DD240308A3 - PROCESS FOR PREPARATION OF TECHNICAL CARBON MIXTURES - Google Patents

Abstract

The invention relates to a process for working up hydrocarbon mixtures, as obtained in gasoline pyrolysis plants, refinery plants and butane dehydrogenation plants, the aim being, by stepwise polymerization to oligo- and polymers of buta-1,3-diene with and without functional end groups, to oligo - And polymers of isobutene and to oligomers and polymers of but-1-ene in a homogeneous and heterogeneous phase without having previously carried out a separation of the component to be polymerized. As a result, a saving of separation processes is possible, so that it is an economical and rational process for the workup of C4 hydrocarbon mixtures. It has been found that buta-1,3-diene in oligomers and polymers with and without functional end groups can be polymerized directly out of the blend without changing product properties over the pure buta-1,3-diene produced polymer. It has furthermore been found that the isobutene of the residual gases of the first polymerization stage can be converted directly from the mixture into oligomers and polymers while retaining the properties of products prepared from pure isobutene. In addition, it has been found that the but-1-ene of the residual gases of the second polymerization stage can be converted directly from the mixture into polybut-1-ene, without that of polybut-1-ene, that of pure but-1-ene was prepared to change known properties. Furthermore, it has been found that the second and the third polymerization stage can be interchanged without negative consequences for the implementation and the products.

Description

- 2 - £ <iV .5Uo Field of application of the invention

The invention relates to an economical and rational process for the workup of hydrocarbon mixtures, the z. B.

in pyrolysis plants for the production of ethylene as compulsory products by stepwise polymerization of the unsaturated components to produce products with different properties. This separation and purification processes are saved and transferred the individual polymerizable components from the mixture into polymers. After each polymerization step, the remaining residual gas, which still contains polymerizable components, is available as feed mixture for further reactions.

Furthermore, the invention allows the preparation of homo-oligomerization and -polymerisaten of buta-1,3-diene, isobutene and but-1-ene with different, variable by the reaction conditions molecular weights and

Microstructures,. , ,.

In addition, the invention also makes it possible to prepare prepolymers of buta-1,3-diene which contain a functional group at each end of the chain by reacting the living polymers with various functionalizers.

Characteristic of the known technical solutions

It is known that buta-1,3-diene can be converted with the aid of alkali metals without and in the presence of regulators selectively from buta-1,3- diene-containing hydrocarbon mixtures into polymers having different molecular weights. Thus, for example, according to RO-PS 51.343, a Ct hydrocarbon mixture with buta-1,3-diene is used for the polymerization, which is formed during the dehydrogenation of butane to butane-1,3-diene. This mixture is added with paraffinic or aromatic hydrocarbons and converted therefrom by a fine dispersion of metallic sodium, the butadiene-1,3-diene in polymers. The viscosity of the products is between 100 and 1500 ocP after the polymerization conditions. Nach'der DD-PS 61.102 liquid buta-1,3-diene polymers are obtained with the aid of alkali metals in the presence of vinyl chloride as a regulator substance and water-soluble cyclic ethers in a mixture with water, if Cs-hydrocarbon mixtures containing about 50% buta- Contain 1,3-diene, brings together with the above initiator and allowed to react at 60 ⁰ C for about 12 hours. The mixture of non-polymerizing hydrocarbons is distilled off leaving the liquid polybuta-1,3-diene from which the initiator must be removed by water scrubbing. The buta-1,3-diene content in the non-polymerizing hydrocarbons can thus be reduced to about 0.5%. In the two patents, no information is provided on the structure of the resulting polymers, but it can be assumed that the content of 1,2-structural units in a similar manner as in the polymerization of pure buta-1,3-diene is greater than 50% (see See, inter alia, W. COOPER, G. VAUGHAN, Progr. Polym., 1.91-160 [1967]; DH RICHARDS, Chem. Soc. Rev. 6, 235-60 [1977]). Alkali metals in the presence of activators, eg. B. of fused aromatics, conjugated unsaturated heterocycles with vinyl side chains and diaryl ketones and LEWIS bases, z. As of aliphatic monoethers, cyclic ethers, acetals and tertiary amines, US-PS 3488340 for buta-1,3-dienpolymerisation from C ₄ cuts are suitable, the latter can come from pyrolysis or paraffin-dehydrogenation. Depending on the ratio of monomer to initiator polymers can be produced with very different molecular weights. Depending on the polymerization temperature arise di- or monovalent anions or mixtures of both. Therefore, when polymerization is terminated with functionalizers, di- or monofunctional polymers or mixtures of both are formed. In addition, it is possible. Making block and random copolymers when anionically polymerizable comonomers are added to the reaction mixture prior to polymerization. , ·

It is also known that isobutene, but-T-ene as well as Er- and Z-but-2-ene can be oligomerized and polymerized in a cationic way. The isobutene shows the greatest tendency to polymerize, which manifests itself in the high reaction rate and the achievable high molecular weights of the polymers.

Thus, it is known from the dissertation by H. Hardening, Friedrich-Schiller-University Jena 1977, and DD-PS 130,937, that isobutene, which is contained in a C ₄ -hydrocarbon mixture, using LEWIS acids, LEWIS acid mixtures or metal sulfate Sulfuric acid complexes can be selectively converted into oligomers and polymers. In both citations, however, it is all about the conversion of the isobutene, while statements on a gradual workup of a d-hydrocarbon mixture are not made.

According to DE-OS 2,708,303 can be prepared using a LEWIS acid and an accelerator liquid butene polymers, if C ₄ -Raffin gas mixtures with 10-70% isobutene and 10-30% n-butenes in exactly maintained temperature intervals of exposure to HCI activated dry AICI ₃ particles suspended. Depending on the temperature interval and initiator concentration, the molar masses of the polymers are between 335 and 1300. The lower the polymerization temperature and the initiator concentration, the higher the proportion of isobutene structural units in the polymer. Higher polymerization temperatures and higher initiator concentrations lead to polymers whose content of isobutene structural units determined by IR and NMR spectroscopy does not coincide with the conversion of the isobutene. However, an explanation for this phenomenon can not be given. The increased poly-n-butene content should lead to more stable lubricants and lubricant additives. V .- .... _;

From Sb. Pr. Vyzk. Chem. Využití UhIi, Dehtu Ropy 12.43 to 59 (1972) it is known that the isobutene can be oligomerized from a C ₄ fraction in the liquid phase over cation exchangers. ::. ''';''".. \ · \ _·:" ·;''; V ^_\;:;:

The continuous or discontinuous reaction yields a mixture of isobutene dimers and codimers with but-1-ene. ... '.- ".- ;; ..:. · -.Vv.-: -' - ./. V: ^ '. Ν. ' ;. } ':. : .-;. -.: .... -; .. '- - · .. - ..'; _v ....-VV

The proportion of codimers increases with increasing temperature, which could be determined with the aid of gas chromatographic investigations. The initiator is sensitive to acetylenes and diolefins, whose content in C₄Cut should be less than 0.01 or 0.1%. '.,.^:, '.' '' --Ϊ́ - '^' '<'..'''"· '·. ·· '-V- .--- V ^:   'Y--'.: '"'''--'^':'''' - "'" ^:

Moreover, it is known that but-1-ene can polymerize by means of heterogeneous and homogeneous ZIEGLER NATTA catalysts to highly isotactic polymers. Catalyst components are generally halides of trihydric and tetravalent titanium in combination with organoaluminum compounds, often a variety of organic compounds, including ausder series of ketones, the carboxylic acid esters and amines, are used as the third component. These LEWIS bases have the task of increasing the stereospecificity of the catalysts. , _: . ;. . . ' ......... V ·· '.; , ·.,. _; .:.

Thus, according to US-PS 4,058,653 from a C _{4 cut} with a but-1-ene content between 75 and 90%, which is free of isobutene, buta-1,3-diene and alkynes, with the aid of ZIEGLER-NATTA catalysts prepared isotactic polybut-1-ene. The catalyst consists of an organoaluminum compound, a transition metal halide from the IV. To Vl. Group of the periodic table and a LEWIS base to increase the stereospecificity. To increase the reaction rate and the isotacticity of the product, an inert hydrocarbon (aromatics, cycloaliphatic) is used as solvent, in which moreover a homogeneous polymerization reaction takes place. In none of the examples given, however, is a C _{4 cut} , as stated in the text of the patent, used.

Also in the dissertation of H. Hardening, Friedrich-Schiller-University Jena 1977, as well as in DD-PS 126.998, the selective but-1-enpolymerisation of a but-1-en-containing C ₄ hydrocarbon mixture is described. Teirkristallines polybut-1-ene, which is particularly suitable for producing films, can according to DE-OS 2,318,901 by polymerization of pure 1-butene or a 1-butene addition ButT2-en and butane-containing C ₄ Are obtained when using as catalyst a mixed contact of TiCl ₃ · η AICI ₃ and diethylaluminum monochloride. To achieve an ether-soluble fraction of 10-30% in the polymer additives of up to 15 mol% of Aluminiumtrialkylzum catalyst and polymerization temperatures between 70 and 100 ⁰ C are necessary. -

According to this process, it is also possible to use α-olefins, especially propene, as comonomers in proportions of up to 10% by weight, based on the but-1-ene, without the desired production properties changing in a fractional manner. All of the processes mentioned here have in common that, although a component is converted into a polymer from a C ₄ -hydrocarbon mixture by certain initiators, it is not assumed in every case of mixtures obtained directly in the pyrolysis and other processes but of certain constituents depleted mixtures, without the residual gases fed to a further processing or statements about reverberation possibilities are made.

Object of the invention

The aim of the invention is to provide an economical and rational process for the preparation of homo-oligomers and polymers of buta-1,3-diene, of isobutene and of but-1-ene with different molecular weights and microstructures which can be varied by the reaction conditions, from C ₄ - To develop hydrocarbon mixtures without prior separation of the component to be polymerized, the disadvantages of the known methods to be eliminated. The object of the invention is to convert the polymerisable components contained in C ₄ hydrocarbon mixtures from gasoline pyrolysis plants, from refinery plants and from butane dehydrogenation plants into products with different properties by reactive separation in the form of successive polymerizations. The polymerization of the individual unsaturated components should always take place from the mixture, ie without prior separation of the component to be polymerized and thus run with the saving of separation processes. After each polymerization step, the remaining residual gas, which still contains polymerizable components, should be available as feed mixture for further polymerization steps.

Furthermore, by the individual polymerization steps, the synthesis of homo-oligomers and polymers of buta-1,3-diene, isobutene and but-1-ene be possible with different, variable by the nature of the initiators used and the reaction conditions applied variable molecular weights and microstructures.

.-. )

Explanation of the essence of the invention

The aim of the invention is an economical and rational process for the preparation of homo-oligomers and polymers of buta-1,3-diene, isobutene and but-1-ene with different, variable by the reaction conditions molecular weights and microstructures .C ₄ -hydrocarbon mixtures to develop without prior separation of the component to be polymerized, the disadvantages of the known methods to be eliminated. The object of the invention is to convert the polymerizable components contained in C 2 -hydrocarbon mixtures from gasoline pyrolysis plants, from refinery plants and from butane dehydrogenation plants into products with different properties by reactive separation in the form of successive polymerizations. The polymerization of the individual unsaturated components should always take place from the mixture, ie without prior separation of the component to be polymerized and thus run with the saving of separation processes. After each polymerization step, the remaining residual gas, which still contains polymerizable components, should be available as a feed mixture for further polymerization steps. : V-. j. ·

Furthermore, by the individual polymerization steps, the synthesis of homo-oligomers and polymers of buta-1,3-diene, isobutene and but-1-ene be possible with different, variable by the nature of the initiators used and the reaction conditions used molecular weights and microstructures.

The object is achieved in that in a first polymerization stage after removal of acetylenic and allenic impurities buta-1,3-diene from a C _{4 cut} with the aid of initiators which cause anionic and coordinative polymerization, in Buta-1..3 -diene oligomers and polymers is converted. The polymerization can be triggered inter alia by alkali metal aromatic complexes, by alkali metals and their alloys and by Org ° aolithium compounds. Depending on the initiator system used, living mono- and dianions are formed as chain supports of the polymerization, which can either be converted by proton-donating agents such as water and alcohols into oligomers or polymers or by functionalizing agents in mono- or bifunctionalized oligomers (Telechelics) and polymers .. '_;"; .., ..., ^...:;; '' .Vv. '...'. · ;. V.-vy ';..' v / v .: '' · '''.;. ·: V ^; , _; ^! ··: - Vv -'- 'V .- - ^: vv-vV -: -, .. "V-. '': ''':''' ν ". : '-. The alkali metal aromatic complexes used to initiate the polymerization are prepared by reacting alkali metals with aromatics, preferably naphthalene, in ethereal solution, e.g. In THF, and used as 0.1-0.5 molar .Lösungen. ..... · ..-, · · -. V.- _; .. VV> - ^; ----- -. / '-. · . ·' .-. ^: V - VV v «- V ν '' V., -: - l /;, -% V-VVVV · '. -. .-. VV.jV ..; - - -V :

The alkali metals may be in the form of their alloys, e.g. Example in the form of sodium-potassium alloy, wherein the incubation time of the polymerization reaction compared to the use of pure metals significantly shortened. The organolithium compounds of the type used to initiate the polymerization

in which R and R 'are alkyl radicals having 1-30 C atoms, preferably 3-15 C atoms, η is the values 1-12, preferably 2-3, and R "-Li or R"' - Li respectively a lithium atom containing, partly aromatic groups substituted with alkyl groups, preferably phenyl groups, in which the lithium atom is in the ortho position, are used either in bulk or as 0.1-0.5 molar solutions in aromatic hydrocarbons, preferably benzene. The polymerization can be carried out in a manner known per se.

It is possible to work in the liquefied C ₄ fraction which is under its own pressure at the respective polymerization temperature, the non-polymerizing hydrocarbons acting as diluents or else using auxiliary solvents such as aliphatic and aromatic hydrocarbons and also aliphatic and cyclic ethers. The polymerization can be carried out at temperatures of -75bis + 150 ° C, -10 vorzugsweise_bei be performed to + 100 ⁰ C at atmospheric pressure or at elevated pressure.

The amount of initiator to be used is determined by the desired molecular weight of the oligomers or polymers, since it is a stoichiometric polymerization. According to the invention, polymers having low molecular weights, e.g. 500 to 10,000, but also with high molecular weights, z. B. 100000 to 500000 are produced.

During the polymerization, which leads to the complete conversion of the but-1,3-diene, no termination reactions occur, so that the living chain ends can be reacted with electrophilic functionalizing agents and so mono- or bifunctionalized products can be obtained. , ·

Suitable functionalizing agents include epoxides, aziridines, lactones and CO ₂ .

, The products produced have the same properties as when using pure buta-1,3-diene polymers, so that even the first step of the process is a rational and inexpensive method to buta-1,3-dierioligomeren and polymers with and without functional To reach end groups without a buta-1,3-diene extraction from the C _{4 cut is} required. , , ,

Furthermore, the object is achieved in that in a second polymerization losbuten from the residual gas of the first Polymerisatio.nsstufe or from a remaining after the buta-1,3-diene extraction butene fraction with the aid of initiators that cause a cationic polymerization, in isobutene or Polymer is transferred: The polymerization may include, inter alia be triggered by metal sulfate-sulfuric acid complexes, by LEWIS acids or by LEWIS acid mixtures. · '. '' ·

The metal sulfate-sulfuric acid complexes used to initiate the isobutene oligomerization are used in a solid form for the oligomerization and can therefore easily, for. B. by filtration, are separated from the reaction product.

The LEWIS acid mixtures, which serve to initiate the isobutene polymerization are prepared shortly before the start of the polymerization of the components, for. B. from AIBr ₃ and TiCl ₄ . In this case, a co-solvent, for. As a cycloaliphatic hydrocarbon such as cyclohexane, use. , ·

The oligomerization and the polymerization can in turn be carried out in a known manner. The oligomerizations are possible both in the gas phase and in the liquid phase; in the latter case, either in the liquefied and at the respective Oligomerisationstemperatur under its own pressure standing C4 cut itself or in a solvent. The solvents used are aliphatic and cycloaliphatic hydrocarbons such as pentane, hexane and cyclohexane. The polymerizations are also possible both in substance, ie in the liquefied C _{4 cut} , as well as in a solvent such as aliphatic and cycloaliphatic hydrocarbons. The polymerization can be carried out at temperatures between -100 and + 100 ° C, preferably between -75 and + 50 ⁰ C atmospheric pressure or at elevated pressure. The oligomerizations take place between -30 ⁰ C and + 100 ⁰ C, preferably between + 20 and + 5O ⁰ C. ', ·. : /, ' ,, \'. , ";

The isobutene oligomers and polymers produced by the process according to the invention have the same properties as the products obtained from pure isobutene, so that this step of the process is also a rational and inexpensive method for obtaining the said products. , ^; ^ ^;

In addition, the object is achieved in that in a third polymerization stage but-1-ene can be converted from the residual gas of the second polymerization stage by means of catalysts which cause a complex-coordinating polymerization in polybut-1-en. -:. -v

The polymerization can be effected, inter alia, by ZIEGLER-NATTA catalysts which consist of a transition metal halide of IV. To VI. Group and an organometallic compound of I. to III. Main group are triggered. Halides of titanium may be used as transition metal halides, while aluminum compounds of type AIR _n X ₃ may be used as metal organ compounds. _n , where R is an alkyl radical having 1-10, preferably 1-4 C atoms, and X is a halogen, preferably chlorine, is.-. ·,. - 'Z .. .-. ·. , ^: · -.... ... , .. · '

To modify the ZIEG LER-N ATTA catalyst, electron donors can be used, inter alia, from the classes of amines, ethers and carbonyl compounds. , ....-:: ^; , \ ^; .f *. -. :

The polymerizations can be carried out in a manner known per se. They are both in the liquefied C _{4 cut} and using an auxiliary solvent from the series of aliphatic and cycloaliphatic:>: v

Hydrocarbons possible. : ..:. ''[^^''.'./'y;' , ':. '-,.', - ^:; ! ::: / .:. .,. - · · ^; .-. .:; : - '/:

The polymerization temperatures are between +20 and + 150 ° C, preferably between +60 and +100 ⁰ C. .. Z

The but-1-enpolymers which have been prepared by the process according to the invention have the same properties as the products obtained from pure but-1-ene, so that this process step also represents a rational and inexpensive method of obtaining the said products , Furthermore, the object is achieved according to the invention in that the polymerization steps 2 and 3 can be carried out in the reverse order, i. that the polymerization of but-1-ene with the aid of ZIEGLER NATTA catalysts before the cationic isobutene oligomerization and polymerization takes place without causing any disadvantages in the mode of implementation and as a result of the polymerization.

The remaining after the third stage of the process according to the invention residual gases, which consist mainly of E and Z-but-2-ene as well as of n- and iso-butane, can be supplied to a further use.

The examples given are intended to explain the process according to the invention without restricting it in any way.

Embodiment ^v example 1

In a 2 liter glass autoclave equipped with stirrer, thermometer and tempering jacket, 200 ml of a C ₄ -hydrocarbon mixture having the composition

1.4% C ₃ -K.hydrocarbon.

5.7% n- and iso-butane • 46.2% but-1-ene and isobutene

9.9% E and Z-but-2-ene. '' - ·

35.9% BuM .3-diene

0.9% Cs hydrocarbons

submitted and 1 200ml dry heptane added. After adding 28.2 mmol of the initiator N, N'-di (o-lithiumphenyl) -N, N'-di-n-butyl-ethylenediamine dissolved in 90 ml of benzene, the homogeneous reaction mixture is stirred at 85 ° C for 12 hours , After completion of the buta-1,3-dienumsetzung, which can be determined by gas chromatography, the polymerization is stopped by the addition of methanol and worked up the polymerization in the usual manner. This gives 43 g of a polybutadiene-1,3-diene which has 34% 1,4-cis, 56% 1,4-trans and 10% 1,2-structural units.

Step Example! 2

The polymerization was carried out in the same manner as described in Example 1, but added after complete buta-1,3-dienumsatz 60 ml of ethylene oxide and heated again to 60 ⁰ C for 2 hours. The yield of polymers whose functionality is 1.88 is 100%. The structural composition is very similar to that of the polymer of Example 1.

Example 3

In a 5 liter capacity polymerization reactor equipped with stirrer, thermometer, manometer and cooling coil, 21 of a C ₄ -hydrocarbon mixture having the composition

0.9% C ₃ hydrocarbons ·

8.0% n- and iso-butane 43.5% but-1-ene and isobutene _:

8.2% E and Z-but-2-ene '. '"... · · ..

39.2% BuM .3-dien

0.2% Cs hydrocarbons,

whose content of acetylenic and allenic impurities is not greater than 75 ppm, submitted and the temperature adjusted to + 10 ° C. Upon addition of 12mmol of sodium potassium naphthalide prepared by reacting naphthalene with sodium-potassium alloy in THF, polymerization immediately commences, as indicated by temperature rise and red coloration of the polymerization solution. The temperature is adjusted to 30 ⁰ C and stopped after complete buta-1,3-dienumsatz, which was determined by gas chromatographic analysis, by addition of methanol. The residual gas is expelled at a slightly elevated temperature and liquefied again, so that it is available for further reactions. '

The polymer, which is obtained in a yield of over 90%, has a molecular weight of 93,000 and an IR spectroscopically determined proportion of 62% 1.2-structural units. , .. - V. ',:'. '. '

Example 4 '' - ''''''''.'''''. ^ T ·'. ' ! "''"''''. ΐ / '""' '"' ^ ^ - '"^{; J} ---- ^; -; "-'-;··':" ^: - ';'; ·· ';" . ^ ^ • ^ r-. ·: ^ ..>. · · --.-. ..-., .-. ^ -..-..- :. -, · · · ·,:, ..-; · .-. - .. - Polymerization reactor used in Example 3 are 2 [of a C ^ hydrocarbon mixture, which is produced as the residual gas after polymerizations according to Example 1, with the composition -; '-' - '

, 0.2% Cs hydrocarbons. , , ;,. >,.: -. ·.

13.4% n- and iso-butane. '::

... "13.6% E- and Z-but-2-en ': ^J: _ ^." ^{-J:: -;} '. \

0.4% BuM .3-dien "· '"': ""' ^: - . ' - ': . ^::: '. ; , ^

filled and the temperature set to about 40 ⁰ C. 6 mmol of AIBr ₃ , dissolved in cyclohexane, are mixed with 0.36 mol of TiCl ₄ and, after a reaction time of 10 minutes, added to the C ₄ mixture. , : ·.-.'...,:. '. · ....;

The temperature rises and is kept constant until the end of the reaction at +50 ⁰ C. The course of the polymerization is monitored by gas chromatography and the polymerization is stopped after completion of the isobutene conversion (about 2.5 hours) by addition of methanol. The unreacted residual gas is collected as described in Example 3. The remaining residue is dissolved in a little petrol and precipitated in hydrochloric methanol. After drying, a water-clear viscous oil with a molar mass of 1300 is obtained with 85% yield

Example 5

For polymerization, a butene fraction remaining after the extraction of 1,3-butadiene is used having the following composition:

- 0.3% C ₃ hydrocarbons

4.9% n-butane

19.2% iso-butane; ,

22.1% but-1-ene. , ,

40.7% isobutene

6.5% E-but-2-ene. , ',

0.3% but-1,3-diene '. ,

In an analogous procedure as in Example 4, but at temperatures between -60 and -70X, is obtained after 10 hours of reaction time in 65% yield, a colorless plastic polyisobutene with a molecular weight of 80,000.

Examples 6-9. ,

In an analogous procedure as in Example 4 and using a Butenfraktion same composition is obtained by varying the reaction temperature polyisobutenes having the following molecular weights

example polymerization molar mass temperature Mn 6 -40X 60,000 · 7 -20X 26,000 8th OX 11,000 9 + 20X 4000

Example 10

In the polymerization reactor described in Example 3, 21 of a butene fraction with 46.7% isobutene are introduced and stirred with 5 g of an initiator having the composition 2VOSO ₄ H ₂ SO ₄ at 5OX.

After about 6 hours, the Isobutenumsetzung is largely connected, whereupon the unreacted residual gas is distilled off and liquefied again. Fractional distillation of the residue, previously filtered through basic alumina, gives 70% of diisobutene and 20% of triisobutene, the remainder being tetraisobutene and higher oligomers. The following table shows the composition of the C _{4 cut} before and after the oligomerization of the isobutene. '.

% before implementation% after

Implementation -

component % vc C ₃ -Kohlenwst. 0.3 n-butane 5.3 isobutane 12.6 1-butene 24.5 isobutene 46.7 E-but-2-ene 7.2 Z-but-2-en 3.0 But-1.3-diene , 0.4

0.1.

, - - '. ·· '::; 9.4 : , - '. ,.-.- - '

  '' -. ". '' /.20,8 ..: .. ''" '"'." '/.' "

41.7

"V: 13.3" "'" "' '" "I" "' '.'" "

'- · -'. 7,9 '. ':' .-. , ·; -. -. .- ,. ,; , '· "'.

Example 11 ".;. '·;.;,. ''.:':"]; - '^:; / ^; ;. ·. ';'<''";/'-;'''','.,' y ' ¹ ^'-"'' -. ". '" \, / ^; ν · .Τ '. ""' ... '"": .. "'; _ / ' ·'','".' , ";". In the glass autoclave described in Example 1, 9 mmol of r-TiCl ₃ and ₃ mmol of aluminum triethyl, dissolved in cyclohexane, are initially charged and 11 of a C ₄ -hydrocarbon mixture having the composition ν

.: 30.5% η and iso-butane ...., -.; /.; , -. ''. ' v. ^:: '

which was formed in a polymerization according to Example 4, added. - '~ ^: '"''''''' ^! ''';.'': - ^: ': ' ^v:

At a temperature of 7OX, the but-1 enpolymerization is carried out after 12 hours up to a 90% conversion. After the usual workup, a solid white polymer is obtained which consists of about 60% of isotactic structural units.

Example 12

In an analogous procedure as in Example 11, but with a butene fraction from which the isobutene was not separated and had the following composition:

0.3% C ₃ hydrocarbons.

4.9% n-butane. :

19.2% iso-butane. '.

  22.1% but-1-ene,

40.7% isobutene.

6.5% E-but-2-ene.

5.6% Z-but-2-ene /. , , ''

0.3% but-1.3-diene

a solid white polybut-1-ene could be obtained in 90% yield. Due to the ether-soluble portion can be expected with about 75% isotactic structural units. : .. · ... - - - - -

Claims (12)

Invention claim: 1. A process for the processing of technical C ^ hydrocarbon mixtures by selective oligomerization and / or polymerization of the buta-1,3-diene, isobutene and But _: 1-ens by means of known initiators or catalysts for the individual reactions, in which after removal.acetylenischer and allenic impurities at temperatures and pressures where the monomer mixture is in the liquid phase, in a first stage buta-1,3-diene, with the aid of alkali metal I-aspartate complexes, alkali metals and their alloys or organolithium compounds in oligomers and / or Polymers is characterized, characterized in that the residual gas of the first Polyrnerisationsstufe as ". Starting mixture of a second polymerization stage in which either isobutene with the aid of Lewis acids, Lewis acid mixtures or metal sulfate-sulfuric acid complexes or but-1-ene is converted by means of Ziegler-Natta catalysts into oligomers and / or polymers, is used and the Residual gas of the second polymerization stage as a starting mixture of a third polymerization stage in which, depending on the reacted in the second polymerization monomer either but-1-ene or isobutene with the aid of said initiators or catalysts is converted into oligomers and / or polymers is used. 2. The method according to item 1, characterized in that the alkali metal aromatic complex is preferably sodium naphthalide, as alkali metals sodium or potassium, as alkali metal alloy sodium-potassium alloy and as organolithium initiators compounds of the type. ' N- (CH₂) -Ή ^ ' -. '. IdR "R ¹¹ Li in which R and R 'are alkyl radicals having 1-30 C atoms, in particular 3-15 C atoms, η has the values 1-12, preferably 2-3, and R "-Li or R"' - Li each containing a Lithiumatiom, partially substituted with alkyl groups aromatic radicals, preferably phenyl groups in which the lithium atom is in the ortho position are. -. , , 3. The method according to item 2, characterized in that the polymerization is carried out in solvents and that are used as the solvent aromatic hydrocarbons, preferably benzene, cycloaliphatic hydrocarbons, preferably cyclohexane, and aliphatic hydrocarbons, preferably hexene and heptene. 4. The method according to item 3, characterized in that the polymerization in the temperature range of - 75 ° C to + 150 ⁰ C, preferably between -10 ⁰ C and + 100 ⁰ C is performed. 5. The method according to item 4, characterized in that electrophilic agents such as oxiranes, aziridines, lactones and CO _{2 are used} to kill the living polymer chains for the production of buta-1,3-dienoligomeren and low molecular weight buta-1,3-dienpolymeren become. 6. The method according to item 1, characterized in that the Isobutenoligomerisation initiators of the type Me _m (SO4) n XH ₂ SO ₄ · yH ₂ O, in which Me a metal of II. And III. Main group and the IV. To Vl. Subgroup of the Periodic Table and χ a value between 1 and 5 and y may be a value between 0 and 5, alone or in combination with LLEW acids such as AICI ₃ , AIBr ₃ , SnCl ₄ , TiCl ₄ , SbCl ₅ , SbF ₅ in the molar ratio between 5: 1 and 1: 5 are used. 7. The method according to item 1, characterized in that for Isobutenpolymerisation mixtures of LEWIS acids, preferably of AIBr ₃ and TiCl ₄ in a molar ratio of 1:10 to 1: 100, preferably from 1:50 to 1:70 are used. 8. The method according to item 7, characterized in that the polymerization is carried out in solvents and that are used as the solvent aliphatic hydrocarbons, preferably cyclohexane, and chlorinated aliphatic solvents, preferably dichloromethane and 1,2-dichloroethane and trichlorethylene. 9. The method according to item 1, characterized in that as catalysts for but-1-ene polymerization '..-,' ÜbergangsmetallhalogenidederlV. to Vl. Group, preferably halides, especially chlorides of titanium, in conjunction with organometallic compounds of I. to III. Main group, preferably aluminum compounds of the type AIR _n X ₃ . _{n are used} with η between 0 and 3, wherein R represents an alkyl radical having 1 to 10 ^ preferably 1 to 4 carbon atoms, and X is a halogen, preferably chlorine. -. :. · 10. The method according to item 9, characterized in that for modifying the catalysts Electron donating, preferably from the classes of amines, ethers and carbonyl compounds, are added. ''^'·''' / * /; ^Y ---- "'-'; - ^ - y '-' - •• - = · · ^· · .-.... .. · .. ·. · - .. · .. · - .. ..,. -:, - ... ,, ,,,,,, ... , -. ... ,, : -. ..., .., .., .. ". 11. The method according to item 10, characterized in that the polymerization is carried out in solvents and that as a solvent aliphatic and cycloaliphatic hydrocarbons, preferably hexane, heptane and cyclohexane ,. be used. , ^: ' 12. The method according to item 11, characterized in that the polymerization at temperatures between +20 and +150 ⁰ C, preferably between + 60 and + 100 ⁰ C is performed. .. '-.