DE3022544A1 - CATALYST FOR THE OLEFIN POLYMERIZATION AND METHOD FOR THE PRODUCTION THEREOF - Google Patents

Description

PATENTANWÄLTE Dipl.-lng. P. WIRTH Dr. V. SCH MIE D-KOWARZIK

Dipl.-Ing. G. DANNENBERG Dr. P. WEINHOLD Dr. D. QUDEL

\ 335024 SiEGFRIEDSTBASSE 8

i TELEPHONE C089)

I 335025 8000 MONKS 40

I SK / SK

j RC-1461-M28

Dart Industries Inc.

P.O. Box 3167 Terminal Annex

Los Angeles ca.90051 / USA

Catalyst for olefin polymerization and Process for its manufacture

030062/0756

The production of aluminum-reduced titanium trichloride catalysts is known and such catalysts are described in US Pat widely used in the manufacture of polyolefins such as polyethylene and polypropylene. The production of these catalysts and their use in polymerization reactions is described, inter alia, in US Pat. No. 3,121,063, 3,475,394, 4,154,702, 3,642,746 and 3,647,772 and in GB PS 1,310,547.

It is also known that the behavior of these catalysts is improved by treatment with electron donor substances can be. Details of such a treatment and examples of suitable electron donors are given, inter alia, in U.S. Patents 3,186,977, 4,110,248, 4,111,836, 4,115,319, 4,126,576, 4,127,504, 4,127,505, 4,142,991 and in GBP 1,310,547 described.

The treatment of aluminum-reduced titanium trichloride catalysts with electron donors containing an OR radical, e.g. with different ethers, but can lead to the formation of by-products that affect the catalysts. For example, they can create unwanted prints in the shipping containers. In other cases, the educated By-products are toxic, introducing a hazardous element that should clearly be avoided.

According to the invention it has been found that the presence of undesirable and potentially dangerous by-products can be eliminated by heat treating the modified, aluminum-reduced titanium trichloride catalysts and then these substances are removed by volatilization or extraction with a suitable solvent. the Heat treatment is most expedient after modification of the catalyst by the special, chosen electron donor, however, it can also be carried out while the modification or activation treatment is carried out will.

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—Γ-

In general, the modified catalyst is placed in a suitable container and the heat treatment is carried out at sufficient temperature and time to complete the reaction. In some cases, this requires removal a gas formed during the modification.

The method used for conducting the heat treatment temperature may be from about 40 to about 110, preferably ° C for about! 0 80 to about 100 ⁰ C and in particular about 90 ⁰ C hot vary.

The duration of treatment can also vary and of course it depends on the particular temperature of the heat treatment. So the treatment time can be between about 10 to about 300 minutes, preferably about 60 to 120 minutes, this usually about 80 minutes take.

The heat treatment leading to the elimination of the by-products can be above or below the ambient pressure take place at about 0.001 to about 2 at, but is preferably carried out at atmospheric pressure »

The heat treatment of the modified, aluminum-reduced titanium trichloride catalyst according to the present invention leads to the formation of a new and advantageous catalyst preparation. If the aluminum-reduced Titantrichloridgrundmaterial treated an electron donor group -OR containing a small amount and is activated by grinding at a temperature of about -10 ⁰ C to about 40 ° C, the following reaction occurs: 3 TiCl _3, AlCl ₃ + x ROR ¹
-Ml-X) (3TiCl ₃ , AlCl ₃ ) XOTiCl ₃ , AlCl ₃ , ROR ') (D.

When heating the above product, namely the aluminum-reduced titanium trichloride modified with the electron donor, according to the method according to the invention, the following reaction occurs:

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(lx) (3TiCl ₃ , AICl ₃ ) XOTiCl _3x AlCl ₃ , ROR ¹ ) - · > (1-X) OTiCl ₃ , AlCl ₃ JxOTiCl ₃ , AlCl ₂ (OR ¹ )) + RCl. (II)

In the above equations, χ is a positive number of 1 or less than 1.

The product obtained after completion of the above reaction is a new catalytic agent of a heretofore unknown composition. This catalyst has a high catalyst efficiency (CE = catalyst efficiency), expressed as the weight of the polymer formed in g per g of the modified TiCl ₅ catalyst used. The polymer formed with the new and improved catalyst according to the invention has an improved isotacticity, ie a higher content of material which is insoluble in heptane (HI = heptane insoluble).

As mentioned above, treating aluminum-reduced 2Q titanium trichloride catalysts is to improve their effectiveness known, various related publications were mentioned.

The starting catalyst used according to the invention can be aluminum-reduced activated titanium trichloride (hereinafter also as AA-TiCl-) or aluminum-reduced, non-activated titanium trichloride (hereinafter also called A-TiCl, designated). Optionally, additional aluminum chloride, titanium tetrachloride or titanium trichloride can be added will.

As a modifier in the activation of the catalyst Particular electron donor compounds used in accordance with the present invention are as follows

"Formula:

12th

R ¹ -XR ^

in which X stands for O, S, Se or Te, and

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12th
R and R, which can be the same or different, alkyl, cycloalkyl, aryl or substituted derivatives thereof or a group of the formula:

- C - R ²

ir

where X is 0, Se, Se or Te and R ^{3 is} alkyl, cycloalkyl, aryl or a substituted derivative thereof.

The only restriction with respect to R ¹ and R ² is that the compounds R Cl and / or R Cl are easily removable from the reaction product or their presence is negligible.

Examples of the modifier R ¹ -XR ² (when X is 0) are organic oxygen-containing compounds such as aliphatic ethers, aromatic ethers, aliphatic carboxylic acid esters and anhydrides, aromatic carboxylic acid esters and anhydrides, and unsaturated carboxylic acid esters and

-anhydrides. Specific examples of such compounds are: (C ₂ H ₅ ) ₂ o, C ₆ H ₅ .O.CH ₃ , C ₆ H ₅ CH ₂ .0.CH ₃ CH ₃ -CH (OC ₂ H ₅ ) ₂ , (CH ₃ ) ₂ .C (OC ₂ H ₅ J ₂ , CH (OC ₂ H ₅ ) 3 CH ₃ CCOC ₂ H ₅ C ₆ H _5. CO ". OC ₂ H ₅ , C ₂ H ₅ O. CO. OC ₂ H ₅

C ₂ H ₅ CCO-OC ₂ H ₅ and (CH ₃ CO) ₂ O.

1 ?

Special cases are compounds in which R and R are part of a heterocyclic system, such as in tetrahydrofuran or ^ butyrolactone.

In the above examples, hydrogen can be replaced by one or more of the following groups: -Cl, -Br, -CH ₂ Cl, -CC ₂ H ₅ , -CH ₂ .OCH 1, -OCOCH, and -COCH ₃ .

³⁵ As also mentioned above, there are certain known problems with such modified catalysts, e.g. insufficient shelf life and potential hazards from the formation of volatile or toxic substances

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from the following reaction:
R.

O + AlCl ₃ > R - OA1C1 ₂ + RC1 (III)

published in the text "Friedel-Crafts and Related Reactions" by G.A. Olah at Interscience Publishers, New York, Page 572 and 585 »was discussed.

ίο Surprisingly, it was found that the above problems Without loss of catalytic activity and effectiveness it can be overcome if one uses an electron donor modified, - aluminum-reduced titanium trichloride catalyst subject to heat treatment at sufficient temperature and duration to eliminate the To effect reaction III formed RCl.

The A-TiCl ^ or AA-TiCl ^ is in an inert atmosphere mixed with the electron donor compound and heated the mixture to react. The heating according to the invention can be used at the same time as grinding in a ball mill for the purpose of activation or further activation of the Catalyst take place, or the mixture can be heated after activation.

The volatile gas products can be removed by evaporation at elevated or reduced pressure.

Other products can be removed by solvent extraction and subsequent filtration or - if they are harmless - Be left in the catalyst mixture.

Other treatments can be performed after the heat treatment. So can be used to adjust the size of the catalyst particles be ground at a low temperature. The subsequent stages can also include the addition of further modifiers, in particular to further improve the effectiveness and control of the particle size.

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The following examples illustrate the present invention.

example 1

7.6 kg of crystalline titanium trichloride compound of the approximate formula TiCl ₅ XO, 33 AlCl ₃ ^ AA-TiCl, from Pureehern Co.) were placed in a vibrator ball mill with an internal volume of 40 1 under a nitrogen atmosphere, the 144 kg of steel balls of 2, 5 cm in diameter. Within an hour of anisole in an amount of 12 wt -.%, Based on the amount of TiCl-OCO, 33 AlCl- ,, dispersed on the catalyst, wherein the mixture rpm for 4 hours at a speed of 1500 at 10 ⁰ C was milled .

A sample of the catalyst was tested in a liquid propylene polymerization test as follows:

0.052 g of the modified TiCl ^ catalyst and 1.2 ml of a 0.66M DEAC solution in n-heptane (DEAC / Ti (mol) = 3.0) were placed in a 1-1 stainless steel autoclave equipped with a stirrer. Then 0.027 moles of Hp were introduced followed by 250 g of liquid propylene. The polymerization took place for 2 hours at 75 ° C., after which the unreacted propylene was deaerated. The polymer thus obtained v. ^r og 133 g and the catalyst productivity was 2557 g polypropylene / g catalyst.

A portion of the polymer was in a Soxhlet extractor for 16 hours extracted with boiling n-heptane and dried the fraction insoluble in this. The weight percentage of the polymer insoluble in n-heptane was 93.5.

Example 2

An anisole-modified titanium trichloride was produced with the amounts and conditions mentioned in Example 1, grinding at 40.degree. A sample of the? The jointly pulverized mixture prepared in this way gave a productivity of 2700 g of polypropylene / g of catalyst and a proportion of 95.6 % insoluble in n-heptane.

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Example 3_

An anisole-modified titanium trichloride was prepared according to Example 1, but the amount of anisole used was 9% by weight, based on the amount of TiCl ^ xO.33 AlCl ₃ . In the test according to Example 1, a sample of the mixture thus prepared and pulverized together showed a productivity of 2500 g of polypropylene / g of catalyst and a proportion of 93.3% insoluble in heptane.

Example 4

A sample of the anisole-modified titanium trichloride obtained in Example 2 was extracted using 10 ml of n-hex _an per g of catalyst and then dried under nitrogen. A sample of the catalyst treated in this way showed the following results in the polymerization test according to Example 1:

Catalyst efficiency

g polypropylene % in n-heptane per g catalyst insoluble materials

before solvent extraction 2692 95 »7

after "2846 96.0

Example 5

Heat treatment of the modified catalyst 100 g of an anisole-modified one prepared according to Example 2 Titanium trichloride catalyst was placed in a sealed glass tube, heated to 85 ° C. and this was released Gas monitors. The evolution of gas ceased after 4 hours of heating. A sample of the heat treated catalyst was tested under the polymerization conditions of Example 1 and showed the following results:

Catalyst efficiency

g of polypropylene % insoluble in n-heptane per g of catalyst . materials

before heating 2385 95.5

according to the "2385 95.2

Samples of the modified catalyst were heat-treated in a similar manner at 90 and 110 ^° C., the evolution of gas having ended at these temperatures after 3 and 0.5 hours, respectively

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- / I / I "^ Ta 3

Those given in the definition of the radicals R, R and R Remainders have the following meaning, for example:

Alkyl: in particular C ₁ -C 6 alkyl, such as methyl, ethyl, propyl,> isopropyl, butyl, isobutyl, sec. "- butyl, tert-butyl, pentyl, isopentyl, hexyl or isohexyl.

Cycloalkyl: in particular a C 1 -C 6 res "b-, such as cyclopropyl, cyclopentyl, cyclohexyl, or cycloheptyl, or their derivatives substituted by methyl or ethyl groups. Aryl: in particular C ₆ -C 10 aryl, such as phenyl, tolyl, xyIyI, benzyl , Phenylethyl, phenylpropyl or naphthyl, alkenyl: in particular C ₂ -C 6 alkenyl, such as vinyl, the propenyl, butenyl, pejxfcenyl or hexenyl radicals.

The groups mentioned can contain one or more halogen atoms, such as Cl, Br, halogenated (Cl, Br) C.-C. Alkyl groups, OCOC ₁ -C ₄ alkyl groups -CH ₂ OC ₁ -C ₄ alkyl groups, OC ₁ -C ₄ alkyl groups, COC ₁ -C ₄ groups ^ can be substituted. Cyclic compounds can also be substituted with 1, 2 or 3> C ₁ -C ₄ alkyl groups, preferably methyl or ethyl groups. * _or COOC _1-4 alkyl groups

Aliphatic acid anhydrides contain in the alkyl or alkenyl group preferably 1 to 6, in particular 1 to 4, Carbon atoms;

aliphatic acetals or orthoesters contain in the alkyl group 1 to 6, especially 1 to 4, carbon atoms.

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Claims (1)

Claims 1.- Catalyst, containing or consisting of (1 ~ x) (3TiCl ₃ , AlCl,) x (3TiCl ,, AlCl ₂ (OR)), where χ is a positive number less than or equal to 1 and R stands for an organic group . 2.- catalyst according to claim 1, characterized in that R represents alkyl, cycloalkyl, aryl or a substituted derivative thereof or a group of the formula -C-R, where It ίο Χ X is 0, S, Se or Te and R is alkyl, cycloalkyl, aryl or a substituted derivative thereof. 3.- Catalyst according to claim 1, characterized in that R is phenyl. h, - Process for the preparation of a storage-stable catalyst for olefin polymerization, characterized in that an aluminum-reduced titanium trichloride catalyst is heated by treatment with a 1 2 I. Electron donor compound of the formula R -X-R, in which J 1 2 X stands for 0, S, Se or Te and R and R, which are identical or different, mean alkyl, cycloalkyl, aryl or a substituted derivative thereof or a group of the formula "^<r" ^RI in which X stands for 0 , S, Se or Te and R 'is alkyl, cycloalkyl, aryl or a substituted derivative thereof has been activated. 5.- The method according to claim 4, characterized in that the electron donor compound is an organic ether or Ester is. 6.- The method according to claim 5 »characterized in that 1 2 the electron donor is a compound of the formula R -0-R 1 2
where R and R, which are identical or different, are alkyl, cycloalkyl, aryl or a substituted derivative thereof or a group of the formula -CR ¹ , Il 030062/0 756 in which X is O, S, Se or Te and R ^{f is} alkyl, cycloalkyl, aryl or a substituted derivative thereof. 7.- The method according to claim 6, characterized in that the electron donor is anisole. 8. Method according to claims 4 to 7> characterized in that the temperature is between about 40 and about 110 ^° C and the duration of the heating is between about 10 minutes to about 12 hours. Process according to Claim 8, characterized in that the temperature is approximately 80 to approximately 100 ^° C. and the heating time is approximately 20 minutes to approximately 3 hours. 10.- The method according to claim 9, characterized; that the Temi
amounts to. the temperature 90 ⁰ C and the duration of the heating 2 hours The patent attorney: 030062/0 756