DE1570286B2 - Process for the preparation of copolymers containing high cis-1,4-proportions of butadiene with styrene or alpha-alkylstyrenes - Google Patents

Description

1 2

The invention relates to a process for the production or corpuscularly dispersible catalyst com of high cis-1,4-fractions containing copolymers - lead to reproducible results. After the combination under low pressure. 5 interpolymerization, the catalyst combi-known are numerous processes for the production of nations from the polymers by washing with copolymers of butadiene-styrene or alcohol can be easily separated, but the butadiene-α-alkylstyrene, with the following catalyst separation also in elimination come because the catalyst systems were used: alkyllithium connector usually only used in very small quantities, lithium and sodium metals, trialkyl * ° and z. B. with alcohol or alcohol aluminum-titanium tetrachloride ^ aluminum metal-mercury-ketone or the like. Can be inactivated.
silver (II) chloride-cobalt (II) chloride, molybdenum-aluminum b) The mixed polyminium hydride-calcium hydride and Friedel-Craftsmeres produced according to the invention have a cis-1.4 proportion of at least 1 and 2 radical catalysts. 80% and practically no or only very little. When using these catalyst systems, the gel content amounts to 15 and are obtained in a stable form, but - with the exception of the catalyst system - without being affected by the ratio of the three catalyst-aluminum metal-mercury (H) -chloride-cobalt (II) - components, the type of catalyst preparation and chloride - the cis-1,4-proportion in the resulting mixture- the interpolymerization conditions influences werpolymeren to below about 60 ° / ₀ (under "cis-1,4-proportion". This is one of the most important features of the is the corresponding value, based on the butadiene-20 new catalyst combinations.
to understand units). The aluminum catalyst system c) The molecular weight of the mixed minium metal-mercury ^ I ^ -chloride-cobalt ^^ - chlopolymeren can be rid of by changing the conditions to produce a butadiene mixed polymer of the catalyst production and the copolymers with a relatively high content of ice - sation can be set. Rubbery 1,4-butadiene portion has been applied; However, since all three interpolymers with a high molecular weight can be easily averaged insoluble in organic solutions in organic solutions through a two-stage interpolymerization, each component can only be prepared as will be explained below,
difficult to handle, so that the preparation of the The amount of homopolystyrene in the copolymer catalyst combination is cumbersome and it is difficult to prepare similar combinations by suitable selection of the polymerization. 30 conditions, practically polystyrene-free products can be obtained.

consists in the development of a process for cooking d) The copolymers obtained have better

position of high ice-1,4-components containing mixed heat aging properties and greater hardness than

polymers of butadiene with styrene or «-alkyl cis-1,4-polybutadiene with the same modulus value, where-

styrenes through interpolymerization by means of ternary 35 through them are able to increase the rigidity of the tire

Catalyst combinations under low pressure to prevent deformation when cornering by improving

Production of high cis-1,4-parts containing the hardness of the tire compound without reinforcing

Copolymers of butadiene with styrene or their resistance to the growth of ab-

oc-alkylstyrenes, such as α-methyl, α-ethyl or α-pro tendency to use, which reduce the tear resistance of the tires

pylstyrene, influenced by interpolymerization by means of ternary 40, is reduced.

Catalyst combinations under low pressure. Examples of the Α component of the catalyst

It has already been suggested certain, for which combinations are:

Homopolymerization of butadiene known three- 1. Nickel or cobalt carboxylates of the formula component η catalysts (cf. German Auslege- (R - CO · O - ) _n M, where R is a monovalent carbon fonts 1130172 and 1158 715) for mixed poly- 45 hydrogen radical , M is nickel or cobalt and η is the merization of butadiene with styrene or «-alkyl valency of M, ie to use salts of aliphatic, styrenes and in this way butadiene, acyclic or aromatic carboxylic acids with copolymers with high cis-1,4 -Proportion to establish. 1 to 20 carbon atoms, e.g. B. the formate, acetate, 2-ethyl-The process according to the invention is characterized by hexoate, palmitate, isooctoate, stearate and oxalate of the fact that the ternary catalyst used is nickel and the naphthenates and benzoates of combinations of reaction products of nickel and cobalt .

A. a carboxylate or an organic grain 2. Of organic complex compounds are plex compound of nickel or cobalt, hydroxyketone complex compounds, such as acetylace

B. a chloride or oxychloride of titanium, zirconium clay-nickel and cobalt; Hydroxyester Complex Compound or vanadium and 55 bonds, such as acetoacetic ethyl ester-nickel and -Ko-

C. an organometallic compound of lithium, bait; 8-hydroxyquinoline complex compounds, such as zinc, cadmium or aluminum of the formula 8-hydroxyquinoline-nickel; Hydroxyaldehyde-Kom-R _n M, where R is a monovalent hydrocarbon complex, such as salicylaldehyde-nickel and -corest and η is the valence of the metal M, bait, as well as salicylaldehydeimine-nickel and carbonyl

in the presence of a diluent at temperature 60 complex compounds such as nickel tetracarbonyl. These doors between -30 and + 150 ° C under low pressure. Nickel compounds are used against cobalt in the liquid phase and in an inert atmosphere. compounds preferred, especially 2-ethylhexoate _s .

The catalyst com-tsooctoate, stearate or naphthenate of nickel used according to the invention,
combinations differ significantly from the B-components of the catalyst combinations

The above-mentioned catalyst combinations and have 65 serve primarily titanium-zirconium and vanadium tetra the following advantageous features: chloride or vanadium oxytrichloride; Titanium tetrachloride

a) At least two of the three components are preferred,
Soluble in organic solvents. The soluble As a C component of the catalyst combinations,

3 4

the hydrocarbon radical alkyl, aryl, aralkyl recovery of mixed polymers of various types, or contains cycloalkyl groups, preferably serve as random block and / or graft copolymers, Triethyl, tripropyl, triisobutyl, tributyl, triiso- are used.

butyl-, trihexyl- and triphenylaluminum, diethyl- According to one embodiment, the mixed poly-

and dibutyl zinc, diethyl cadmium and butyllithium; 5 merization carried out in one step by using both mono connections Triäthyl- and triisobutylaluminum mers and the diluent at the same time in the are preferred. Catalyst system are introduced. After a

These catalyst components have another embodiment, the polymerization is surprisingly carried out in two stages, namely in the first stage for the cis-1,4-butadiene copolymerization, as is the butadiene polymerization at a temperature of itself for the cis-l, 4-butadiene homopolymerization about -30 to about +150 ⁰ C, preferably about 0 to according to patents 1214002 and 1213120 proved to approximately + 8O ⁰ C, and then a styrene nachZusatz had. Interpolymerization at a temperature of about

Preferred catalyst combinations are made 0 to about 150 ⁰ C, preferably about 30 to about 120 ° C. of the following: ¹ S In both cases, the pressure must be sufficient to

Nickel naphthenate-titanium tetrachloride-triethyl or to keep the conversion system in the liquid phase. Triisobutylaluminum, nickel-2-ethylhexoate-titanium- By means of the two-stage copolymerization metrachloride-triethyl- or triisobutylaluminum, preferred copolymers can be obtained kelisooctoate-titanium-tetrachloride-triethyl- or triiso- aluminum, with butadiene-stearate-triisobutylium-triisobutylium being very satisfied with a triisobutylaluminum - 2 ° setting speed to a polymer with ethyl- or triisobutylaluminum, nickel benzoate- an intrinsic viscosity of at least 1.0 converted titanium tetrachloride-triethyl- or triisobutylalumini-, whereas the styrenes compared to butadiene to, acetylacetone-nickel-titanium tetrachloride-triethyl- slowly copolymerize; however, the mixture of titanium tetrachloride, triethyl or triisobutylaluminum, can be increased at the rate of polymerization by increasing the polymerization temperature or triisobutylaluminum, acetoacetic ethyl ester nickel.
8-hydroxyquinoline nickel-titanium tetrachloride-triethyl- Die two-stage, especially with a catalyst

or triisobutylaluminum cobalt naphthenate titanium combination consisting of a carboxylate salt or a tetrachloride-triethyl- or triisobutylaluminum, co-organic complex compound of nickel, titanium baltic benzoate-titanium tetrachloride-triethyl- or triisotetrachloride and trialkylaluminum, butylaluminum, acetoacetic ethyl ester nickel-vanadium- 30 obtained copolymers are usually chewing oxytrichloride-triethyl- or triisobutylaluminum, chuk-like solids with intrinsic viscosities of nickel naphthenate-titanium tetrachloride-diethylcadmium about 1.0 to 5.0, the products obtained in one step and nickel naphthenate-titanium tetrachloride-butyllithii, on the other hand, mostly sticky solids. The mixed poly

The mixing ratio and the mixture mers have cis-1,4 'proportions of 80% or more; the temperature of the catalyst components when using a catalyst combination the interpolymerization. It is preferred to consist of a carboxylate or an organic one a molar ratio of the Α component to the C-component complex compound of nickel, titanium tetrachloride component of about 0.5 to 3.0, preferably about 0.8 to and trialkylaluminum, the content is ge-2.0, and a molar ratio of the C component to the homely to 90 to 98%.

B component from about 0.3 to 5.0, preferably 40. The cis-1.4 component of the butadiene units and the about 0.7 to 2.5. Content of styrene or -alkylstyrene in the copolymer

The catalyst combinations are infrared spectroscopy, the solvents Grenzviskosiorganischen determined mostly be soluble or in certain activities in toluene at 30 ⁰ C. The gel content of the cases is corpuscularly dispersible; The mixing of copolymers is done by filtering the benzene three components usually in a 45 solution through a sieve with a mesh size inert atmosphere in an anhydrous, liquid of 0.075 mm and is usually zero.
Hydrocarbon solvents or diluents, to facilitate control of the Mischpolymerisationsüblicherweise at a temperature between about process is usually a diluent -50 and + 8O ⁰ C, preferably applied between about -5, usually within 40 volume percent and + 4O ⁰ C. Optionally can after preparation 5 ° from the monomer mixture. As a dilution or for the purpose of modifying the catalytically active solvent for the catalyst, aromatic speed, aging or heat treatment by hydrocarbons, such as benzene, toluene and xylene; be guided. If the new catalyst aliphatic hydrocarbons, such as pentane, hexane, combinations are stored at room temperature, what remains is heptane, isooctane and gasoline; Alicyclic carbon whose activity over a longer period of time 55 hydrogenated, such as cyclohexane and decalin, hydrogenated unchanged. It is advisable not to bring the aromatic hydrocarbons, such as tetra and deca catalyst combinations, into contact with water and hydronaphthalene, diisopropyl ether and mixtures of oxygen, but the effect of these is such solvents. Aliphatic hydrocarbons on the copolymerization activity and the stiff or their mixtures with aromatic Kohlericis-1,4-formation activity of the catalyst system not 60 are water-resistant for the production of mixed polyas as strong as with the Ziegler and lithium catalysts with high molecular weight, on the other hand they are aromatic. table hydrocarbons and their mixtures with

The amount of catalyst used is not from aliphatic hydrocarbons, such as toluene isobespecialists Meaning; it is usually min-octane, preferred for solution copolymerization, at least 0.5 mmol to 1.0 mol of the total amount of 65. The solvents or diluents should - ge monomers. just like the monomers - of course free of

To carry out the copolymerization, catalyst poisons such as oxygen and water can be,
various interpolymerization processes under The separation of the catalyst from. Mixed poly

meren can be done in the following ways:

After completion of the reaction, a small amount of phenyl-ß-naphthylamine is optionally used Solvent added to completely dissolve the copolymer or to reduce the viscosity of the reaction mixture, and then dipping the mixture into a large amount of a nonsolvent, such as methanol, isopropanol or methanol-acetone, poured in to precipitate the copolymer. The means of the three-component catalyst nickel-2-ethylhexoate-titanium tetrachloride-triethylaluminum The raw copolymers obtained initially have a brown color due to the remaining Catalyst, but gradually turns white after multiple washes with methanol.

The rubber-like copolymers obtained can be incorporated by any method Usual reinforcing agents, vulcanization accelerators, fillers and other additives are mixed up.

example 1

0.48 mmol of nickel 2-ethylhexoate are mixed with 0.28 mmol of titanium tetrachloride in a 360 ml pressure bottle which has previously been flushed with dried nitrogen and charged with 45.6 ml of anhydrous toluene, whereupon the mixture is kept at room temperature for 10 minutes is left standing; then 0.4 mmol of triethylaluminum is added. The catalyst obtained is kept for another 20 minutes at room temperature, then cooled to -40 ⁰ C and treated with 0.2 moles of liquefied butadiene under nitrogen. The bottle is now sealed and kept rotating ^{in a thermostat at 40 ° C. for 10 hours.} Then are added to 0.47 mol of styrene under nitrogen and stirred for 15 hours at 6O ⁰ C. The polymerization is stopped by adding a small amount of a methanol solution of phenyl-beta-naphthylamine, the obtained polymer was washed with methanol and dried in vacuo.

Yield 7.7 g of a rubbery polymer, intrinsic viscosity 2.10, no gel content. Infrared analysis yielded 12.5% styrene (based on total polymer) as well as 92.1% cis-1,4-, 3.6% trans-1,4-, and 4.3% Vinyl content (based on butadiene content). For the purpose of checking whether the styrene component matches the butadiene component is copolymerized, 3.0 g of the copolymer are dissolved in 200 ml of η-hexane and placed in a separating funnel Washed several times with 150 ml of N, N'-dimethylformamide, if necessary with the polymer extract mixed homopolystyrene; it was found that 80% of the styrene with the Butadiene were copolymerized.

Examples 2 and 3

The following results are obtained according to Example 1, but using 0.4 mmol of nickel 2-ethylhexoate obtain:

example

Butadiene

Styrene

Mole

yield
G

viscosity

Od

Styrene

O/ /O

Butadiene content in%
trans I.

vinyl

0.2
0.2

0.2
0.47

3.2
5.4

2.33
2.08

Example 4

The polymerization is according to Example 1 using 0.25 mol of butadiene and 0.25 mol Styrene and 0.6 mmol of nickel 2-ethylhexoate, 0.25 mmol of titanium tetrachloride, 0.5 mmol of triethylaluminum and 57.3 ml of anhydrous toluene carried out, namely the first stage 6.5 hours at 40 ° C and the second stage after adding the styrene for 15 hours at 60 ° C. Yield 5.0 g, intrinsic viscosity 2.22, gel-free. Infrared analysis showed 5.8% styrene (based on total polymers) and 92.2% cis-1,4-, 4.0% trans-1.4 and 3.8% vinyl shares (based on butadiene content).

Example 5

The polymerization is according to Example 4, from 1.0 mmol of nickel-2-ethylhexoate with a catalyst consisting, 0.35 millimoles of titanium tetrachloride and 0.5 mmol of triethylaluminum performed, namely the first step for 16 hours at 4O ⁰ C and after addition of styrene 10 hours at 60 ⁰ C. The mixed polymer obtained has an intrinsic viscosity of 2.40 and is gel-free. Infrared analysis showed 3.4% styrene (based on total polymer) and 90.4% cis-1.4, 5.5% trans-1.4 and 4.1% vinyl components (based on butadiene content).

Examples 6 and 7

The procedure is as in Example 1, but using 57.3 ml of anhydrous toluene as well

4.3
18.5

90.9
92.1

4.4
4.4

4.7
3.6

the following catalyst compositions:

example

Ni-naphthenate
mmol

0.6
0.4

TiCl ₁

0.5
0.5

A1 (C, H ₅ ) ₃

0.5
0.5

Ni / Al molar ratio

1.2
0.8

The polymerization is carried out with 0.25 mole of butadiene and styrene 6.5 hours at 4O ⁰ C in the first stage and 15 hours at 6O ⁰ C after the addition of the styrene. The following results are achieved:

At-
psiel the end
prey
G Visco
sity
to) gel
% Styrene
7o Butadienant
ice I trans
% 4.6
5.3 Hurry
vinyl 55 ₆
7th 10.0
15.0 1.10
0.70 0
0 11.8
22.1 91.2
90.1 4.2
4.6

Example 8

The catalyst is prepared according to Example 1 from 0.7 mmol of nickel acetoacetic ethyl ester, 0.5 mmol of titanium tetrachloride and 0.5 mmol of triethylaluminum and 57.3 ml of anhydrous toluene Hours carried out at 6O ⁰ C after the addition of the styrene. Yield 5.1 g, intrinsic viscosity 1.59, gel-free. Infrared analysis showed 2.4% styrene (based on total polymer) and 91.0% cis-1,4-,

5.6% trans-1,4 and 3.4% vinyl shares (based on butadiene content).

Example 9

The catalyst is prepared according to Example 8 with the exception that instead of nickel acetoacetic ethyl ester, nickel-8-hydroxyquinoline is used. The polymerization lasts 20 hours at 40 ^° C. in the first stage and 10 hours at 60 ^° C. after the addition of the styrene. The mixed polymer obtained has an intrinsic viscosity of 1.79 and is gel-free. Infrared analysis showed 3.8% styrene (based on total polymer) and 89.1% cis-1,4, 7.0% trans-1,4 and 3.9% vinyl shares (based on butadiene).

Example 10

The catalyst is according to Example 1 from 0.32mMol Nickel-2-ethylhexoate, 0.28 mmol of titanium tetrachloride, 0.4 mmol of triethylaluminum and 45.6 ml of water

IO free of toluene, then the bottle to - 40 ° C then cooled and a mixture of 0.2 mol of liquefied butadiene, and 0.05 mol of styrene introduced under nitrogen, then the vessel is gas-tight manner and in a thermostat for 25 hours at 4O ⁰ C rotated . Yield 1.9 g, intrinsic viscosity 0.68, gel-free. Infrared analysis showed 2.2% styrene (based on total polymer) and 91.7% cis-1,4, 4.4% trans-1,4 and 3.8% vinyl shares (based on butadiene content).

Examples 11 and 12

According to Example 1, catalysts are obtained from 1.0 mmol of a nickel compound, 1.0 mmol of titanium tetrachloride and 1.0 mmol of triethylaluminum and 57.3 ml of anhydrous toluene. The polymerization is carried out according to Example 10 in 25 hours at 4O ⁰ C with a monomer mixture of 0.25 mol of liquefied butadiene, and 0.25 mol of styrene. The results are as follows:

example Component A yield
G viscosity
(η) gel
7o Styrene
° / o Butadiene components
ice I trans | vinyl
% 10.4
9.3 3.6
3.9 11th
12th Ni benzoate
Ni-acetylacetone 8.2
1.5 0.2
0.6 0
0 15.6
5.3 86.0
86.8

Claims (3)

Patent claims: 1. Process for the production of high cis-1,4-proportions containing copolymers of butadiene with styrene or α-alkylstyrene by copolymerization using ternary catalyst combinations, characterized in that one is used as the ternary catalyst combinations Conversion products of A. a carboxylate or an organic complex compound of nickel or cobalt, B. a chloride or oxychloride of titanium, zirconium or vanadium and C. an organometallic compound of lithium, zinc, cadmium or aluminum of the formula R _n M, where R is a monovalent hydrocarbon radical and n is the valence of the metal M, in the presence of a diluent at temperatures between -30 and + 150 ° C below Low pressure in liquid phase and inert atmosphere used. 2. The method according to claim 1, characterized in that one catalyst combinations, in which the molar ratio of A to C is about 0.5 to 3.0, preferably about 0.8 to 2.0, and from C to B is about 0.3 to 5.0, preferably about 0.7 to 2.5, is used. 3. The method according to claim 1 and 2, characterized in that in a first stage the Butadiene polymerizes and in the second stage the polybutadiene obtained with a styrene copolymerized. 009 541/376