DE1420381A1 - Process for the production of high molecular weight polyethylenes - Google Patents

Description

H20381

FARBWERKE HOECHST AG., Formerly Master Lucius & Brüning

File number: P 14 2o 38I.T - Fw I4o7 b Date: December 3, 1968

Process for the production of high molecular weight polyethylenes (2nd additional application to patent no

The subject of patent no. 1 oil 9 ^ 66 is a method for Production of high molecular weight polyethylenes by polymerizing ethylene with catalyst mixtures of organoaluminum Compounds and compounds of the metals titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, thorium and uranium, which is characterized in that one from the catalyst mixtures separates heavy metal compounds formed by reduction from the other reaction products and the separated compounds - if necessary after further cleaning - in any combination with organometallic compounds of aluminum for the polymerization of ethylene is used.

It has now been found that titanium (IV) compounds, which are advantageous as heavy metal components in the production of contacts contain organic residues, have them used.

Particularly suitable as such are titanium dichloride diacetate, titanium dichloride diacetylacetonate, Titanium dichloride dibutylate, titanium monochloride triethylate, ortho-titanic acid tetraethyl ester, ortho-titanic acid tetra-butyl ester or titanium tetra (ß-chloroethyl ester). The organic titanium (IV) compounds used according to the invention are dissolved or suspended in inert organic solvents

ound reduced with organoaluminum compounds, preferably ethyl-C ₀ , aluminum sesquichloride, to brown to black-brown, air-sensitive products, whereby it is advantageous to add the resulting solid Ti contact at room temperature by stirring about the reaction mixture aging.

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The reduced Ti component is carried by the reaction solution Separated by filtration and can optionally be further purified by washing out with an inert dispersant.

The Ti contact is activated by adding organoaluminum Compounds, preferably aluminum triethyl, ethyl aluminum sesquichloride or diethyl aluminum monochloride.

The catalysts according to the invention can be used to produce particularly good type of ethylene polymers.

Example 1:

35.5 parts by weight Titandichloriddiacetat be in 4oo parts by volume of a predominantly saturated aliphatic hydrocarbon - suspended, and a mixture of "/ 3 parts by volume of ethyl aluminum sesquichloride and 5o parts by volume of the above dispersing agent during the period of 30 minutes with stirring (Kp (7βο) = 2o2 231 ^O C) The reaction mixture gradually turns dark brown. After the end of the dropping in, stirring is continued for 8 hours at room temperature and the dark brown contact formed is separated from the reaction products obtained in the dispersant in a stirring frit. The contact is then washed twice with fresh dispersant and finally Slurried with further dispersant to form a suspension, 100 parts by volume of the above-mentioned suspension contain 10 mmoles of titanium (III) compound.

With 200 parts by volume of this suspension, 7.2 parts by weight of ethylaluminum sesquichloride is polymerized in 360 parts by volume of the above-mentioned dispersing agent. After 6 hours of polymerization and suitable work-up, 600 parts by weight of polyethylene are obtained. Specific viscosity: 2, o6j tensile strength: 196 kg / cm; Elongation at break: 86o %; Bulk density: 300 g / l; Density: o.927.

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Example 2:

According to Example 1, a contact of 63Λ parts by weight of titanium dichloride diacetylacetonate and 50 parts by volume of ethylaluminum sesquichloride in 600 parts by volume of 1,2-dichloroethane is obtained. In loo parts by volume of the catalyst suspension obtained by slurrying in the method mentioned in Example 1 dispersants are 37.5 mmol contain titanium (III) compound.

40 parts by volume of this suspension and a solution of 8.6 parts by weight of ethylaluminum sesquichloride in 43o parts by volume of the above dispersant are used for the polymerization, and the rest of the procedure is as above. After 5.5 hours, 700 parts by weight of polyethylene with a specific viscosity of 2.72 and mechanical properties similar to those given in Example 1 are obtained.

Example 3:

A mixture of 32.7 parts by weight of titanium dichloride dibutylate and 50 parts by volume of the dispersant mentioned in Example 1 to form a mixture of 30 parts by volume of ethylaluminum sesquichloride and 300 parts by volume of the same dispersant added, gives a brown precipitate, which is slurried in the dispersant after the usual cleaning. 250 parts by volume of the suspension contain 40 mmol of titanium (III) compound. The polymerization is carried out as in Example 1, using 100 parts by volume of contact suspension and 11.8 parts by weight of Sthylaluminiuir.sesquichlorid in 59o Parts by volume of the quoted dispersion medium. After six hours The duration of the experiment is 850 parts by weight of a polyethylene with a bulk density of 42o g / l, the mechanical test values of which are those in Example 1 given are very similar. Density: o.937

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Example 4:

4o, 4 parts by weight of titanium monochloride triethylate are with 100 parts by volume of the dispersant mentioned in Example 1 diluted and in a mixture of 35 parts by volume of ethyl aluminum sesquichloride and 500 parts by volume of the cited dispersant dripped in at room temperature for an hour. After the usual work-up, a finely divided brown contact is obtained, the suspension of which is in that mentioned in Example 1 Dispersant 17.6 mmol of titanium (III) compound in 100 parts by volume contains.

For the polymerization, 115 parts by volume of the contact suspension 13 * 4 parts by weight of ethylaluminum sesquichloride in 67o parts by volume of the dispersant are used and the procedure is as usual. After 6 hours of polymerization, 35o g of polyethylene are obtained with a specific viscosity of 3.86, a tensile strength of 285 kg / cm, an elongation at break of 635 % and a density of 0.939.

Example 5:

52.8 parts by weight of ortho-titanic acid tetraethyl ester (titanium tetraethylate) are diluted with> o parts by volume of the dispersing agent mentioned in Example 1 and this mixture is converted into a mixture of 57 parts by volume of ethylaluminum sesquichloride and 400 parts by volume of the above-mentioned dispersing agent over a period of 40 minutes with a nitrogen blanket and stirring dripped in. After several hours of stirring, the work is carried out as usual. The contact suspension contains, in 100 parts by volume, 16.8 mmol of titanium (III) compound. Polymerization is carried out with 150 parts by volume of contact suspension and 9 * 8 parts by weight of diethylaluminum monochloride in 480 parts by volume of the above-mentioned dispersant in the usual manner. After 6 hours 53o parts by weight of polyethylene are obtained. Specific viscosity: 6.3S-, tensile strength: 255 kg / cm ² ; Elongation at break: 791 ? ₃ ; Density: 0.938.

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Example β:

In the same way, a catalyst is made from 6o.7 parts by weight of ortho-titanic acid tetrabutyl ester (titanium tetrabutylate) and 45 parts by volume of ethyl aluminum sesquichloride in 400 parts by volume of the dispersant mentioned in Example 1. loo volurr. parts of the contact suspension contain 22 mmol of titanium (III) compound.

Ho parts by volume of this suspension are used for the polymerization with a solution of 8 parts by weight of ethylaluminum sesquichloride in 400 parts by volume of the above-mentioned dispersant, which is allowed to flow in continuously as usual. After 5 1/2 hours the yield of polyethylene is 48o parts by weight. The mechanical properties of the product are similar to those described in Example 1.

Instead of titanium tetrabutylate, you can also use titanium tetrachloride (ßchlorethylester), made by reacting titanium tetrachloride with ethylene oxide. A titanium catalyst is obtained that in combination with ethyl aluminum sesquichloride also converted ethylene into a high polymer.

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Claims (1)

- 6 - Pw I4o7 b Patent claims: 1. Process for the production of high molecular weight polyethylenes according to Patent No. 1 ol9 Wü> 6, characterized in that compounds containing organic residues are used to produce the solid catalyst component. 2. The method according to claim 1, characterized in that as titanium (IV) compounds containing organic residues titanium dichloride diacetate, titanium dichloride diacetylacetonate, "titanium dichloride dibutylate, Titanium monochloride triethylate, ortho-titanic acid tetraethyl ester, ortho-titanic acid tetrabutyl ester or titanium tetra- (S-chloroethyl ester) to be used. 3 · The method according to claim 1, characterized in that as a reducing agent for the organic radicals containing Ti tan- (IV) compounds and as an activating component for the solid reduction products ethyl aluminum sesquichloride is used. New documents [Art. ι § , Abs. 2 Hr. 1 s _c - 3; _Λ h ^. _{y ia} . _v . _4th 9. 1967). 909839/1308