about 3.

In the case of the halogen-containing solid titanium component, at least 80 % by weight, preferably at least about 90% by weight, of the tetravalent titanium compound is insoluble in boiling n-heptane, and at least 50% by weight, preferably at least about 70% by weight, of the tetravalent titanium compound are insoluble in TiCl ^ at 8O ^{0 C.}

The surface of the insoluble at 8O ⁰ C in TiCl ₄ part lind that of the component (3) itself to be at least 40 m / g, preferably at least about 100 m / g, more preferably about 100 to about 300 m / g.

A particularly suitable component (3) is characterized in that in its X-ray spectrum the most intense line that occurs in the spectrum of magnesium dichloride and magnesium dibromide of the normal type, as shown by the Standard ASTM 3-0854 and 15-836 for chloride and bromide defined, has a reduced relative intensity and is asymmetrically widened and thus forms a halo that

809847/1042

shows an intensity peak which is shifted in relation to the interplanar distance d of the maximum intensity line, or the spectrum is characterized in that the maximum intensity line is no longer present and a halo occurs in its place with an intensity peak which, in relation to the distance d of the line described above is shifted. In the case of MgClp, the halo intensity peak is between d = 2.44 Å and 2.97 1.

In general, the composition of the component (3) can be represented as containing 70 to 80% by weight of magnesium dichloride or magnesium dibromide and that the difference is 100% of the titanium compound and the electron donor.

The component (3) may, in addition to the above compounds, an inert solid filler in an amount of $ 80 or more based on the weight of component (3) »included.

Examples of such fillers are LiCl, CaCO ,, CaCl ₂ , Na ₂ SO ^, Na ₂ CO ^, Na ₂ B ^ O ₇ , CaSO ^, AlCl ₅ , B ₂ O ₃ , Al ₂ O ₃ , SiO ₂ , TiO ₂ , Naphthalene and durene.

When component (3) is prepared in the presence of an inert solid filler, the surface area generally decreases. In particular, when component (3) is _{mixed homogeneously with an agglomerating compound, in particular B 2} O, or AlCl ^, the resulting product generally has a surface area below 10 to 20 m / g. The performance of catalysts obtained from such component (3) is still acceptable, particularly with regard to the yield of polymer.

In preparing the ingredient (3), it is recommended to use the active ingredient together with a carrier or an inert carrier such as SiO ₂ and Al ₂ O ,, higher

809847/1042

Use porosity. The titanium and magnesium halogenated compounds or titanium and magnesium halogen compounds and the electron donor thus represent a reduced proportion, based on the total amount, and thus the production of catalysts is possible in which the amount of undesired materials, like halogen, is minimal.

While the Mg / Ti ratio is generally higher than 1, it is lower than 1 when containing TiOp and similar inert titanium compounds such as titanium salts of oxygen inorganic acids, can be used as inert fillers.

The halogen-containing solid titanium component ( 3) can be produced by various methods . Before given it can be prepared by reacting a solid reaction product between the magnesium compound and the electron donor with the tetravalent titanium compound, the solid reaction product being suspended in the tetravalent titanium compound or both the tetravalent titanium compound and an inert organic solvent such as heptane, hexane or kerosene , is held.

Examples of useful magnesium compounds are those of the formulas MgX ₂ , R ₁ MgX _2-1 , Mg (OR) _2-1 X ₁ and MgMe (OR) X, where X is a halogen atom such as chlorine or bromine or iodine, preferably chloride, R denotes a group from the class of alkyl groups, preferably with 1 to 12 carbon atoms, and aryl groups, preferably with 6 to 12 carbon atoms, Me denotes Al or Si and 1 denotes a positive number of 0 <1 <2.

Furthermore, in the preparation of the component (3), a hydrated magnesium _{halide, which generally contains 0.1 to 6 moles of H 2} O / mole of halide, can be used as the starting material. MgO, Mg (OH) ₂ , Mg (OH) Cl, magnesium carbonate, a magnesium salt of an organic acid, magnesium silicate, magnesium aluminate, magnesium alcoholate and their halogenated ones

809847/1042

Derivatives can also be used. An organomagnesium compound containing at least one Mg-C bond can also be used as a starting material. Examples of such compounds are Grignard reagents and compounds of the formula MgR ₂ , in which R is an alkyl, cycloalkyl or aryl group with up to and including 20 carbon atoms.

Examples of the electron donor used in the manufacture of component (3) can be used are those as mentioned above in connection with component (2) became. The electron donor used in the preparation of the component (3) may be the same as the electron donor (2), or it may not be the same.

Suitable tetravalent titanium compounds are, for example, compounds of the formula

Ti (OR ') _g X ₄ _ _g

in which R ¹ denotes an alkyl group with 1 to 12 carbon atoms, a cycloalkyl group with 5 to 12 carbon atoms and ■ an aryl group with 6 to 12 carbon atoms, X denotes a halogen atom, such as chlorine, bromine or iodine, and g denotes a number of 0 to 4 stands.

Specific examples of these titanium compounds are titanium _{tetrahalides such as TiCl 4} , TiBr ₄ or TiJ ₄ ; Alkoxytitanium trihalides, such as Ti (OCH,) Cl ,, Ti (OC ₂ H ₅ ) Cl ₃ , Ti (0-nC ₄ H _g ) Cl ₃ , Ti (OC ₁₂ H ₂₅ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃ or Ti- (0-iso-C ₄ HgBr ₃ ; alkoxy ti tan-dihalides, such as Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ C1 ₂ , Ti (O-HC ₄ H ₉ ) ₂ C1 and Ti (OC ₂ H ₅ J ₂ Br; trialkoxytitanium monohalides, such as Ti (OCH ₃ ) JC1, Ti (OC ₂ H ₅ J ₃ Cl, Ti (0-nC ₄ Hg) ₃ Cl and Ti (0C ₂ H ₅ ) ₃ Br; tetraalkoxy titanium compounds such as Ti (OCH ₃ J ₄ , Ti (OC ₂ H ₅ ) ₄ and Ti (0-nC ₄ H _g ) ₄ , and aryloxy titanium halides such as Ti (OC ₅ H ₅ ) _n Cl ₄ _ _n , Ti (OC ₅ H ₄ .CH ₃ ) _n Cl ₄ _ _n and Ti [OCgH ₂ .4-tC ₄ H _g -2.6. (CH ₃ ) ₂ ] _n Cl ₄ _ _n . Of these are the titanium tetrahalides are particularly preferred

809847/1042

most preferred. They can be used as mixtures with the electron donor (2).

Various methods such as those described below can be used to prepare the component (3) will.

(1-a) A general method is that a particular composition or carrier containing a magnesium halide and a complex between the magnesium halide and an electron donor in which the molar ratio of Mg / electron donor is higher than 2 and preferably in the range of 2 to 15 is used as the starting material, treating the composition or the carrier with a liquid tetravalent titanium compound under such conditions that a certain amount of titanium compound is bound to the carrier, and then separating the solid reaction product from the liquid phase under such conditions that practically no titanium compound which is soluble in boiling n-heptane and ι remains in the product.

n-heptane is soluble and can be extracted with TiCl ^ at 80 ° C,

The special feature of the carrier that is treated with the liquid titanium compound is that it shows an X-ray spectrum in which the diffraction line of the maximum intensity, which in the spectrum of the corresponding normal type magnesium halide occurs, has a reduced relative intensity, and is asymmetrically broadened, so that a halo is formed in which the intensity peak is shifted with respect to the maximum intensity line, or that the maximum intensity line is not present in the spectrum and is instead one Halo occurs with an intensity peak that is displaced in relation to the distance d of the maximum intensity line. However, when such a magnesium halide is bound to another carrier such as magnesia, the spectrum of the

809847/104?

Magnesium halide sometimes does not appear in the X-ray spectrum. In this case, the presence of amorphous magnesium halide can be confirmed by analyzing the product obtained in the extraction of the carrier-containing magnesium halide with, for example, an alcohol .

This carrier, ie the starting material for the preparation of component (3) of the catalyst according to the invention, can be obtained in various ways.

In a preferred method, a mixture of magnesium halide, in particular magnesium dichloride or magnesium dibromide, is milled with an electron donor, optionally in the presence of a titanium compound and / or an inert co-carrier and / or an agent that facilitates milling, such as silicone oil, until the above described halo with the intensity peak, shifted, based on the maximum intensity line, occurs in the X-ray spectrum of the ground product.

The ground product is treated with a halogenated titanium compound, in particular TiCl ^, optionally in the presence of an electron donor, at temperatures (generally between room temperature and 200 ^° C.) and during such times which are sufficient to bind a suitable amount of titanium compound.

The solid reaction product is then separated from the liquid phase, e.g. by filtration, sedimentation, etc., under such temperature conditions that the amounts of extractable titanium compounds ^{in the solid product after extraction with boiling n-heptane and with TiCl ^ at 80 ° C.} the 20 and 50 wt.% are, are no longer present.

In this process, magnesium alkoxyhalides, magnesium aryloxyhalides, magnesium alkoxides, magnesium aryloxides and magnesium carboxylate can be used instead of the magnesium

80984 7/1042

halides can be used. In this case, halogenating agents can be used at the time of milling.

(1-b) A method according to method (1-a) except that the starting product containing the magnesium halide and the electron donor is prepared in solution instead of a milling treatment. In particular, the magnesium halide such as MgX ₂ , Mg (OR) _2-1 X ₁ , R _1, MgX _2-1 or MgMe (OR) X, with the electron donor in the presence of a solvent which is inert to the magnesium halide and / or the electron donor such as hexane, heptane, kerosene, benzene, toluene, xylene or chlorobenzene at a desired temperature, and the product is treated with the same titanium compound as in the method (1-a) in the presence or absence of the reaction medium.

(1-c) A method which consists in treating a magnesium compound with a halogenating agent such as chlorine, hydrogen chloride, thionyl chloride, silicon tetrachloride, silicon alkyl chloride, hydrogen bromide or an aluminum halogen compound, reacting the product with an electron donor, and then further reacting the product with treated with a titanium halide. The treatment of the magnesium compound with the halogenating agent is preferably carried out in the presence of a reaction medium, but it can also be carried out in the absence of the reaction medium.

The magnesium compound treated with the halogenating agent in the above manner then becomes a co-pulverization treatment according to the method (1-a) or the treatment in solution according to the method (1-b) and then treated with the titanium halide according to the method (1-a).

(1-d) A method which consists in dissolving the magnesium compound and the electron donor according to the Process (1-b) treated, the product of halogenation treatment in the same manner as in Process (1-c) under-

809847/1042

throws and then the resulting product with the titanium halide treated in the same manner as in method (1-a).

(1-e) Another method of making a for the formation of the carrier suitable for component (3) consists in that one has a magnesium compound, an electron donor (preferably an organic acid ester) and another electron donor in any order desired the process (1-a) or (1-c) and the reaction product with an organoaluminum compound or a halogenating agent, such as silicon halides or tin halides.

The order of the reaction can be changed. For example, it is possible to create a complex that is between the magnesium compound and the electron donor is formed, ~ with the organoaluminum compound j) the ^ d.em halogenating agent "to treat and treat the resulting product with the electron donor according to method (1-a) or (1-b).

The treatment of the magnesium compound with the organoaluminum compound, silicon halide or is preferred Tin halide carried out by placing the magnesium compound in an inert solvent, such as a hydrocarbon, suspended and the organoaluminum compound or halogenating agent (e.g. silicon halide or tin halide), either alone or as a solution in an inert solvent, adding to the suspension. In general, the reaction proceeds sufficiently at room temperature and there is no heating especially required. However, heating is generally advantageous because it accelerates or activates the reaction will.

The resulting product is made with an inert hydrocarbon solvent to remove traces of free organoaluminum compound or halogenating agents, such as Silicon halide or tin halide, then the product is treated with a titanium compound, especially TiCl ^

809847/1042

measured the process (1-a) implemented and the solid reaction product is separated off, so that essentially no titanium compound, which ^{can be extracted with boiling n-heptane and with TiCl ^ at 80 0} C, remains on the solid component.

The details of these procedures are given in JA-OS 28189/76 (published March 9, 1976), in JA-OS 92885/76 (published on August 14, 1976) and described in DE-OS 2,605.

When a magnesium halide in those described above Method is used and especially when the catalyst component is prepared by pulverization, the magnesium halide is preferably as anhydrous as possible (a Water content of not more than 1 wt.

When a magnesium aryloxy halide or aralkoxy halide is used as the magnesium compound in the manufacture of the component (3) Isc it is preferable to use a method to use, which consists in reacting it with an organic acid ester as an electron donor and then reacting the product with a titanium halide in the same manner as in the previously described methods. The details this procedure is described in JA-OS 147 688/77 (published December 8, 1977).

If organomagnesium compounds, magnesium alkoxides, magnesium aryl oxides, magnesium oxyhalides or magnesium aryloxy halides are used as the magnesium compound, it is also possible to implement a reaction product between the magnesium compound and a halogenating agent and an electron donor (preferably an organic acid ester with a titanium halide in the preparation of component (3)) .

809847/1042

(i- £) When a magnesium compound of the formula MgR ₂ is used, it is combined with a compound that _{can destroy the Mg-R bond of MgR 2} , such as a halogen-containing silicon or tin compound, or with an ester, amine, a carboxylic acid or its metal salt, ketone, aldehyde or a mixture of such a compound and aluminum, etc. reacted. Then the reaction product is treated with an excess of TiCl; implemented in the presence of the electron donor (2). The solid reaction product is then separated off at an elevated temperature.

The resulting solid product as a suspension in an inert hydrocarbon is treated with 1 to 20 mol per titanium atom contained in the support of an electron donor, in particular an organic acid ester, such as an aromatic carboxylic acid ester, at room temperature up to 200 ^{° C.}

The solid reaction product treated according to this process is carefully removed from the unreacted electron donor separated and then reacted with a halogenated titanium compound. Then the reaction product separated from the liquid phase by process (1-a).

It is important that in the processes described above at least 80 wt.% Of the titanium compound contained in the component (3) in boiling n-heptane should be insoluble, and that not more than 50% wt. Of the titanium compound with TiCl ^ at 80 ⁰ C should be extractable. In fact, the presence of a titanium compound is löäichen both the activity adversely and the stereospecificity of the catalyst, particularly when the polymerization is carried out in the presence of hydrogen with respect to.

According to the invention is an olefin having at least 3 carbon atoms and polymerized containing 0 to 10 mol% of ethylene or a diolefin in the presence of a catalyst

8098 4 7/1042

or copolymerized containing components (a), (b), (2) and (3) as described above.

Examples of suitable olefins are ct-olefins with 3 to 16 carbon atoms, such as propylene, 1-butene, 4-methyl-1-pentene, 1-octene, 1-decene and 1-hexadecene. Examples of diolefins are butadiene, 1,4-hexadiene, 1,7-octadiene and ethylidene rbornen.

The method of the invention is particular for manufacture very stereoregional polymers or copolymers of cc-olefins with at least 3 carbon atoms in high Yields suitable. The polymerization can be a homopolymer! - be cation, random copolymerization or block copolymerization. For example when propylene is copolymerized with ethylene it is possible to polymerize propylene until homopolymerization in an amount of about 60 to about 90 percent on the overall composition, and then a mixture of propylene and ethylene or ethylene to polymerize. Alternatively, a mixture of propylene and ethylene can be polymerized to form a copolymer obtained containing ethylene in a proportion of not more than about 10 MoI-Ji.

The polymerization can be carried out either in the liquid phase or in the vapor phase. When the polymerization is carried out in the liquid phase, an inert solvent such as hexane, heptane or kerosene can be used as the reaction medium. The olefin itself can be used as a reaction medium be used. In the liquid phase polymerization, it is preferred to be 0.0001 to 1 mmol calculated as Titanium atom, on component (3), 0.001 to 100 mmol, calculated as the aluminum atom, on component (a), 0.001 to 100 mmol, calculated as the aluminum atom of component (b) and 0.001 to 100 mmol of component (2) to be used and the amount of aluminum in components (a) and (b) to 1 to 100 moles, preferably 1 to 300 moles, per mole of titanium in the loading

B098 4 7 / 1Q42

component (j), whereby all information is per litec refer to liquid phase.

In vapor phase polymerization, a fluidized bed or a fluidized layer or a stirred fluidized bed is used or a stirred fluidized layer is generally used. The component (3) is used either as a solid or diluted with hexane or an olefin, and ingredients (a), (b) and (2) are either diluted or not diluted with hexane or an olefin prior to charging to the polymerization reactor. An olefin and optionally Hydrogen are introduced into the polymerization reactor in the form of gases. The proportions of catalyst components are the same as for polymerisation in the liquid phase.

The polymerization temperature is generally from 20 to 20O ⁰ C, preferably 50 to 180 ⁰ C. In particular, the strong gter eoregelmäßige polymerization of propylene at a temperature of 50 to 14O ° C and a pressure of atmos-

2 2

ipheric pressure up to 50 kg / cm%, preferably 2 to 20 kg / cm.

1, manufacture of component (3)

20 g of anhydrous magnesium chloride and each of the electron donors listed in Table I are placed in a stainless steel (SU-32) ball mill container with an internal capacity of 8OO ml and an internal diameter of 100 mm, the 8.8 kf stainless steel (SUS-32) - Contains balls, each having a diameter of 15 mm, and then treated for 24 hours by blow-out acceleration of 7G in a nitrogen atmosphere. 10 g of the resulting solid is suspended in 100 ml Titantetraehlorid and heated with stirring at 80 ⁰ C and treated Z h. The solid product is filtered off and washed thoroughly with purified hexane until no more free titanium tetrachloride is detected in the washing liquid . Is this way solid titanium components containing Haigen,

8098 4 7/1042

prepared as described in Table I for use as ingredient (3).

The titanium-insoluble part of the component (3) is determined by the following method.

The total amount of titanium in the component (3) used as the catalyst component is determined according to ^ determined by the chlorimetric hydrogen peroxide method.

The amount of trivalent titanium is determined by the potassium permanganate method and the amount of tetravalent titanium is determined by subtracting the amount of trivalent titanium - determined by the total amount of titanium.

5 g of the ingredient used as the catalyst ingredient (3) are mixed and stirred in 100 ml of boiling n-heptane for 1 h. The n-heptane is separated off and the residue is washed twice with n-heptane at room temperature in a nitrogen atmosphere and dried under reduced pressure. The amount of titanium and the proportion of the part insoluble in boiling n-heptane are determined by the same procedure is being computed.

Furthermore, 5 g of constituent (3) are suspended in 100 ml of titanium tetrachloride and stirred for 1 h at 80 ° C. in a nitrogen atmosphere. The titanium tetrachloride is separated off and the residue is washed four times with hexane in a nitrogen atmosphere and dried at room temperature and reduced pressure. The amount of titanium is determined using the same method and the proportion of the part that is insoluble ^{in titanium tetrachloride at 80 ° C. is calculated.}

The specific surface area of the halogen-containing solid titanium component used as component (3) and the specific surface area of the solid titanium component which

8 0 9 8 4 7/1 CH

is extracted with titanium tetrachloride at 80 ⁰ C, are measured according to the nitrogen adsorption method.

In the following tables, Et = ethyl; Me = methyl; and Bu = butyl.

8 0 9 S ;, 7/10 4

Table I.

Catalyst electron donor (amount)

Insoluble in tetravalent titanium. %) of component (3)

boiling 80 ⁰ C TiCl ^ n-heptane

Surface (m / g) of component (3) before and after extraction with TiCl /, at 8QQC

before

after

Composition d. Component (3) electrical halogen nendonor

Ti Ti (molar (atomic ratio) ratio)

το
ο 1-1 ^Α 3 s) 98 98 203 200 1.3 99 I. (S3 ^Et 2 ° 1.8 I. OO
• ο 1-2 (iso-C, G) 96 96 193 188 1.9 52 CD
-C-
(VJ. 1-3 ε) 97 98 183 170 1.8 50 s) 90 95 191 189 45 2822c 1-5 O ₂ St (5.3 89 96 188 176 43 0 1-6 β) 94 173 160 (3.1 5 ^Η 1Ο ⁾ 2 ° Ύ * 1 (L. ti

2. Manufacture of the component (5)

Halogen-containing solid titanium components are produced in the same way as in (1), with the exception that that any of the magnesium compounds and titanium compounds listed in Table II instead of magnesium chloride and titanium tetrachloride is used, and that 2 ml of ethyl benzoate are used as an electron donor. The results are in Table II summarized.

809847 / 1OA?

Cat.Ti connection no.

Mg compound

Table II ■ «

(g) In four percent ti unl. surface area (m / g) composition

Salary (Oe \ f.%) Of existing. (3) d. Component register?)

on stock (y?) before and after d. Electron shark

boiling. 80OC extract. With donor gene

2-1 TiCl ₄ ^ 3-0.5 ⁰¹ L ₅ ³⁵ n-heptane ΓιΟΙλ TiCl /, b .80 "- ¹ C TiCMolver- Ti {, atom mated) VX 2-2 TiCl ₄ Et _n -MgCl _Q 20 before after hold.) 54 45 ' 2-3 -I, ((QV). -MgCl- Q 20 97 9S 1 91 ¹ J ⁶ 50 2-4 TiCl ₄ Mg (OEt) Cl 22 98 9S 195 190 49 47 Me 96 93 187 ISl '8608 2-5 TiCl ₄ Mg (O- / QVt-Bu) Cl 20 93 90 200 197 1.3 58 p + ^ * Me '^ 45 CJ O 2-6 TiCl ₄ MgAl (OBt) Cl ₄ 20 92 89 201 195 42 2-7 TiCl ₄ °> 2-8 TiBr ₄ MgCl 20 95 90 19G 182 1.4 2-9 «(« T, _{0. 5} ci,. ₅ MgCl 20 93 91 173 170 !> 3 2-10 Ti (O- / o> -t-Bu) Cl H ₈ Cl ₈ 95 95 306 ■ 197 ii * 92 88 199 195 1.6 91 210 200 1.7

3 manufacture of the component (5)

(3-1) 5 g (52.5 mmol) of commercially available magnesium dichloride are suspended in 100 ml of hexane. 105 mmol of butanol, 52.5 mmol of 2-ethylhexanol and 10.5 mmol of butyl toluate are added dropwise at room temperature. The mixture is stirred at 110 ^° C. for 1 h. To the mixture is added dropwise 79 mmol of diethylaluminum dichloride, and the mixture is stirred for 1 hour. The resulting solid is filtered off and washed well with hexane. The solid is suspended in 100 ml of titanium tetrachloride and the suspension is ^{stirred at 100 °} C. for 2 h. The supernatant liquid is removed and 100 ml of titanium tetrachloride are added. The mixture is stirred for 1 h at 100 ^° C., filtered hot and washed with hexane to form component (3). The product is referred to as component (3) catalyst No. (3-1).

(3-2) The same procedure as in (3-1) was repeated except that 157.5 mmol of silicon tetrachloride are used instead of diethylaluminum chloride and that the mixture was stirred at 60 ⁰ C after the addition of silicon tetrachloride, and during 10 hours. The resulting solid titanium component containing halogen is referred to as component (3) catalyst no. (3-2).

(3-3) 5 g (43.7 mmol) of diethoxymagnesium are suspended in 50 ml of kerosene. 10.9 mmol of butyl benzoate are added. Then anhydrous hydrogen chloride is passed ^{into the suspension for 1 h at 0 °} C. and the suspension is ^{stirred at 20 °} C. for a further hour. The component (3) is prepared by preparing in the same manner as described in the preparation of the catalyst No. (3-1), except that the amount of titanium tetrachloride is adjusted to 300 ml and that the temperature, in which the product is treated with titanium tetrachloride, is changed ^{to 110 ° C.} The resulting product is referred to as Ingredient (3) Catalyst No. (3-3).

8098/4 7/1042

Catalyst Nos. (3-1), (3-2) and (3-) are listed in Table III .

4. Manufacture of the component (3)

(4-1) 5 g (52.5 mmol) of commercially available anhydrous magnesium dichloride are suspended in 200 ml of toluene and 315 mmol of ethanol are added dropwise at room temperature. The mixture is stirred for 1 hour at room temperature. 630 mmol trioctyl aluminum is added dropwise at ⁰ C and the mixture is stirred for 6 hours at 8O ⁰ C. The resulting solid is filtered off and washed well with hexane. The resulting solid is suspended in 100 ml of toluene, and 7.5 mmol of p-methoxyethyl benzoate are added dropwise at room temperature. The mixture is ^{stirred at 70 °} C. for 1 h. The solid is filtered off, washed well with hexane and dried. The product is treated with titanium tetrachloride under the same conditions as in the preparation of Catalyst No. (3-1). Component (3) is obtained. This product is referred to as component (3) catalyst No. (4-1).

(4-2) The procedure for preparing component (3) Catalyst No. (4-1) is repeated except that 630 mmoles of tin tetrachloride can be used instead of trioctyl aluminum. In this way component (3) catalyst no. (4-2).

The resulting catalysts Nos. (4-1) and (4-2) are shown in Table III.

5. Manufacture of the component (3)

(5-1) 5 g of commercially available magnesia is suspended in 100 ml of kerosene and 20 g of thionyl chloride is added. The mixture is stirred at 70 ⁰ C. for 18 h and 1.3 g Äthylcyclohexylcarboxylat be added. The mixture is stirred at 70 ° C. for 1 hour and filtered. The separated solid is

8098 U 7/1 0 4?

washed; a solid reaction product is obtained. The solid product is suspended in 300 ml of titanium tetrachloride and ^{stirred at 100 °} C. for <2 h. The product is filtered hot and washed with hexane to give a solid product. The product is referred to as component (3) catalyst No. (5-1).

(5-2) 5 g of commercially available magnesium hydroxide is suspended in 100 nil kerosene and chlorine gas is added. The suspension is ^{stirred at 80 °} C. for 6 h. Then 1.5 g of ethyl benzoate are added and the mixture is stirred at 70 ° C. for 1 h. It is filtered and washed; a solid reaction product is obtained. The solid product is treated with titanium tetrachloride in the same manner as in the preparation of Catalyst No. (5-1). The product is referred to as component (3) catalyst No. (5-2).

(5-3) 5 g of magnesium benzoyl chloride are suspended in 100 ml of hexane and hydrogen chloride is added at 0 ^° C. The suspension is ^{stirred at 30 °} C. for 6 h. 1.5 g of n-butyl benzoate are then added and the mixture is stirred at room temperature for 1 hour. Hexane is evaporated and 100 ml of titanium tetrachloride are added to the resulting solid. The mixture is ^{stirred at 110 °} C. for 2 h. The supernatant liquid is removed and 100 ml of titanium tetrachloride are added. The mixture is ^{stirred at 110 °} C. for 1 h, filtered, washed and dried. A product is obtained which is referred to as component (3) catalyst no. (5-3).

Catalyst Nos. (5-1), (5-2) and (5-3) are listed in Table III.

809847/1042

Table III

Component In tetravalent Ti Surface area (m / g) of the loading Composition; of the component (3)

(3) Kataly- insoluble content (wt.%) Component (3) before and after electron donor ' halogen generator number on component (3) d.Extraction with TiCl2, .b. Ti Ti

boiling 80 ° C 8QQC (molar ratio) (atomic ratio)

n-heptane

3-1 3-2 3-3

97 96 98

TiCl ₄

before

270 280 143

after

250 270 125

2.1
1.9
1.7

4-1 4-2

5-1 5-2 5-3

97 98

96 96 97

195 140

130

150

184 135

100

75

130

1.5
1.3

0.7
1.3

Examples 1 to 31 and Comparative Examples 1 to 3

Propylene is polymerized, each of the halogen prepared by the above processes 1 to 5 containing, solid titanium component and in organoaluminium components (a) and (b) and electron donors listed in Table IV (2) used. The results are shown in Table IV.

In Examples 1 to 24 and Comparative Examples 1 to 3, a 2 liter autoclave is used. In the examples 25 to 31 a 1! Glass flask is used. The amount of component (3) as a titanium atom is 0.015 mmol Examples 1 to 19; 0.001 mmol in Example 20; 0.002 mmol in Examples 21 to 24; 0.05 mmol in Examples 25 to 31; and 0.015 mmol in Comparative Examples 1 to 3

809847/1042

2822301 - 43 - 2 3 Table 4 Hexane Hexane 1 750 750 Comparative example Hexane 7th 7th solvent 750 70 70 Amount of solution
medium (ml) 7th 4th 0.5 Pressure of propylene
(kg / cm ² G) 70 there Yes Polymerization tem
temperature (C) 4th - Et _x al
3 Polymerization time
(H) Yes - 1.5 Presence of what
hydrogen Et, Al
3 Et ₂ AlCl Et ₂ AlCl Component (a) 1.5 1.5 1.5 Amount (mmol) - 1
^Me - {0) - ^C0 2 ^M. ? 0.5 Component (b) - 0.15 - Amount (mmol) 0 1-1 1-1 X / Al ratio
Electron donor (2) ^Ml 0.5 4,500 11,000 Amount (mmol) 1-1 94.3 65.2 (3) Catalyst No. 15,000 0.38 0.24 Yield (g-pp / mmol Ti) 93.2 8.6 35.5 Isotacticity (%) 0.39 Bulk weight (g / ml) 3.9 Melt index

8098 4 7 / 10-2

Table 4 (continued)

example 1 2 3 solvent Hexane Hexane Hexane Amount of solution
medium (ml) 750 750 750 Pressure of propylene
(kg / cm ² G) 7th 7th 7th Polymerization tem
temperature ( ⁰ C) 70 70 70 Polymerization time
(H) 4th 4th 4th Presence of what
hydrogen There there" there Component (a) Et ₃ al Cn-C ₈ H ₁₇ ) JAl Me ₃ Al Amount (mmol) 0.75 0.75 0.75 Component (b) Et ₃ AlCl (n-Bu) ₂ AlCl Et ₂ AlCl Amount (mmol) 0.75 1.5 2.25 X / Al ratio 0.5 0.67 0.75 Electron donor (2) ^ ^G ~ (O) -CO ₂ Me ^Me ° - \ Q) - ^c0 _? ^Et ι ^ e- (O) -CO ₂ Et Amount (mmol) 0.375 0.375 0.375 (3) Catalyst No. 1-1 1-2 1-3 Yield (g-pp / mmol Ti) 21,400 17,300 15,200 Isotacticity (%) 96.0 95.2 94.8 Bulk weight (g / ml) 0.45 0.41 0.39 Melt index 2.4 2.1 2.8

809847/1042

Table 4 (continued)

example 4th 5 6th solvent Hexane Hexane Hexane Amount of solution
medium (ml) 750 750 750 Pressure of propylene
(kg / cm2G) 7th 7th 7th Polymerization tem
temperature ( ⁰ C) 70 70 70 Polymerization time 4th 4th 4th Presence of
hydrogen there there there Component (a) U-Bu) ₃ Al Et ₂ AlH (1-Bu ^ ₉ Al (OEt) _o> Amount (mmol) 1.125 0.75 1.0 Component (b) U-Bu) ₂ AlCl Et ₂ AlCl (i-Bu) ₂ AlCl Amount (mmol) 1.125 0.75 1.25 X / Al ratio 0.5 0.5 0.56 Electron donor (2) \ ^) - CO _? Et Me - ^ - CO ₂ Ke Amount (mmol) 0.563 0.428 0.625 (3) Catalyst No. 1-4 1-5 1-6 yield
(g-pp / mmol Ti) 12,000 12,800 13,100 Isotacticity (96) 94.0 93.8 92.9 Bulk weight (g / ml) 0.42 0.40 0.41 Melt index 3.0 4.1 4.3

809847/1042

Table 4 (continued)

example

solvent

Amount of solvent (ml)

Pressure of propylene (kg / cm ^ G)

Polymerization ^{temperature (0} C)

Polymerisation time (h)

Presence of
hydrogen

Component (a)

Amount (mmol)
Component (b)

Amount (mmol)
X / Al ratio

Hexane 750

7 70

yes et ₃ al

0.75 Et ₂ AlCl

0.375 0.33

Electron donor (2) KeO- (C)) -Co _? st amount (mmol) 0.375

(3) Catalyst No. 2-1

Propylene Propylene 500 g 500 g 25th 30th 60 70 1 1 Yes Yes Et, Al
D. (1-Bu) ₃ Al 0.5 0.5 Et ₂ AlCl (i-Bu) ₂ AlCl 0.25 0.5 0.33 0.5 0.25 0.23 2-2 2-3

yield

Ti)

Isotacticity (%) bulk density (g / ml) melt index

17,700

96.0 0.40 2.0 18,300

94.4
0.42
1.8

17,000

93.2 0.43 1.5

809847/1042

Table 4 (continued)

example 10 11 12th solvent Propylene Propylene Propylene Amount of solution
medium (g) 500 500 500 Pressure of propylene
(kg / cm ² G) 30th 25th 30th Polymerization tem
temperature (° C) 70 60 70 Polymerization time
(H) 1 1 1 Presence of
hydrogen there there there Component (a) Et ₃ al Et ₃ al U-Bu) ₃ Al Amount (mmol) 0.5 0.5 0.5 Component (b) Et ₂ AlCl Et ₂ AlCl Et ₂ AlCl Amount (mmol) 0.75 0.25 0.25 X / Al ratio 0.6 0.33 0.33 Electron donor (2) M. C-Zo) -CC ₂ Me 'He - ( O / ^C ° ol'te Et- (Ö) -CC _? _Et Amount (mmol) 0.25 0.25 , 0.33 (3) Catalyst No. 2-4 2-5 2-6 yield
(g-pp / mmol Ti) 15,700 13,900 13,200 Isotacticity (%) 93.6 94.6 94.8 Bulk weight (g / ml) 0.42 0.41 0.42 Melt index 1.3 1.7 1.0

809847/1 0Λ 2

Table 4 (continued)

example 13th 14th 15th solvent Propylene Propylene Propylene Amount of solution
medium (g) 500 500 500 Pressure of propylene
(kg / cm ² G) 25th 30th 30th Polymerization tem
temperature ( ⁰ C) 60 70 70 Polymerization time
(H) 1 1 1 Presence of
hydrogen Yes Yes there Component (a) Et ₃ al Et ₃ al Et ₃ al Amount (mmol) 0.5 0.5 0.5 Component (b) Et ₂ AlCl Et ₂ AlCl Et ₂ AlCl Amount (mmol) 0.25 0.25 0.5 X / Al ratio 0.33 0.33 0.5 Electron donor (2) ft Je- (O) -CC ₂ Me _Me0 - (0) -CC _? M. e Me- (O) -CO ₂ Me Amount (mmol) 0.33 0.33 0.33 (3) Catalyst No. 2-7 2-8 2-9 yield
(g-pp / mmol Ti) 15,100 17,800 14,900 Isotacticity (%) 94.1 93.8 93.1 Bulk weight (g / ml) 0.41 0.42 0.40 Melt index 1.4 3.0 1.2

809847/1042

Table 4 (continued)

example 16 17th 18th solvent Propylene Hexane 'Kerosene Amount of solution
medium (ml) 500 g 750 750 Pressure of propylene
(kg / cm2ö) 25th 7th 7th Polymerization tem
temperature (C)
Polymerization time
(H) 60
1 70
4th 60
4th Presence of
hydrogen Yes there Yes Component (a) (1-Bu) ₃ Al (C ₈ H ₁₇ ) ₃ A1 (1-Bu) ₂ AlH Amount (mmol) 0.5 0.75 0.75 Component (b) Et ₂ AlCl C ₈ H ₁₇ AlCl ₂ Et ₂ AlCl Amount (mmol) 0.25 0.3 0.9 X / Al ratio 0.33 0.57 0.55 Electron donor (2) He- / qVcO Me NeO - ^ - CO ₀ Bu Ke - @ - CO _? Et Amount (mmol) 0.33 0.375 0.556 (3) Catalyst No. 2-10 4-1 4-2 yield
(g-pp / mmol Ti) 14,400 13,000 12,600 Isotacticity (%) 94.5 94.3 93.8 Bulk weight (g / ml) 0.40 0.40 0.40 Melt index 1.4 2.5 4.8

809847/1042

Table 4 (continued)

example 19th 1.5 0.75 20th 21st solvent Heptane , 5 ^A1C1 1.5 4-3 Propylene Propylene Amount of solution
medium (ml) 750 1.5 0.600 500 g 500 g Pressure of propylene
(kg / cm ² G) 9 0.75 95.0 30th 30th Polymerization tem
temperature (C) 85 Electron donor (2) ^Ue ~ (o) " ^C ° p. ^Me 0.41 80 70 Polymerization time
(H) 4th Amount (mmol) 3.5 0.5 1 Presence of
hydrogen Yes (3) Catalyst No. Yes Yes Component (a) (n-Bu), Al yield
(g-pp / mmol Ti) 1 £ t _o ; i ^ 0) Me ₃ Al Amount (mmol) Isotacticity (%) 0.5 0.5 Component (b) Et, Bulk weight (g / ml) EtAl (OEt) Cl EtAl (OBu) Cl Amount (mmol) Melt index 0.5 0.5 X / Al ratio 0.5 0.5 - ° - (o) - ^c00 - ^c e ^H i 7 r ^ kcc et 0.33 0.33 5-1 5-2 21,600 15,400 95.0 94.3 0.45 0.43 2.1 1.5

809847/1042

Table 4 ( example 22nd 0.5
Et ₂ AlCl ^ Continued) 2822301 8,700 21,300 solvent Propylene 0.25 23 24 94.1 96.3 Amount of solution
medium (g) 500 0.33 Propylene Propylene 0.38 0.40 Pressure of propylene
(kg / cm2G) 25th Ue- (Q) -CC 500 500 1.0 1.9 Polymerization tem
temperature ( ⁰ C) 60 0.25 25th 30th Polymerization time
(H) 1 6-1 60 70 Presence of
hydrogen there ========== 1 1 Component (a) Et, Al 10,400 Yes there Amount (mmol)
Component (b) 93.9 Et _2a Al (0C ₈ H ₁₇ ) _{0> 1} et ₃ al Amount (mmol) 0.44 0.5
EtAl (OC ₈ H ₁₇ ) Cl 0.5
Me ^ _
Me ^ ~ X / Al ratio 3.5 0.25 0.25 Electron donor (2) 0.33 0.33 Amount (mmol) ) Bu (lie) _o N- \ 0 / C °. _s Et Et- (O) -CO ₂ Et (3) Catalyst No. 0.2 0.33 6-2 6-3 yield
(g-pp / mmol Ti) Isotacticity (%) Bulk weight (g / ml) Melt index

809847/1042

- 52 Table 4 (continued)

example 25th 1 0.83 26th 27 solvent Kerosene 0.4 1-2 Kerosene Kerosene Amount of solution
medium (ml) 500 Electron donor (2) (MeCO) ₂ O 507 500 500 Pressure of propylene
(atm) 1 Amount (mmol) 98.5 1 1 Polymerization tem
temperature ( ⁰ C) 60 (3) Catalyst No. 0.35 60 60 Polymerization time
(H) 1 Specific activity (g-
pp / mmol Ti «h · atm
of propylene) 1 1 Component (a) Et ₃ al Isotacticity (%) Et ₃ al. Et ₃ al Amount (mmol) 1.5 Bulk weight (g / ml) 1.5 1.5 Component (b) (i-Bu) ₂ AlCl Et ₂ AlCl Et ₂ AlCl Amount (mmol) 1.5 1.5 X / Al ratio 0.5 CH 0.5 (/ 5VcO ₂ O fo] - ^CHO 0.83 ^^ 0.83 1-2 1-2 1,344 2,086 97.8 92.1 0.35 0.35

809847/1042

Table 4 (continued)

example 28 1.5 29 30th 954 solvent Kerosene 0.5 Kerosene ' Kerosene 91.3 Amount of solution
medium (ml) 500 CH ₃ COOH 500 500 0.37 Pressure of propylene
(atm) 1 0.83 1 1 Polymerizat! Onstem
temperature ( ⁰ C) 60 1-2 60 60 Polymerization time 1 r—— - - - 1 1 Component (a) Et ₃ al 1,879 Et ₃ al Et ₃ Al ' Amount (mmol) 1.5 88.5 1.5 1.0 Component (b) Et ₂ AlCl • 0.35 Et ₂ AlCl Et ₂ AlCl Amount (mmol) 1.5 1.0 X / Al ratio 0.5 0.5 Electron donor (2) ^Bu ~ \ O / ~ ^CG0H CH ₃ (CH ₂ J ₄ COOC ₅ H ₁₁ Amount (mmol) 1.5 0.56 (3) Catalyst No. 1-2 1-2 ———————-— · ————— ■ - · ——— · —— ■ · - ₌ - - ——— - - - - -: Specific activity (g-
pp / mmol Ti »h · atm
of propylene) 673 Isotacticity (%) 95.1 Bulk weight (g / ml) 0.35

809847/1042

Table 4 (continued)

example 31 solvent Kerosene · Amount of solvent (ml) 500 Pressure of propylene
(atm) 1 Polymerization ^{temperature (0} C) 60 Polymerisation time (h) 1 Component (a) Et ₃ al Amount (mmol) 1.0 Component (b) Et ₂ AlCl Amount (mmol) 1.0 X / Al ratio 0.5

Electron Donor (2) amount (mmol)

CH ₃ COCH ₂ COOC ₂ H ₅ 0.56

Specific activity (g-pp / mmol Ti h atm of propylene)

Isotacticity (%) bulk weight (g / ml)

1,014 97.6 0.37

Claims (6)

Dr. F. Zumstein Sr. - Dr. E. Assmann - D <-. R. Koenigsberger Dipl.-Phys. R. Holzbauer - Dipl.-Ing. F. Klingseisen - Dr. F. Zumstein jun. PATENTANWÄLTE 800O Munich 2 · Bräuhausstraße 4 · Tel.phone collective no. 225341 ■ Telegrams Zumpat - Te.ex 529979 Case F6046-K135 (Sanseki) / MS claims 1. Process for the preparation of a polymer or copolymer from an olefin having at least 3 carbon atoms, by polymerization or copolymerization of an olefin with at least 3 carbon atoms and containing 0 to 10 mol -? {l ethylene or a diolefin in the presence of one Catalyst containing an organic aluminum compound, an electron donor and a solid titanium compound, characterized in that the catalyst contains: (1) containing an organoaluminum compound composition (a) an organoaluminum compound free from halogen atoms directly bonded to the aluminum atom and represented by the following formula R ¹ ₃ A1 is represented in which R is a group from the class hydrogen atoms, alkyl groups with 1 to 12 carbon atoms, cycloalkyl groups with 5 to 12 carbon atoms, aryl groups with 6 to 12 carbon atoms, alkoxy groups with 1 to 12 carbon atoms, cycloalkoxy groups with 5 to 12 carbon atoms and aryloxy groups with 6 to 12 carbon atoms, R represents the three groups ^s itonnen the same or different, · * ". '''O 809847/1042 (b) an organoaluminum compound containing halogen atoms, bonded directly to the aluminum atom expressed by the formula ^R V ^1X m ^] in the ^R 3-nm R has the meaning given above, 2
R is a group from the class hydrogen atoms, Alkoxy groups with 1 to 12 carbon atoms and aryloxy represents groups with 6 to 12 carbon atoms, X represents a halogen atom and O <n <3, O <m <3 and 0 <n + m = 3, where the (X / Al) ratio of halogen atoms (X) to the Aluminum atom (Al) is 0 <X / Al <1. (2) an electron donor and (3) a halogen-containing solid titanium component which is the reaction product of a magnesium compound, an electron donor and a tetravalent titanium compound, the ratio of electron donor (mol) / titanium atom being not less than 0.2 and. the ratio of halogen atoms / titanium atom is not less than 4; the component (3) is further characterized in that at least 80 wt.% of the tetravalent titanium component contained in it is insoluble in boiling n-heptane, that at least 50 wt. of the tetravalent titanium compound ^{are insoluble in TiCl ^ at 80 0} C and that the surface of the ^{product insoluble in TiCl ^ at 80 0} C and the surface of component (3) as such are greater than 40 m / g. 2- The method according to claim 1, characterized in that ■ that the electron donor (2) is a compound from the Group that contains: organic carboxylic acids with 1 to 22 carbon atoms, organic carboxylic acid anhydrides with 2 to 22 carbon atoms, esters with 2 to 18 carbon atoms, organic acid halides with 2 to 15 carbon atoms Ether with 2 to 20 carbon atoms, ketones with 8098 /, 7/1045 3 to 15 carbon atoms, aldehydes with 2 to 15 carbon atoms, organic acid amides with 2 to 8 carbon atoms, amines and nitriles. 3. The method according to claim 1, characterized in that per liter of liquid phase, the amount of component (a) Is 0.001 to 100 mmoles calculated as Al atom; the Amount of component (b) is 0.001 to 100 mmoles; the amount of component (2) is 0.001 to 100 mmol; and the amount of the component (3) is 0.0001 to 1 mmol in terms of the Ti atom. 4. The method according to claim 1, characterized in that that the olefin is an α-olefin having 3 to 16 carbon atoms used. 5. Catalyst for the polymerization or copolymerization of an olefin having at least 3 carbon atoms and containing 0 to 10 mol% ethylene or a diolefin, wherein the catalyst contains: (1) an organoaluminum compound composition containing: (a) an organoaluminum compound that is free of halogen atoms bonded directly to the aluminum atom are given by the following formula R ¹ ₃ A1 in which R _{1 is} a group from the class hydrogen atoms, alkyl groups with 1 to 12 carbon atoms, cycloalkyl groups with 5 to 12 carbon atoms, aryl groups with 6 to 12 carbon atoms, alkoxy groups with 1 to 12 carbon atoms, cycloalkoxy groups with 5 to 12 carbon atoms and aryloxy groups with 6 to 12 carbon atoms, where the three R groups can be the same or different, means 8 0 9 i: · '■ ν / 1 Q u 2 (b) an organoaluminum compound containing halogen atoms, which are directly bonded to the aluminum atom by the formula ^R V ^1X m ^R2 3-nm in the R has the meaning given above, 2
R is a group from the class hydrogen atoms, AIk- oxy groups with 1 to 12 carbon atoms and aryloxy groups having 6 to 12 carbon atoms, X is a halogen atom and O <n Ο »O <m <3 and O <n + m = 3, where the ratio (X / Al) of halogen atoms (X) to that Aluminum atom (Al) O (, X / Äl <C 1, (2) an electron donor and (3) a halogen-containing solid titanium component which is the reaction product of a magnesium compound, an electron donor and a tetravalent titanium compound, the ratio of electron donor (mol) / titanium atom being not less than 0.2 and the ratio of halogen atoms / titanium atom not being less than 4 lies, and the component (3) is further characterized in that at least 80% wt., are the tetravalent titanium compound which is contained in it insoluble in boiling n-heptane, at least 50% Gev. the tetravalent titanium compound in TiCl ^ at 80 ⁰ C are insoluble, and that the surface of the ^{product insoluble in TiCl ^ at 80 0} C and the surface of component (3) as such are greater than 40 m / g. 6. Catalyst according to claim 5, characterized in that the electron donor (2) is a compound of the Group containing: organic carboxylic acids with 1 to 22 carbon atoms, organic carboxylic acid anhydrides with 2 to 22 carbon atoms, esters with 2 to 18 carbon atoms, organic acid halides with 2 to 15 carbon atoms, ethers with 2 to 20 carbon atoms, ketones with 3 to 809 ^ 47/1042 15 carbon atoms, aldehydes with 2 to 15 carbon atoms, organic acid amides with 2 to 8 carbon atoms, Amines and nitriles. 8098 /. 7 / 1CU?