DE1096359B - Process for the production of new organotitanium compounds - Google Patents

Description

GERMAN

The present invention relates to the preparation of a new class of organotitanium compounds which a direct carbon-titanium bond and an acyloxy-titanium bond own.

It is known, aryltitanium trialkoxy compounds, which an aryl radical on a titanium atom through a direct Carbon-titanium bond containing the remaining three valences of the titanium atom through Alkoxy radicals are saturated via oxygen-titanium bonds, as catalysts for the polymerization of olefinic ones To use hydrocarbons and the like. In practice it has been found that compounds this Type are mainly useful in the polymerization of non-polar monomers. Polar monomers, such as methyl methacrylate, vinyl chloride, allyl alcohol and similar monomers of this type can be polymerize less well with the help of these catalysts.

Chemical compounds of the formula

in which M is a metal from group IVa of the periodic table, for example titanium, R is a resonance-stabilized radical, such as the cyclopentadienyl radical, which is bonded to the metal atom through a carbon atom that belongs to a five-membered ring, and in which R 'is alkoxy -, Cycloalkoxy or aryloxy radicals or halogen atoms and η denotes the number 1 or 2, can also be used as catalysts for the polymerization of olefins and, in particular, are more effective than the aryltitanium trialkoxy compounds in the polymerization of polar monomers. However, their effectiveness was still in need of improvement, and there was a desire for catalysts with even higher activity, in particular for the polymerization of polar monomers.

The invention relates to the preparation of new compounds that have a better catalytic effectiveness the polymerization of olefinically unsaturated monomers.

Method of manufacture
of new organotitanium compounds

Applicant:

National Lead Company,
New York, NY (V. St. A.)

Representative: Dr. F. Zumstein,

Dipl.-Chem. Dr. rer. nat. E. Assmann

and Dipl.-Cb.em. Dr. R. Koenigsberger, patent attorneys,

Munich 2, Bräuhausstr. 4th

Claimed priority:
V. St. v. America May 21, 1958

Daniel Francis Herman, Orange, N.J.,

and Roger Michel Weil, New York, N.Y. (V. St. A.),

have been named as inventors

carboxylic acid, the alkyl radicals of which can be substituted by halogen, mercapto or oxy groups and the reaction product is separated from the precipitated alkali or alkaline earth metal halide. It should be noted that the exact configuration of electrons in a double bond system, in particular a conjugated five-membered ring, such as the cyclopentadienyl radical usually through the structure symbol

According to the invention
my formula

are connections of the universal and as in resonance between two (or several) formulas, for example

in which R denotes an optionally substituted cyclopentadienyl or indenyl radical which is bonded to the titanium atom by means of carbon and in which X denotes a halogen atom or an alkoxy radical, R 'an alkyl, haloalkyl, mercaptoalkyl or oxyalkyl radical, χ 1 or 2, y 0, 1 or 2 and ζ 1 or 2, the sum of x _t y and ζ 4 , represented by an organotitanium halide or an organoalkoxytitanium halide, in which the organo radicals R correspond, with an alkali metal or alkaline earth metal salt of an aliphatic mono-

and the like

is viewed. Some theorists advocate a configuration according to which every carbon atom has every Time is equal to the others and all are "unsaturated" to the same extent. Apart from the exact one. In the nature of the bond involved, it is known what is meant by a "conjugated five-membered ring"

009 697/519

3 4

is, and for the sake of simplicity, this ring will therefore be the ethers of these solvents, such as, for example

in the following in the usual way, d. H. by the formula tetrahydrofuran, and other polar solvents, such as

for example dimethylformamide, acetone and dimethyl sulfoxide, called. Except for the exclusion of moisture 5 and air, no further precautions are required. The proportions used of the Reaction components can be used depending on the desired

reproduced. Likewise, by stating that the product should fluctuate somewhat. In general, the Er metal atom to which the cyclopentadiene is linked is due to "a rate of the halogen in the organotitanium halide molecule carbon atom", the possibility not being stoichiometric due to the acylate radical. To ensure that the bond to the metal is completely substituted, an excess of atoms among the S carbon atoms of the ring can be divided up over the amount of halide present. be set without running the risk of replacing the Ti-C-AIs examples of substituted cyclopentadienyl bonds in the organotitanium halide with acyl in the starting materials and process products. The reason for this is not entirely clear, in particular the alkyl-substituted cyclopentadienyl but it is assumed that this behavior with the remainder, such as methylcyclopentadienyl, is called. As radicals R 'non-ionic nature of the Ti-C bond in contrast to the following may be mentioned: methyl, ethyl and propyl (which is related to the acetic the ionic nature of the Ti-X bond, acid, propionic acid or butyric acid correspond), If the Amount of alkali metal acylate used is higher alkyl radicals that correspond to the fatty acids, such as ao lower than those required for the stoichiometric reaction with the lauric, myristic, oleic and stearic acid, the halogen of the organotitanium halide, as well as halogen-substituted derivatives of these radicals, to which so If the substitution is incomplete, and the obtained especially chloromethyl, dichloromethyl and trichloro product consists of a mixed organotitanium methyl belonging to the chloroacetic acid, dichloroacetic halide acylate of the general formula
acid and trichloroacetic acid correspond, mercaptoalkyl, 25

z. B. mercaptomethyl and mercaptoethyl (those of THo- R ^ TiXy (OOCROz
glycolic and mercaptopropionic acid), and

Oxyalkyl radicals, e.g. B. oxymethyl (which corresponds to the glycolic acid in which R, R 'and X have the meanings given above). In each of these cases the acid must have and χ a number from 1 to 2, y a number sufficiently acidic to be able to form alkali salts, since 30 1 to 2 and ζ a number from 1 to 2, where the the reaction according to an ionic mechanism between the sum of x, y and ζ is practically 4,
the alkali salts of the acylate group corresponding to a mixed organotitanium acid and the halogen ion of the organotitanium halide alkoxyhalide, z. B. Cyclopentadienyl-dibutoxytitanium seems to proceed, using an insoluble alkali metal salt monochloride, only the halogen is formed, which by precipitation replaces the equilibrium of atoms with acylate residues, the alkoxy groups in favor of the desired reaction, ie the replacement, however, not,
of the halogen ion through the acylate group. example 1

The in the method according to the invention as an

Organotitanium halides that can be used as the starting materials In a 100 ml two-necked flask, 5 g of bis corresponding to the general formula 4 ° (cyclopentadienyl / titanium dichloride, (C ₆ Hg) ₂ TiCl ₂ , 3.3 g

Sodium acetate and about 50 g tetrahydrofuran.

R _B TiX _m brings. The flask is equipped with a stirrer, reflux condenser

and devices for introducing an inert gas

in which R and X have the meanings given above (nitrogen). Then you bring the temperature

sit and η a number from 1 to 2 and m a number from 45 to the boiling point of the solvent (68 ° C) and holds

2 to 3, where at least one of the radicals X is 1 hour at this temperature. During the implementation

Is halogen atom. As examples of such compounds, the color of the reaction mixture changes from red to

be monocyclopentadienyl dibutoxytitanium monochloride, orange brown. The red crystals of the bis (cyclopene

Monocyclopentadienyltitanium triiodide, dicyclopentadienyltadienyl) titanium dichloride dissolve to the extent that

called titanium dibromide and indenyl titanium trichloride. 50 steps of the reaction, and a whiter one forms

In the process according to the invention, the second precipitate of that which is insoluble in tetrahydrofuran

The main starting material used is the alkali salt pre- sodium chloride.

preferably the sodium, potassium or lithium salt of the After cooling, the precipitate is filtered off, moreover desired acylate corresponding acid. First played with tetrahydrofuran and then with ether for various acylate groups are washed and dried beforehand. The completeness of the bypassers mentioned in the definition of the remainder R '. Salt formation can be determined by extracting and weighing the sodium from other alkali metals such as cesium chloride.

Rubidium and the like can also be used if necessary. The bis (cyclopentadienyl) titanium diacetate, in tetra earth but they do not offer any particular advantages and hydrofuran dissolved, filtrate containing is listed under versind also more expensive than the salts of the more common 60 reduced! Pressure to remove the solvent Alkali metals. The corresponding salts of the alkaline earth are distilled. The residue obtained is practically pure metals including those of magnesium are bis (cyclopentadienyl) titanium diacetate in one yield can also be used. of 38%.

The reaction between the organotitanium halide and Example 2
the alkali salt of the aliphatic acid runs below 65

mild walnut conditions using a man working as described in Example 1, used

suitable inert volatile solvent smooth. However, 4.7 g of sodium monochloroacetate instead of 3.3 g

Solvents suitable for this purpose include sodium acetate. After filtering and processing

especially polar solvents due to their good vaporization of the solvent practically pure bis (cyclo-

Solvent power for the reaction components. Below 70 pentadienyl) titanium di (monochloroacetate), which is the

ι uyö 3

5 6

acetate is similar, but has greater stability than this filtrate for removing the solvent below, slightly heated at the set pressure. The analysis of the remaining material in Example 3 shows that it consists of bis (cyclo-

pentadienylj-titanium monochloroacetate chloride mixed with

The method described in Example 1 is a more highly substituted product under 5. Use of 6.1 g of sodium dichloroacetate instead of the " ""~"

3.3 g of sodium acetate repeatedly. The implementation proceeds in example 7

similar to the reaction described above - 7 g of di-indenyltitanium are heated under nitrogen

onen, but it runs faster. After a few minutes of chloride (C ₉ H ₇ ), TiCl ₂ and 7.4 g of sodium trichloroacetate under reflux, the reaction is complete, as in 60 ml of dry tetrahydrofuran with stirring 1 ^x / ₂ a determination of the 100% obtained sodium hours under reflux. After cooling, the dichloride is shown. The liquid residue is treated and filtered by action mixture. The residue is washed vigorously with carbon tetrachloride, an amorphous solid tetrahydrofuran, and dried. Substance precipitates is obtained. The precipitate is filtered off and 1.9 g of sodium chloride. The combined filtrates, when heated, consist of practically pure bis (cyclopentadienyl) - 15 _ma n under reduced pressure and under an emit titanium di (dichloroacetate), which has a melting point of substance stream to remove volatile solvents. It has about 8O ⁰ C. Yield 100%. thus receives indenyltitanium di- ^ richloracetate as residue)

_. . ,. in a yield of 80%.

Example 4

The procedure described in example 1 is described under 20 example 0

Use 7.5 g of sodium trichloroacetate in place of one with a reflux condenser, stirrer and thermometer

of sodium acetate repeatedly. The reaction proceeds, put in a 200 ml flask equipped with 3.6 g of sodium

as described above, and it is a stoichiometric thioglycolate and a solution of 4 g bis (cyclopen-

Amount of sodium chloride removed by filtration. The tadienyl) titanium dichloride in 100 ml of glacial acetic acid. To

The filtrate is then mixed with ether, which immediately results in 25 2-hour heating at 80 ° C under nitrogen atmosphere.

Light orange crystals are formed, which are filtered through a sphere, the cooled reaction mixture.

Filter off isolated. The solid filter cake consists. Concentrating the filtrate gives a red one

practically from pure bis (cyclopentadienyl) titanium di-sticky residue, which in the infrared analysis of a

(trichloroacetate) of F. = 177 ⁰ C. With a slightly over acetic acid solution the presence of bis (cyclopen-

At the temperature below the melting point, cerium tadienyl) titanium di (thioglycolate) occurs. The extraction of the

Setting up. Yield 100%. shows sodium chloride formed as a by-product

The compound is more stable than that according to the two, a 60% yield of the organotitanium compound.

play 1 to 3 products received and react. .

Room temperature not with moisture. The example 9

However, binding can be achieved by reaction with moisture. 35 The procedure described in Example 1 is used

like atmospheric moisture, but in organic solution 6.8 g bis (cyclopentadienyl) titanium dibromide and

solvents dissolved water or pure water with 7.5 g sodium trichloroacetate. After removing the as

moderately elevated temperatures with the formation of by-product sodium bromide can be

Titanium ions are condensed. bis-cyclopentadieny-titanium-dichloroacetate) easily

__ .., _ 40 precipitate with ethyl ether and will be in good yield

^Beis P ^{iel 5} won.

5.9 g of cyclopentadienyl dibutoxytitanium monochloride and Example 10 3.7 g of sodium trichloroacetate are 1 hour under a

Nitrogen atmosphere in the presence of 50 g of dry one works as described in Example 1, used

Tetrahydrofuran with mechanical stirring to return, however, 8.6 g of bis (cyclopentadienyl) titanium iodide and 7.5 g

nut heated. The originally coarse sodium trichloro-sodium trichloroacetate. This gives a good yield

acetate crystals disappear during this period of time, bis (cyclopentadienyl) titanium di (trichloroacetate) as in

and fine crystals separate out. After cooling, example 9.

the solid substance is filtered off and washed vigorously with Example 11

Tetrahydrofuran and dries. The weight of the than 50 *

Sodium chloride obtained by-product is 1.15 g. 5.00 g ( 0.02 mol). This gives cyclopentadienyl dibutoxytitanium 55 bis (cyclopentadienyl) titanium dichloride, 12.25 g (0.04 mol) of trichloroacetate in good yield in the form of a reddish brown sodium stearate and 57 ml of dry tetrahydrofuran-colored, somewhat viscous liquid. Sprayed on a. The mixture is subjected to reflux temperature (68 ⁰ C) a glass plate and the air, liquid rapidly into a clear hard amber whereby the originally orange-red slurry colored film converts the heated and held for 1 hour at this temperature. 60 turns yellow. The product is separated off from the sodium chloride Example 6 by extraction with tetrahydrofuran. After discovery

away from the solvent, 13.5 g of a low

The melting solid substance described in Example 1 is repeated (theory 14.9 g). By

drive using 5 g of bis- (cyclopentadienyl) - infrared analysis, the structure of the material is shown as bis-

titanium dichloride and 2.3 g sodium monochloroacetate. While 65 (cyclopentadienyl) titanium distearate confirms,

Most of the red respondents to the implementation. .

Crystals of the above titanium compound. According to example IZ

The cooled reaction mixture is filtered to remove. 5 g of bis (cyclopentadienyl) titanium dichloride are treated

removal of sodium oleate formed as a by-product and 12.2 g of sodium oleate, as described in Example 11,

chloride and unreacted titanium compound becomes the 70 and thus receives 15.1 g of a red-brown, somewhat viscous

Product identified as bis (cyclopentadienyl) titanium dioleate by infrared analysis is identified. A film applied to glass forms when exposed to air; a dry film.

Example 13

The procedure is as described in Example 1, except that 7.3 g of calcium trichloroacetate are used for the reaction 5 g bis ^ cyclopentadieny ^ titanium dichloride. You get orange-colored crystals of bis (cyclopentadienyl) titanium di (trichloroacetate) due to precipitation with ethyl ether after the calcium chloride has been filtered off in good yield.

Example 14

3.1 g of sodium glycolate, about 2 g of glycolic acid and a solution of 4 g of bis- ^ yclopentadienyli-titanium dichloride in 30 ml of glacial acetic acid are placed in a 50 ml flask equipped with a reflux condenser, stirrer and devices to maintain a nitrogen atmosphere a. During a 2-hour reaction time at 8O ⁰ C, the color of the solution from red to light orange changes, and it is made a flocculent precipitate. This precipitate is filtered off, washed with ether and dried and turns out to be sodium chloride. Infrared analysis of the product in the filtrate shows the presence of bis (cyclopentadienyl) titanium diglycolate.

The organotitanium acylates obtained according to the invention are useful as polymerization catalysts for unsaturated polymerizable compounds and for many other purposes due to the special Combination of chemical properties that are readily apparent to those skilled in the art are useful. aside from that they can by hydrolytic condensation by means of measured amounts · water or other hydrolyzing Agents such as alcohols, alkalis and the like are polymerized, the acylate groups are replaced by hydroxyl groups, which then release water with the formation of polymers condense through a Ti-O-Ti-O- "backbone" and are characterized by side groups with a Ti-C bond.

Claims (1)

Claim: Process for the preparation of new organotitanium compounds of the general formula in which R is an optionally substituted cyclopentadienyl or indenyl radical which is bonded to the titanium atom by means of carbon, X is a halogen atom or an alkoxy group, R 'is an alkyl, haloalkyl, mercaptoalkyl or oxyalkyl radical, χ 1 or 2, y 0, 1 or 2 and ζ 1 or 2, the sum of x, y and ζ 4, characterized in that an organotitanium halide or an organoalkoxytitanium halide, in which the organo radicals R correspond, with an alkali or alkaline earth metal salt of an aliphatic monocarboxylic acid, the alkyl radicals thereof can be substituted by halogen, mercapto or oxy groups, implemented and the reaction product is separated from the precipitated alkali or alkaline earth metal halide. © 009 697/519 12.60