DE1165864B - Process for the production of hydrocarbon-soluble mixed catalysts for the polymerization of 1,3-butadiene - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Boarding school KL: C 08 d

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File number:
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German class : 39 c - 25/05

F 37592 IVd / 39 c
August 16, 1962
March 19, 1964

The invention relates to the production of mixed catalysts containing titanium-iodine compounds, which are suitable for the polymerization of butadiene to form polymers with a predominantly cis-1,4 structure.

From Belgian patent specification 551 851 and British patent specification 848 065 it is known that one in the reaction of titanium tetraiodide with aluminum trialkyls to catalysts which the Allow production of butadiene polymers with cis contents of more than 85%. In particular When this process is transferred to an industrial scale, the low solubility of the Titanium tetraiodide is large in hydrocarbons due to the associated poor meterability Trouble. The formation of deposits when standing up also has a disadvantageous effect of titanium tetraiodide solutions occur. The difficulties with the dosage also do not let through Use of titanium tetraiodide suspensions correct, as these are due to the high specific Allow the weight of titanium tetraiodide to be handled poorly. In addition, disproportionation reactions also lead here for the formation of crystalline deposits on the vessel walls. From the Belgian Patent specification 584 121 also shows that one in the production of catalysts from titanium tetraiodide and aluminum alkylene can add ethers, alcohols or carboxylic acids. Additions of this kind are intended to Increase cis content of the butadiene polymers obtained therewith when the polymerization in pentane as Solvent is carried out. Apart from that, this method also has the disadvantages, which result from the poor solubility of titanium tetraiodide. In addition, the addition of alcohols Ethers or carboxylic acids in the catalyst production increased consumption of aluminum alkyls result, which is undesirable for economic reasons.

The numerous difficulties involved in handling and dosing titanium tetraiodide make reproducible catalyst production impossible. The use of titanium tetraiodide catalysts could for these reasons have not yet been implemented on an industrial scale.

It has now been found that hydrocarbon-soluble mixed catalysts for the polymerization of 1,3-butadiene by reactions of aluminum trialkyls and / or mono- or dialkylaluminum hydrides, the alkyl groups of which contain 1 to 20 carbon atoms, with titanium-iodine compounds, with the exclusion of air and humidity at a temperature between -10 and + 50 ° C in processes for the production of
mixed catalysts soluble in hydrocarbons
for the polymerization of 1,3-butadiene

Applicant:

Paint factories Bayer Aktiengesellschaft,

Leverkusen

Named as inventor:

Dr. Nikolaus Schön,

Dr. Gottfried Pampus, Leverkusen,

Dr. Josef Witte, Cologne-Stammheim

can be produced particularly advantageously if the titanium-iodine compounds used are special titanium-iodine alcoholates of the formula Ti (OR) J ₃ , in which R is a straight-chain or branched alkyl, cycloalkyl or aralkyl radical having 1 to 20 carbon atoms, and optionally adding halogenated hydrocarbons or -olefinic hydrocarbons to the mixed catalysts in amounts of 0.5 to 20 moles per mole of titanium compound.

In the catalyst systems prepared according to the invention, the molar ratio between the titanium compound is and organoaluminum compound 1: 2 to 1:20. For the method according to the invention particularly suitable titanium compounds are, for. B .:

Cn-C ₈ H ₁₇ O) TiI ₃ , (1-C ₈ H ₁₇ O) TiI ₃ , (nC ₄ H ₉ O) TiI ₃ , (nC ₁₂ H ₂₅ O) TiI ₈ .

Aluminum trialkyls can be used as organoaluminum compounds as well as mono- or dialkylaluminum hydrides can be used.

Suitable aluminum compounds for the preparation of the catalysts according to the invention are called:

A1 (C ₂ H ₅ ) ₃ , Al (iC ₄ H ₉ ) ₃ , Al (nC ₃ H,) ₃ , Al (nC ₁₂ H _2B ) ₃ , Al (IC ₄ H ₉ ) H ₂ , Al (iC ₄ H ₉ ) ₂ H.

The titanium alkoxy triiodides of the formula Ti (OR) J ₃ can be prepared in substance by reacting titanium tetraiodide with the alcohols in question in a molar ratio of 1: 1. However, the reaction is advantageously carried out in an anhydrous aliphatic or aromatic solvent which does not contain any mobile hydrogen atoms, in particular

409 539/593

3 4

Hydrocarbons carried out. For this purpose, the compounds Λ-olefins such as isobutylene, vinylcyclo reaction mixture to temperatures of at most hexene, diisobutylene, (2,4,4-trimethylpentene-1), styrene 180 ⁰ C, for example to the boiling point of or hydrocarbon halides, preferably Al -Toluene, heated until the reaction of titanium tetraiodide kylchloride, bromide and iodide such as isopropyl chloride, with the alcohol has completely escaped and the iodine formed 5 isopropyl iodide, isopropyl bromide, n-butyl chloride, hydrogen dehydrogen. For complete decyl iodide, iodoform, chloroform, cyclohexyl chloride, and removal of the hydrogen iodide, heating against benzyl iodide in amounts of 0.5 to 20 moles per mole of the end of the reaction can be carried out under reduced pressure. Titanalkoxytrijodid be added. Said Evaporation of the solvent can be the additives cause at constant Konzentra-Titanalkoxytrijodide depending on the type of the used ¹⁰ functions to titanium and aluminum, a lowering of the alcohol as an oily-to-fixed, usually schwarzbraun- molecular weights of the butadiene polymers obtained, colored substances obtained expediently such Molgewichtsverschiebung can be exclusion of light at temperatures below 20 ⁰ C without these additions only by changing the Titanaufbewahrt be. concentration or by increasing the polymerisation

Reach another way to produce the titanium ion temperature.

alkoxytrijodide results from Coproportionierung the production of the mixed catalysts for the

of titanium tetraiodide with a titanic acid ester during the polymerization of butadiene takes place with the exclusion of heating of the two compounds in substance or by air and moisture in aliphatic and / or better in solution to temperatures up to at most aromatic hydrocarbons at temperatures lSO '^ C. Solvents can also be aliphatic, 2 ° of - 10 to 5O ⁰ C, by reacting the titanium compounds cycloaliphatic or aromatic hydrocarbons of the formula Ti (oR) J ₃ can be used with the organoaluminum. This process is particularly compound implemented, the sequence of which is advantageous if the addition of the corresponding titanic acid ester is not critical.

is easily accessible. Carrying out the polymerization with the help of

The titanium compounds of the formula Ti (OR) J _{3 are} catalysts according to the invention after an extraordinarily well-known process at temperatures of -40, improved solubility compared to titanium tetraiodide. If the solubility of up to 8O ⁰ C in the ver-tetraiodide for the catalyst preparation in hydrocarbons generally used under solvents. The solvent used is 1%, so the solubility with increasing length, preferably aromatic hydrocarbons, such as the alkoxy radicals introduced, can be increased to over 30%. 3 ° benzene, toluene, used.

A moderate increase in solubility is fine. The catalysts can be solidified in such quantities if one uses titanium tetraiodide in one, that for 100 g of butadiene 0.2 to 2.0 millimoles Solvents with an alcohol in a ratio of 1: 1 titanium compound are used, added without eliminating the hydrogen iodide. The deactivation of the catalysts afterwards

Such mixtures can also be used for the polymerization and the isolation of the poly compounds of the formula Ti (OR) J ₃ for the production of merizates by adding, if necessary, polymerization catalysts, but organic acids, alcohols or bases, and also arises as a result of the hydrogen iodide present one of the usual stabilizers and by precipitation with increased consumption of organoaluminum compound. for example alcohol or acetone or by reducing the iodine content of the titanium compounds in the solvent in vacuo or with water vapor, ie a transition to compounds of the abortions.

Formula Ti (OR) ₂ J ₂ leads to a reduction in activity The use of titanium alkoxy triiodides of

of the catalysts produced therefrom. If you increase the formula Ti (OR) I ₃ instead of titanium tetraiodide in which the iodine content by adding less alcohol, production of catalysts for the butadiene _{poly by bringing to mixtures of Ti (OR) I 3} and TiJ ₄ 45 merisation for technical, in particular goes over , the high activity of the continuously operating polymerization process catalysts is retained, the solubility an extraordinary advance. Due to the good solubility, however, with increasing titanium tetraiodide concentration, titanium alkoxy triiodide concentration can be reduced. Form of their solutions in catalyst preparation

Instead of monohydric alcohols you can dose at 50 without difficulty, while at the the production of titanium alkoxy triiodides also increased use of titanium tetraiodide due to the low, Valuable alcohols are used, provided the solubility in hydrocarbons is below 1% of the titanium compounds obtained, large amounts of solvent can still be introduced is sufficient. On 1 mole of titanium tetraiodide is needed; this fact is particularly evident in a contidious one Trap the 1 equivalent of hydroxyl equivalent to 55 natural methods for the solvent balance of Amount of alcohol used. Furthermore, in place of great disadvantage. Solutions of titanium alkoxy triiodides Alcohols and carboxylic acids or vinylogous can easily be converted into carboxylic acids in a technical plant how to store ß-dicarbonyl compounds and transport them through pipelines, Production of analogous titanium compounds is used whereas titanium tetraiodide suspensions are also used. As a result of the carbonyl groups, however, deposits increase at 60 equal titanium concentrations the production of the catalyst is the consumption of organodes, the walls of the vessels, pipes and valves, aluminum compounds, also improve due to the high specific weight of the Carboxyl groups make their solubility in significantly less than titanium tetraiodide particles in pipelines difficult to a lesser extent than alkoxy groups. can be transported and due to the hardness

A change in the mode of action of the titanium tetraiodide crystals according to the invention to mechanical components Catalysts produced can cause damage, especially to mobile ones can be achieved that following the implementation of parts such as pumps, valves and pipe elbows Titanium alkoxy triiodides achieve a considerable level with the organoaluminum genes.

A reproducible catalyst preparation, i. H. exact compliance with the titanium-aluminum ratio is only possible through the use of the easily metered titanium alkoxy triiodides. The so Guaranteed constant catalyst activity is required to produce polymers on a larger scale to be able to produce with certain molecular weights at fixed space-time yields.

When using titanium tetraiodide solutions or suspensions, the poor dosability, but especially the formation of deposits leading to concentration fluctuations and thus to different ones Catalyst activities that seriously interfere with a technical process have as a consequence.

The process according to the invention thus enables the proper use of catalysts Based on titanium-iodine compounds by means of titanium alkoxy triiodides on an industrial scale. One Production of such catalysts on the known basis of titanium tetraiodide could be based on the The difficulties mentioned have not yet been realized on an industrial scale.

The catalysts prepared according to the invention give butadiene polymers in excellent space-time yields at low catalyst concentrations which have a structure of more than 80%> mostly more than 90 ° / ₀ cis-1,4 linkages and have a very low cold flow.

The polymers can be used alone or in a blend with other elastomers to form products process excellent technological properties.

In the following examples, the parts indicated are parts by weight.

Preparation of titanium alkoxy triiodides by reacting titanium tetraiodide with alcohols in

1: 1 molar ratio a) titanium dodecylate triiodide

ίο In a stirred vessel with the exclusion of Air and moisture in 60 parts of dry benzene suspended 11.1 parts of titanium tetraiodide. While stirring 3.73 parts of dodecyl alcohol diluted with 30 parts of dry benzene were slowly added.

The evolution of hydrogen iodide began immediately at the beginning of the addition. The reaction mixture was then heated under reflux for a further 6 hours. The titanium tetraiodide had formed a dark brown solution implemented. At a temperature

ao door from 30 to 45 ⁰ C, the solvent was distilled off in vacuo. The residue remained 12.3 parts of a substance which solidified in crystalline form on cooling and showed the following analytical values: iodine 60.9%; Carbon 23.1%; Hydrogen 4.1%; calculated values: iodine 62.2%; Carbon 23.5%; Hydrogen 4.1%; for Cn-C ₁₂ H ₂₅ O) TiJ ₃ .

In the same manner as described above, using other alcohols, the following Titanalkoxytrijodide and two reaction products made with fatty acids, which are black-brown, oily substances at room temperature.

Iodine content [ / "] Implementation time calculated | found hours a) Cn-C ₈ H ₁₇ O) TiI ₃ 68.3 69.6 6th b) Ci-C ₈ H ₁₇ O) TiI ₃ 68.3 68.7 8th c) Cn-C ₄ H ₉ O) TiI ₃ 75.9 75.2 5 d) (C ₂ H ₅ O) TiI ₃ 80.5 78.8 3 e) (CH ₃ O) TiI ₃ 82.5 80.7 2 f) (C ₄ H ₉ OCH ₂ CH ₂ O) TiI ₃ 69.7 69.0 6th g) (<^ H '> OJTiJ ₃ 72.1 69.9 6th h) (CH ₃ (CHa) ₇ CH = CH - (CHa) ₇ COO) TiI ₃ 53.6 52.3 6th i) (C ₁₇ H ₃₅ COO) TiI ₃ 53.5 53.0 6th

(C ₂ H ₅ O) TiI ₃ and

)) tiJ _{3 had} implemented and a homogeneous dark brown solution was formed. At 30 to 4O ⁰ C, the solvent was distilled off under reduced pressure.

are dark brown substances that are solid at room temperature. 55 A brown-black, oily substance remained, punch, (CH ₃ O) TiI ₃ and (C ₄ H ₉ OCH ₂ CH ₂ O) TiI _3, the iodine content of which was 76.2% . For butoxytitanium triiodide obtained as a black solid. an iodine content of 75.9% is calculated

Preparation of titanium alkoxy triiodides by reacting titanium tetraiodide with titanium esters

3 TiJ ₄ + Ti (OR) ₄ -> 4 (RO) TiJ ₃

With the exclusion of air and moisture, 16.6 parts of titanium tetraiodide were placed in a vessel with a stirrer suspended in 80 parts of anhydrous benzene. After adding 3.4 parts of titanium tetrabutoxide, the The reaction mixture is heated to a gentle boil for 1 to 2 hours, while stirring, until the titanium tetraiodide is present Investigation of the solubility

The solubility of the various alkoxytitanium triiodides was determined in toluene, one for polymerization of butadiene very suitable solvent, determined to make the difference to titanium tetraiodide and some other titanium compounds as well as the influence of the chain length of the alcohols used to indicate the solubility. The solubility of titanium tetraiodide when added was also used for comparison various alcohols in a molar ratio of 1: 1

Measured standing for 24 hours. The stated values were determined by titrimetic content determinations of the saturated solutions as well as by analyzing and determining the residues.

solubility Tempe
rature
° C in toluene 20th Weight
percent 22nd TiJ ₄ 0.25 21 TiI ₄ + nC ₁₂ H ₂₅ OH 8.1 21 TiI ₄ + nC ₄ H ₉ OH 6.8 21 (nC ₁₂ H ₂₅ O) TiI ₃ 30.6 22nd (HC ₈ H ₁₇ O) TiI ₃ 20.6 20th 0-C ₈ H ₁₇ O) TiI ₃ 21.0 23 01-C ₄ H ₉ O) TiI ₃ 17.5 22nd (C ₂ H ₅ O) TiI ₃ 17.0 23 (CH ₃ O) TiI ₃ 1.5 22nd (C ₄ H ₉ OCH ₂ CH ₂ O) TiI ₃ 1.2 20th (/ H ^y > OJTiJ ₃ 13.3 20th [CH ₃ (CH ₂ ) ₇ CH = CH (CHu) ₇ - COO] TiI ₃ 8.1 (C ₁₇ H ₃₅ COO) TiI ₃ 7.2

Example 1 Catalyst Preparation and Polymerization

In a stirred vessel with exclusion of air and moisture, 0.61 part (nC ₁₂ H ₂₅ O) TiI ₃ and 0.79 part aluminum ^{triisobutyl were added to 1000 parts of anhydrous toluene at a temperature of 0} ° C., a black-brown catalyst solution being formed.

To test the polymerization activity of the catalyst solution, 100 parts of butadiene were passed in at ⁰ ° C. The increase in the viscosity of the solution showed that the polymerization started immediately. The temperature was kept between 20 and 25 ° C. After 7 hours, the polymerization was terminated by adding 2 ^ parts of a phenolic stabilizer and 2 parts of ethanolamine in a little methanol, and the polymer was precipitated with methanol and dried at 50 ° C. in vacuo. 100 parts of polybutadiene with a viscosity of 4.4 were obtained.

The infrared spectrum showed the following structure, ice: 92.5%; trans: 0.9%; 1.2: 6.6%.

Example 2

Under the same conditions as in Example 1, the polymerization activity became a series of others Catalytic converters checked. Catalyst compositions and polymerization results are in Table I. compiled.

Example 3

A series of further experiments were carried out under the conditions of Example 1, the mode of action of the catalysts was thereby determined by adding olefins (isobutylene, diisobutylene, 1-vinylcyclohexene-3, styrene) and organic halogen compounds 0-C ₃ H ₇ I, iC ₃ H, Cl, nC ₄ H ₉ Cl, nC ₁₂ H _Z6 J, CHCl ₃ , CHJ ₃ , benzyl iodide, cyclohexyl iodide) changed, the molecular weights of the polymers obtained being reduced. The results of the tests are shown in Table II.

Table I.

Titanium compound Parts Al connection Parts the end
prey Polymeri
sation duration η IR spectrum, "/" trans 1.2 % hours ice cream 1.0 11.2 [CH ₃ (CH ₂ ) ₇ CH = CH (CH ₂ ) ₇ COO] TiI ₃ 0.71 Al (iC ₄ H ₈ ) ₃ 1.2 100 7th 3.5 87.8 1.2 5.4 (nC ₁₂ H ₂₅ O) TiI ₃ 0.61 Al (iC ₄ H ₉ ) ₃ 0.92 100 6th 3.6 93.4 1.2 7.1 (HC ₁₂ H ₂₅ O) TiJ ₃ Ο 0.61 Al (iC ₄ H ₈ ) ₃ 0.9 100 5 2.1 91.7 1.4 8.9 OvC ₁₂ H ₂₅ O) TiJ ₃ 0.61 Al (iC ₄ H ₉ ) ₃ 1.55 50 7th 3.3 89.7 0.9 7.8 (nC ₈ H ₁₇ O) TiI ₃ 0.42 Al (iC ₄ H ") ₃ 0.51 90 6th 4.3 91.3 0.9 6.9 (HC ₈ H ₁₇ O) TiI ₃ 0.40 Al (iC ₄ H ₈ ) ₃ 0.75 100 4th 4.0 92.2 2.8 10.7 (nC ₈ H ₁₇ O) TiI ₃ 0.40 Al (C ₄ H ₉ ) H ₂ 0.51 60 6th 4.5 86.5 2.1 8.5 (nC ₈ H ₁₇ O) TiI ₃ 0.41 Al (C ₂ H ₅ ), 0.45 69 6th 4.0 89.4

*) The catalyst was prepared with the addition of 0.16 parts of isopropyl chloride.

Table 1 (continued)

10

Titanium compound Teüe Al connection Parts the end
prey
% Polymeri
sation duration
hours V IR-
cis Spectn
trans in the "/.
1.2 (nC ₈ H "O) TiJ ₃ ^a )
Cn-C ₄ H ₉ O) TiI ₃
(CH ₃ O) TiI ₃ 0.43
0.38
0.34 Al (iC ₄ H ₉ ) ₃
Al (iC ₄ H ₈ ) ₃
Al (iC ₄ H ₉ ) ₃ 0.82
0.80
0.78 45
100
100 8th
4th
7th 3.3
4.0
4.3 87.6
92.3
89.2 2.6
0.4
2.7 9.8
7.3
8.1 (Xj ³ / - ^O ) ^TiJ 3 0.4 Al (iC ₄ H ₉ ) ₃ 0.78 92 5 3.7 90.2 1.2 8.6 (C ₄ H ₉ OCH ₂ CH ₈ O) TiI ₃
(C ₂ H ₅ O) TiI ₃ 0.41
0.24 Al (iC ₄ H ₉ ) ₃
Al (iC ₄ H ₉ ) ₃ 0.75
0.42 70
100 8th
4th 3.4
4.5 90.5
92.1 0.8
1.0 8.7
6.9 TiJ ₄
C ₁₂ H ₂₅ OH 0.55
0.18 j Al (iC ₄ H ₉ ) ₃ 1.28 100 6th 2.9 90.7 2.1 7.2

·) The catalyst was prepared in n-hexane instead of toluene.

Table II

catalyst additive - Teüe yield
% Polymeri
sation duration
hours Mooney
(ML 4 ',
100 ⁰ C) IR spectrum
ice I trans 1.0 ,%
1.2 CHJ ₃
Benzyl iodide
Cyclohexyl iodide 100 5 85 91.2 0.6 7.8 Vinyl cyclohexene 1.0 100 4.5 38 91.1 0.6 8.3 Isobutylene 0.15 100 5 54 92.7 1.2 6.7 Isobutylene 0.30 100 4th 38 89.6 1.3 9.2 Diisobutylene 0.44 100 7th 52 91.6 - 7.1 0.42 parts (nC ₈ H ₁₇ O) TiI ₃ Styrene 0.52 80 5 65 89.1 1.6 - 0.78 parts Al (iC ₄ H ₉ ) ₃ iC ₃ H ₇ J 0.50 100 5 52 92.3 1.7 6.1 1-C ₃ H ₇ Cl 0.12 100 4.5 64 88.1 1.0 10.2 nC ₄ H ₉ Cl 0.14 80 5 68 90.2 0.8 8.8 HC ₁₂ H ₂₅ J 0.91 90 5 33 90.9 1.0 δ 3
8, J. CHCl ₃ 0.09 100 5 31 90.8 1.4 8.2 - 100 4th 73 91.3 0.9
1.9
1.2 7.3 0.38 parts (nC ₄ H ₉ O) TiI ₃
0.82 parts Al (iC ₄ H _fl ) ₃ 0.29
0.87
0.84 80
100
60 6th
8th
5 54
45
43 91.0
89.4
91.3 8.1
8.7
7.5

Claims (2)

Patent claims: 1. Process for the preparation of hydrocarbon-soluble mixed catalysts for the polymerization of 1,3-butadiene by reacting aluminum trialkyls and / or mono- or dialkylaluminum hydrides, the alkyl groups of which contain 1 to 20 carbon atoms, with titanium-iodine compounds, with the exclusion of air and Humidity at a temperature between -10 and + 50 ° C, characterized in that the titanium-iodine compounds are titanium alkoxy triiodides of the formula Ti (OR) J ₃ , in which R is a straight-chain or branched aliphatic, cycloaliphatic or araliphatic hydrocarbon radical with 1 to 20 carbon atoms means used and, if appropriate, the mixed catalysts Halohydrocarbons or «-olefinic hydrocarbons in amounts of 0.5 to 20 mol per Moles of titanium compound added. 2. The method according to claim 1, characterized in that the Titanalkoxytrijodide together with such amounts of organoaluminum compound used that the molar ratio of titanium compound to aluminum compound is between 1: 2 and 1:20. 409 539/593 3.64 © Bundesdruckerei Berlin