CS196291B2 - Process for preparing catalytic component for the polymerisation of alpha-olefines - Google Patents

Abstract

A catalyst component for alpha-olefin polymsn. is prepd. by adding (A) oxygen and the reactn. prod. of TiCl4 and an org. ether, to (B) TiCl3 opt. mixed with a metal halide, and then grinding the mixt. Gives high yields (e.g. is approx. 98%) of crystalline polymers. Pref. the org. ether is dialkyl ether, an alkyl allyl ether, dioxan, or is derived from an alkylene glycol or a polymer thereof and component (B) is a solid cpd. of formula Ti3AlCl12.

Description

SUMMARY OF THE INVENTION The present invention provides a process for the production of a specific catalyst component for the polymerization of .alpha.-olefins in high yields.

It is known that catalysts produced by pulverizing pure titanium tetrachloride into powder can be used to polymerize α-olefins having at least 3 carbon atoms, such as propylene. These components may be obtained by reducing titanium tetrachloride with hydrogen or titanium metal, or by grinding solid chloride to a powder having a composition substantially corresponding to the formula Ti 3 AlCl 12 obtained by reducing titanium tetrachloride with metallic aluminum, or pulverizing a mixture of pure titanium tetrachloride or solid chloride of corresponding substantially to the formula Ti 3 AlCl 12 with an organic ether and / or other known components, such as electron donating compounds. .

The crystalline yield in the preparation of an α-plephene polymer, for example polypropylene, is improved. form of the high-molecular-weight polymer, there is also a simultaneous improvement, the yield of the overall product as well as an improvement in its quality. In the polymerization of α-olefins, the yield of the crystalline polymer is usually more affected by a change in the properties of the catalyst component than by a correspondingly significant change in the polymerization conditions or a change in the polymerization process. However, the yield is to some extent influenced by the choice of polymerization method or polymerization conditions. Improving the properties of the catalyst component is therefore an important issue not only for catalyst manufacturers but also for polypropylene manufacturers.

A process for preparing a catalyst component for polymerizing N-olefins is known which comprises obtaining a reaction product to titanium tetrachloride with an organic ether, adding the product to titanium tetrachloride or a mixture of titanium tetrachloride with a metal halide; and finally pulverizing. Although this improves the properties of the resulting reaction product, it is not entirely satisfactory. It would therefore be desirable to have a new catalyst that would further improve product quality.

It is therefore an object of the present invention to provide a catalyst component used for the polymerization of olefins which allows the production of crystalline polymers in high yields.

This object of the invention, as well as others as set forth below, has been achieved by providing a process for the polymerization of α-olefins using a polymerization catalyst comprising a catalyst component obtained by adding oxygen and a titanium tetrachloride reaction product. with an organic ether of titanium tetrachloride or a mixture of titanium tetrachloride with a metal halide (hereinafter referred to as titanium tetrachloride mixture) and subsequent comminution of the catalyst component into a powder, when used as a catalyst, surprisingly, the proportion of crystalline formed; % of the polymer produced from the overall produced polymer as compared to prior art processes using conventional catalyst components. .

Accordingly, the present invention provides a process for the preparation of a catalyst component for the polymerization of .alpha.-olefins, characterized in that 0.1 to 5 mole% of oxygen, based on the number of moles, is added to the titanium tetrachloride or titanium tetrachloride-aluminum chloride mixture. titanium tetrachloride or moles. mixtures of aluminum chloride and 0.1 to 30% by weight, based on the amount of titanium tetrachloride or a mixture of titanium tetrachloride with aluminum chloride, of the reaction product titanium tetrachloride with an organic ether having at least one ether group in the molecule, such as dialkyl ethers, for example diethyl ether, n-propyl ether, isobutyl ester, methylbutyl ether and the like, alkyl aryl ethers, such as anisole, " diaryl ethers such as diphenyl ether and the like, dioxanes such as 1'-dioxane, 2-methyl-13-dioxane and the like, wherein the amount of titanium tetrachloride in the reaction product with the organic ether is greater than 0 but less than · 100th weight ° / o, based on; iai ^{^^^!} Community - '· organic ether, the mixture obtained - "is tó®Ř · PO"' for .'nanejvýš "100th they threw the flick-epThis-y it is also from -20 DEG C. to -80 DEG C. in an inert gas atmosphere, if it is ground, if oxygen is added, the addition of oxygen is preferred. Titanium dioxide - according to the invention - compounds compounds,. · Suitable reducing agents are "hydrogen," metallic titanium, "metallic aluminum, metal hydrides" such as "for example sodium hydride," magnesium "hydride" or silicon hydrides (saline) and organometallic compounds, such as organic aluminum compounds comprising triethyl aluminum and dialkylaluminium halogen as titanium tetrachloride mixture; is a particularly preferred reaction product of a composition substantially corresponding to the formula ThAlCln, which obtains a "reaction" of about 3 moles of titanium tetrachloride. with about 1 mole of metallic aluminum.

Suitable organic "ethers" for use in the process of the invention are organic ethers having at least one ether group per molecule. Quantitative differences in the resulting product are due to changes in the type of ether used. Best results are obtained when lower dialkyl ethers, alkylaryl ethers or organic ethers obtained from alkylene glycol or its polymer are used. · “‘ I ·

The reaction product of the titanium tetrachloride and the organic ether of the invention is obtained. by reacting the titanium tetrachloride and the organic ether at temperatures ranging from the temperature at which the ether is in the liquid state to its boiling point. It is preferred that the titanium tetrachloride to be used in the process of the invention is sufficiently pure. It is also preferred that gaseous gas is used in the process of the invention. high purity oxygen. Oxygen and said reaction product may be added at any time before, during or after milling of the titanium tetrachloride mixture, if the mixture of titanium tetrachloride, oxygen and said reaction product has reacted sufficiently and mix evenly.

Suitable comminution devices for use in the grinding process of the present invention are conventional comminution devices commonly used for comminuting to fine powder such as ball mill, vibratory mill, air mill, tower type crusher, orbital mill, impact mill. crusher, etc. The length of time required for pulverization can be determined by conventional methods. It will depend on the type of comminution equipment used and the "comminution" of the comminuted material. The milling process is preferably carried out in an inert gas atmosphere at a temperature in the range of -20 to -80 ° C, preferably from 0 to 60 ° C. Working in an inert gas atmosphere is, of course, not necessary when grinding is carried out during the addition of oxygen.

The molar oxygen concentration should be in the range of · 1.5 to ‘mol 5 mol. % Relative to the number of moles of titanium tetrachloride. If the amount of the oxygen exceeds 5%, it will decrease. · The catalytic activity is abruptly reduced and the yield of the "crystalline" polymer is reduced. If the amount of oxygen falls below 0.1 · mol. %, 'mute' addition of '' oxygen 'no' noticeable effect / ·, '’'

The amount of said reaction products, based on the titanium tetrachloride mixture, should be in the range of 0.1 to 30% by weight. %, Preferably 1 to 15 wt. . In the reaction product, titanium tetrachloride should be present in an amount greater than ‘0% by weight, but less than 100% by weight. Preferably in the range of 1 to 70 wt. %, "Based on" "amount of ether organic ether.

The catalyst component of the present invention, consisting of a titanium compound, is together with an organic aluminum compound of a "catalyst" known as a Ziegler-type catalyst component. It can be used both with the aluminum compound and optionally with other known catalytic components, such as electron donating compounds. In all of these forms it is very effective for the polymerization of b-obefins. ·> ·

The invention is illustrated in more detail by the following specific examples, which are not to be construed as limiting the scope thereof.

1962'9 1

Example 1 ^?

200 g of a titanium tetrachloride composition having a composition substantially corresponding to the formula TisAICl is introduced into an internal mill vibration mill. 1 liter. There is an atmosphere of gaseous argon in the mill and the mill contains 0.8 liters of steel grinding balls. 12 mm in diameter. Titanium tetrachloride mixture. se. it is ground at - 35 ° C for 30 hours in an argon atmosphere. The product is then added to the mill content by reacting 10 g of diethyl ether with 2 g of titanium tetrachloride and then grinding is continued for a further 5 hours at 35 ° C. Then 1 mol. % of gaseous oxygen, based on the number of moles of titanium tetrachloride, and further milled at 35 ° C for an additional · 5 hours. The catalyst component is obtained.

A 1.5 liter stainless steel autoclave was charged with argon and charged with 0.5 g of the catalyst component obtained, 0.75 g of diethylainlumine-chloro chloride and -500 ml of heptane. The autoclave is then heated to 70 ° C. Celsius and · add 200 ml hydrogen · and veneer. Propylene is polymerized at 70 ° C for 2 hours at a partial pressure of 0.6 MPa.

The polymerization is interrupted by adding butanol to the autoclave, then shaking the autoclave to decompose the catalyst and filter.

, Yippee. The solid reactants are washed with a mixture of isopropanol and methanol and dried under reduced pressure to give a solid polymer; The amount of polymer obtained is indicated in the attached tables as · (B).

Then, the obtained 'solid polymer' is extracted for 6 hours with boiling heptane to give a heptane insoluble polymer. The amount of polymer · insoluble · in heptane in the attached tables 'marked with' (C). ,

The amount of polymer remaining in the solvent is indicated as (A). Thus, the yield of the isotactic polymer (D) can be calculated according to the formula '' D = C / (A -} - B) X 100. ·

The polymerization activity (E) of the catalyst is. it is possible to calculate the amount of catalyst according to the formula 'E = A-J-B'.

The 'yield' of the Atletic polymer can be calculated according to the formula

100 — D 'The results are shown in' Table I. '

Example · 2 ···; ''

The procedure is the same as in Example 1, but with Γ mol. % Oxygen, based on the number of moles of titanium tetrachloride, is added before the initial grinding of the titanium tetrachloride mixture. Then. ml. continues for 35 hours. A reaction product of 8 g of diethyl ether with 2 g of titanium tetrachloride is then added and the milling is continued for a further 5 hours to give a catalytic portion ^; ka. The results are shown in Table I.

Example 3

The procedure is as in Example 1, except that the reaction product of 18 g of diethyl ether with 3 g of titanium tetrachloride is added prior to grinding a titanium tetrachloride composition having a composition substantially corresponding to the formula Ti3AlClCl.

The grinding is carried out for 10 hours, then, with. 1 mol. % of the oxygen, based on the number of moles of titanium tetrachloride, and then the grinding is continued for a further 30 hours to obtain a melt. catalytic component. The results are shown in Table I.

Too lla d4 '·' · '. The procedure is as in Example 1, with only 1 · mol. -o / o oxygen, based on the number of moles of titanium tetrachloride, is added prior to grinding the titanium tetrachloride mixture (composition practically corresponding to the formula TiiAlCl2). Grinding is carried out for 20 hours. The reaction product is then treated with 16 g of diethyl ether of sago titanium tetrachloride and milling is continued for a further 20 hours to give a catalyst component. The results are shown in Table 1.

Example 1 a d 5 '

The procedure is as in Example 1, except that the reaction product is 6 g of diethyl ether with 3 g of titanium tetrachloride and 1 mol. % of oxygen, based on the number of moles of titanium tetrachloride, is added prior to grinding the titanium tetrachloride mixture (having a composition practically corresponding to the Ti5AlCl2 formula. Grinding takes place for 40 hours to give a catalyst component.

Example 1 a d. 6. . .

, 4. ·

The procedure is as in Example 1, except that s, e-1 mol. %. of oxygen, based on the number of moles of titanium tetrachloride, is added before the grinding of the titanium tetrachloride mixture (having a composition practically corresponding to the formula Ti3 Al1Cl2). Mlett runs for 20 hours. ' A reaction product of 12 g of diethyl glycol dimethyl ether with 2 grams of titanium tetrachloride is then added and the grinding is continued for a further 20 hours to give the catalyst component. ’

Example 1 a d 7,.

The procedure is as in Example 1, except that the reaction product is added to 10 g of anisole with 2 g of titanium tetrachloride prior to grinding the titanium tetrachloride mixture (having a composition substantially corresponding to the formula TiCl 3 Al 12). - runs for 35 hours; Then adding 1 mol. % oxygen, based on the number · moles of chloride

The titanium dioxide was milled and the milling was continued for a further 5 hours to give a catalyst component. The results are shown in Table 1.

Example 8

The procedure was as in Example 1 except that 0.15 mol was added. % of gaseous oxygen, based on the number of moles of titanium tetrachloride.

Example 9

The procedure was as in Example 1, except that 5 mol. % of gaseous oxygen, based on the number of moles of titanium tetrachloride. The results are shown in Table 1.

Example 10

The procedure is as in Example 1, except that the titanium tetrachloride mixture (composition of which corresponds practically to the formula Т13; 5А1С113.5) is used for at least 10 hours. The reaction product of 16 g of diethyl ether with 2 g of titanium tetrachloride is then added and the milling is continued for a further 25 hours. 1 mol. % of gaseous oxygen, based on the number of moles of titanium tetrachloride, and the grinding is continued. The reaction time was 5 hours to give the catalyst component. The results are shown in Table 1.

Example 11

The procedure was as in Example 1, with only 1 mol. % of gaseous oxygen, based on the number of moles of titanium tetrachloride, is added before the grinding of the titanium tetrachloride mixture (having a composition corresponding essentially to T1z, 5AlClO, 5). Milling takes place for 30 hours. The reaction product of 18 g of diethyl ether with 2 g of titanium tetrachloride is then added and the milling is continued for a further 10 hours to give a catalyst component. The results are shown in Table 1.

Comparative example 1. ,

The procedure is as in Example 1, except that the titanium tetrachloride mixture (having a composition substantially corresponding to the formula Ti 3 AlCl 2) is subjected to grinding for 35 hours. Then, instead of oxygen and prod, the reaction of diethyl ether with; 5 g of diethyl ether alone are added to the titanium tetrachloride. The milling is then continued for a further 5 hours to give a catalyst component. The results are shown in the table

II.

Comparative Example 2

The procedure is the same as in Comparative Example 1, only 20 g of diethyl ether is added before grinding the titanium tetrachloride mixture (having a composition corresponding practically to the formula).

TI3AICI12). Then the grinding is continued for a further period.

40 hours to obtain a catalyst component. The results are shown in Table II.

Comparative example

The procedure is as in Example 1, except that the titanium tetrachloride mixture (having a composition substantially corresponding to the formula Ti 3 AlCl 2) is subjected to grinding for 20 hours. Thereafter, a mixture of oxygen and the reaction product of diethyl ether with titanium tetrachloride was added separately but simultaneously with 2 g of titanium tetrachloride and 8 g of diethyl ether. The milling is continued for a further 20 hours to give the catalyst component. The results are shown in Table II.

Comparative Example 4

The procedure is the same as in Comparative Example 3, only. the titanium tetrachloride mixture (having a composition substantially corresponding to the formula Ti 3 AlCl 2) is subjected to grinding for 30 hours. 16 g of diethyl ether and 4 g of carbon tetrachloride are then added, individually but simultaneously, and the grinding is continued for a further 10 hours to give a catalytic component. The results are shown in Table II. - ·

Comparative Example 5.

The procedure is as in Example 1, except that the titanium tetrachloride mixture (having a composition substantially corresponding to the formula Ti 3 AlCl 2) is subjected to grinding for 35 hours. Thereafter, instead of oxygen and the reaction product of diethyl ether with titanium tetrachloride, 1 mol. % of oxygen alone based on moles of titanium tetrachloride. The milling is then continued for a further 5 hours to give the catalytic component. The results are shown in Table II.

Comparative example 6

The same procedure as in Example 1 was followed, except that the titanium tetrachloride mixture (having a composition substantially corresponding to the formula Ti 3 AlCl 2) was subjected to grinding for 35 hours. Then, instead of oxygen and the reaction product of diethyl ether with titanium tetrachloride, a reaction product of 10 g of diethyl ether with 2.1 g of titanium tetrachloride is added. The milling is then continued for a further 5 hours to give the catalyst component. The results are shown in the table

II. '‘

Comparative example 7

The procedure is the same as in Comparative Example 6, except that a reaction product of 10 g diethyl ether is added before grinding the titanium tetrachloride (having a composition substantially corresponding to the formula Ti 3 AlCl 2). 2.1 g of titanium tetrachloride. Grinding is continued for 40 hours to give a catalyst component. The results obtained are shown in Table II ...

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Comparative example 8

The procedure is the same as in Comparative Example 1, except that 0.05 mol. % oxygen, based on the number of moles of titanium tetrachloride. The results obtained are shown in Table II.

Comparative example 9

The procedure was the same as in Comparative Example 1, except that 6 mol. percent oxygen gas based on the number of moles of titanium tetrachloride. The results obtained are shown in Table II.

The results of Tables I and II show that when polymerization is carried out using a catalyst comprising a catalyst component prepared by the process of the invention, a significantly higher yield of crystalline polymer is achieved than when polymerization is achieved. is carried out using a catalyst comprising a catalyst component prepared by a process not included within the scope of the present invention.

It will be apparent to those skilled in the art from the detailed description of the method of the invention that many changes and modifications can be made to the method of the invention without departing from the scope of the invention as previously described.

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Table I _; . . ./. ·?>

Results of experiments' _·: Example 1 Example 2 Example 3 Example 4 Example Example 6 Example 7 Example 8 Example 9 · Example lo Example 11

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199291

Claims (3)

Ρ Ř Ε D..M Ё Τ A process for the preparation of a catalyst component for the polymerization of α-olefins, characterized in that 0.1 to 5 mol% of oxygen, based on the number of moles of titanium chloride or the number of titanium tetrachloride, is added to the titanium tetrachloride or the titanium tetrachloride 'mixture'. moles of a mixture of titanium tetrachloride with aluminum chloride as well as 0.1 to 30% w / w - based on the amount of titanium tetrachloride or a mixture of titanium tetrachloride with aluminum chloride - the reaction product of titanium tetrachloride with an organic ether having at least one ether group per molecule; are dialkyl ethers, for example, diethyl ether, n-propyl ether, isobutyl ether, methylbutyl ether and the like, alkyl aryl ethers such as anisole, para-phenylanisole and the like, diaryl ethers such as diphenyl ether and the like. dioxanes such as 1,4-dioxane, 2-ethyl-1,4-dioxane and the like, ethylene glycol ammonium ethyl ether or diethylene glycol dimethyl ether, wherein the amount of titanium tetrachloride in the reaction product with organic ether is greater than 0 but less than 100% by weight o, based on the amount of organic ether, and _{: the} mixture obtained is milled for a maximum of 100 hours at a temperature ranging from -20 ° C to + 80 ° C under an inert gas atmosphere, unless grinding is performed during the addition of oxygen. 2. The process of claim 1, wherein the titanium tetrachloride-aluminum chloride mixture is a solid chloride having a composition substantially corresponding to the formula Ti3AlCl12. 3. The process of claim 1 wherein the addition and grinding of the oxygen and the reaction product of the titanium tetrachloride with the organic ether are carried out individually.