DE1570779C - Process for the preparation of cis-1,4-polybutadiene - Google Patents

Description

1 2

■ The invention relates to a method for manufacturing added and the product has been subjected to a Alterungsvon polybutadiene with a high content of cis treatment at 20 to 100 ⁰ C formed. 1,4 structure using a novel invention, the fourth component must be added to the catalyst, which is soluble in hydrocarbons, before the first and third components have a high activity and the component in the layer has reacted with one another. For example, the molecular weight of the polymer is to be re-gels the catalyst components in the. Standing orders mixed together:

It is derived from British patent specification 905 099 ... _. .

knows that one can produce polybutadiene with a high content (1) The second component can be made into the first cis-1,4 structure, if one adds butadiene io, then one gives the fourth and finally in the liquid phase together with a catalyst - ^{add the third} component,
brings the (1) from at least one nickel salt a (2) the fourth component is given to the first ge-carboxylic acid or from organic complex compounds, then the third and finally fertilize the nickel, (2) from at least one compound add the second component,
bond, such as Borfiuorid or its Komplexverbin: i _{5 (3) The} third component is hired to the second, and (3) _b of at least one organometallic _{Dami one ibt the yierte and schließl} f _ch of an alkali metal or a metal compound of _{DJE first Com te add>}
Group II or IH of the periodic table.

The process is suitable for the production of Furthermore, in the production of the Kataly-Polybutadiene with a high content of cis-1,4-Struk- sators according to the invention, the mixture from this door in high yield, but it can be in some four Components at a temperature of 20 to points can still be improved. In particular, the 100 ^° C., preferably from 30 to 80 ^° C., the catalyst used in this process is not. The aging time also depends on others completely soluble in the hydrocarbon, ie it depends on the conditions, but is generally given in concentrated solution a black lower case for a few minutes to a few hours,
blow; Although it appears to be soluble in dilute solution, it shows the appearance of tyndallene and aging are the indispensable effects. Does a polymerization system contain great conditions in the preparation of the amounts of impurities according to the invention or is the monomer used as a catalyst. By using this concentration low, the activity is lowered. Conditions now make it possible to use this catalyst during the polymerization. catalytic converter soluble in a hydrocarbon solvent

From the German Auslegeschrift 1104 703 is a lysator with an extremely high activity for the Process for the production of polybutadiene with polymerization, which is capable of the high content of cis-1,4 structure through polymerization, molecular weight of the polymers easy to regulate ' in the presence of a solution in hydrocarbons 35 For example, it is impossible to use a catalyst Catalyst from metal alkyl compounds and Ver to obtain the properties given above, bonds or complex compounds of metals if the order of addition is changed in such a way that of the VIII. Group of the Periodic Table. that the fourth component after mixing the To regulate the molecular weights, the poly- three other components are added or that merization in the presence of -olefins or not 4 ° the fourth and the second component after the reconjugated Diolefins carried out. Purpose of setting the first with the third component to the invention is creating a process by which to be given.

a high molecular weight butadiene polymer with the help of the British patent 905 099

a catalyst obtained among the known three-component catalyst

specified conditions a sufficiently high 45 one in concentrated solution a black

Has activity in the polymerization, in which the precipitate; the catalyst seems to be in

Dissolving expensive organometallic compounds or boron fluoride in dilute solution shows all in one

a smaller amount can be used and hydrocarbon solvents have the Tyndall effect,

which further solves the regulation of the molecular weight of the catalyst to be used according to the invention

Polymer facilitated. 50 however, at the last aging carried out,

The invention thus relates to a method even if the first component is insoluble, or

for the production of cis-1,4-polybutadiene by stereo- if by reacting the first with the second

selective polymerization of butadiene in liquid component a precipitate was formed, and

Phase and in the presence of a catalyst system, which shows the catalyst obtained as the end product

from at least one nickel salt of a carboxylic acid 55 no Tyndall effect.

or from an organic complex compound of the The catalyst solution is composed of three components

Nickel as the first component (A), from BF ₃ or brown or black, while the solution of the Katadessen complex compounds as the second component. lysators made up of four components is yellow or orange.

nent (B) and made of at least one organometallic Therefore the colors of the two catalyst compound an alkali metal or a metal of the 60 solutions, d. H. the absorption spectra in the visible

Group II or III of the periodic table as third light, different from each other. It is believed that

Component (C) was obtained. The process is complex compounds with both catalysts

characterized in that the polymerization is the central nickel atom. It is generally an-

carries out in the presence of a catalyst, recognized that the color of the metal complex production as the fourth component (D) a conjugation with the valency level of the central atom

gated, aliphatic diolefin has been used, or changes with the nature of the surrounding ligand,

component D being the catalyst system. For these reasons, it is believed that it is

the implementation of the first with the third component in the present catalyst to a complex

3 4

Compound that is produced by the catalyst from component (an aliphatic hydrocarbon with two

distinguishes between three components. conjugated double bonds), different. Ver

The present catalyst is capable of using a one in place of a nickel compound such as

larger amount of polymer per unit weight of catalyst in the catalyst according to the invention a 'cobalt

lysator and to be generated per unit of time, d. i.e., if you have 5 connection, you can do the above

does not receive much greater polymerization properties with it. Second, after the

speed for a given amount of catalyst, each component of the catalyst

than with a three-component catalyst. sators added in a set order, and

Furthermore, it can be used in many cases to poly- the catalyst is formed by aging

merizates with a higher molecular weight produced in the case of a mixture. By setting the al-

the molecular weight can be measured at a higher rate of polymerization than with the tempering temperature

the catalyst obtained from three components. It's easy to regulate the polymers, and the catalyst

It should also be mentioned that the polymerization reaction causes a significantly higher polymerization

tion using such a small amount of speed.

Catalyst takes place in which with the catalyst from 15 The above-mentioned method thus has the three components no polymer would be formed. Features of the present procedure do not appear. In this way it is possible to reduce the amount of more expensive The first component of the organometallic compound or boron fluoride used according to the invention consists of at least a gene unit polybutadiene, and a nickel salt of a carboxylic acid or a molecular polymer with a sufficient amount 20 organic complex compounds of nickel, such as speed, even if the poly-nickel formate, nickel acetate, nickel octenate, nickel merization system contains large amounts of impurities naphthenate, nickel stearate, nickel benzene, nickel or if the monomer concentration is very carbonyl, nickel salicylaldehyde, nickel acetylacetone, low. Furthermore, the nickel acetoacetate, bis- (a _: furyldioxime) -nickel and the remaining catalyst residue in the polymers are so small that the desired effects on the properties and the compounds are some in the appearance of hydrocarbon solutions of the product can be avoided. agents insoluble. However, they are well ground with

As the physical properties and the three other components in the specified

workability of cis-1,4-polybutadiene very mixed up from its sequence and aged sufficiently, see above

Molecular weight is affected, it is important to gradually dissolve it.

to regulate the molecular weight of the polymer. The second component comprises boron fluoride or the process according to the invention is a regulation of its complex compounds, for example Bordes molecular weight of the polymer easily by fluoride etherate. ■ ^c . Change of aging temperature possible. Here, the third component comprises at least one, the organometallic compound of an alkali metal or measured intrinsic viscosity in toluene at a temperature of 30 ° C can be varied easily in the range of 0.5 of a metal of group II or HI of the period to 6.0 if one the aging system, such as butyllithium, amyl sodium, diethyl zinc, temperature varies between 20 and 100 ° C / In this diethyl cadmium, triethyl aluminum, diethyl aluminum case, up to a certain temperature, the mol- nium fluoride and diethyl aluminum chloride are. The molecular weight of the polymer formed is as high as 40. The fourth component of the catalyst is higher, the higher the aging temperature. aliphatic hydrocarbons conjugated with two

Furthermore, it is favorable that the change in the double bonds, such as butadiene, isoprene and di-polymerization rate in some methylbutadiene.

The aging temperature range is low, although the catalyst is usually used in amounts of

this value is related to the types and proportions of 45 0.025 to 2.6 mg atoms of nickel (based on the first

Catalyst components changes. Therefore, component) can be used per 100 g of butadiene. The arrival

Without the rate of polymerization, significant parts of the individual catalyst components are like

worth changing, the molecular weight of the poly follows: 0.02 to 2 moles of component 1, 0.2 to 10 moles

merisate by changing the aging temperature of component 2 and 0.2 to 20 mol of component 4

regulate in this area. 50 per mole of component 3.

In the German Auslegeschrift 1115 024, the individual components are preferably mixed in the form of their hydrocarbon solutions for stabilizing a catalyst. As written, in which a diolefin is brought into contact with a catalyst hydrocarbon solvent, aroma is brought into contact with the combination of hydrocarbons such as benzene, toluene or a diethylaluminum halide AlR ₂ X, 55 xylene, aliphatic hydrocarbons such as pentane, where R is a Alkyl radical and X represents a halogen atom, hexane or heptane, or alicyclic carbon dioxide, with a substance soluble in hydrocarbons, such as cyclohexane and decahydronaphthalene. Complex compound of a cobalt salt was obtained. This process is an attempt to maintain the catalyzed polymerization temperature with the liquid state in the table activity over a long period of time and in the presence of a carbon by adding a diolefin to the hydrogen solvent to be polymerized Buaus AlR ₂ X and the tadiene soluble in hydrocarbons. The preparation of the complex compound of the cobalt salt existing catalyst and the polymerization must exist in a catalyst. Inert gas such as nitrogen, helium or carbon dioxide,

The method according to the invention distinguishes 65 to be undertaken. -,

differs significantly from the procedure mentioned, and one can use the same Kotilenwasserstöfflösuhgs-

In the following points: Once there are the catalysts, as is the case with the manufacture of the catalyst

satellite components, with the exception of the fourth grain, were used as polymerization

turn. The polymerization temperature is -20 to +150 ⁰ C, but it draws a polymerization temperature of 0 to 100 ⁰ C before, if one wishes to obtain polymers with a high proportion of cis-l, 4 units.

The polymerization can, if desired, by adding a reaction inhibitor such as water or alcohol or amines.

You can add the solid polymer either by adding a larger amount of alcohol to the polymer solution or obtained by removing the solvent with water by azeotropic distillation. An antioxidant, such as phenyl-ß-naphthylamine, can also be added to the solution of the polymer to add. If necessary, you can also add an extender oil or other chemicals.

The catalyst used according to the invention is extremely active and is sufficient for even in small amounts the polymerization from, which is why the catalyst residues cannot be removed from the polymers formed needs.

The polymer formed usually contains more than 90% aes-1,4 units, as in the method according to D. M ο r e r ο (La Chimica e L'industria, 41, p. 758 [1959]) can be determined analytically. It is even possible to obtain butadiene polymers with more than 97% cis-1,4 units. According to the invention The butadiene polymer obtained can be provided with additives and shaped by processes known per se and be vulcanized; it can be used for different Use for purposes such as tires, belts, or inner tubes.

In the examples, the intrinsic viscosity [η] was determined at 30 ^° C. in toluene.

B e i% ρ ie 1 e 1 to 3

Nickel naphthenate (0.01 mg atom of Ni), dissolved in 5 ml of toluene, is placed in a pressure-tight reaction tube filled, whereupon 0.136 mmol of boron trifluoride etherate, dissolved in 5 ml of toluene, added. The mixture is reacted for 10 minutes at 20 ° C. Then add 3.0 mmol of butadiene, dissolved in 5 ml of toluene, and 0.15 mmol of triethylaluminum, dissolved in 5 ml of toluene, in the order given. the mixed solution of the four components is 15 minutes at a temperature given in Table I. subjected to an aging treatment. The catalyst solution is yellowish orange and clear.

Then 22 ml of toluene and 3.91 g of butadiene are added to the catalyst and the polymerization is carried out for 45 minutes at 40 ^° C. Finally, methanol is added in order to interrupt the polymerization. The results are given in Table I.

Table I.

Temperature of 10 ° C over a period of 10 minutes, and the polymerization is carried out at a temperature of 40 ° C over a period of 70 minutes.
The following result is obtained:

Yield 15.2%

M ·· ■ ·· 2.56

cis-1,4 units 96.2%

trans-1,4 units 1.8%

1.2 units 2.0%

E xample 1 4

Instead of the butadiene used as a catalyst component in Example 1, isoprene is used in the same amount used. Similar to Example 1, the catalyst solution is colored and yellowish orange clear. Butadiene is polymerized for 55 minutes, giving the following result:

^{Extraordinary} yield 55%

at Aging Out
prey M. cis-1.4 trans-1,4 1.2 game temperature V. 3.27 V. V. V. 1 60 75.4 2.83 97.8 1.2 1.0 2 50 76.5 2.55 96.6 2.1 1.3 3 40 72.1 98.1 1.1 0.8

[η] 2.78.

cis-1,4-proportions 96.7%

trans-1,4-shares 1.2%

1.2 shares 2.1%

B e i s ρ i el 5

Nickel naphthenate (0.01 mg atom Ni), dissolved in 5 ml of hexane, is mixed with 3.1 mmol of butadiene, dissolved in 5 ml Hexane, added, whereupon 0.15 mmol of triethylaluminum, dissolved in 5 ml of hexane, to the mixture are.

Then added 0.15 mmol of boron trifluoride etherate dissolved in 5 ml of toluene added, and aging the mixture for 15 minutes at 6O ⁰ C. The catalyst thus prepared is yellowish orange in color.

In the presence of the catalyst, then 3.91 g of butadiene in 22 ml of hexane are polymerized for 45 minutes at 4O ⁰ C.
The following result is obtained:

Yield 80.2%

M ■ · 3.23

cis-1,4 shares 97.5%

trans-1,4-shares 2.1%

1,2-shares .. · ■. 0.4%

As a control, an experiment is carried out in which

no butadiene is used as a catalyst component. The catalyst is prepared by contacting triethylaluminum with nickel naphthenate at 0 ° C. over a period of 10 minutes and by adding boron trifluoride etherate at O'C over a period of 10 minutes. Then, with the same solvent and of butadiene is polymerized for 60 minutes at 40 C ^c.

The following result is obtained:

60

As a control, an experiment is carried out in which no butadiene was added as a catalyst component will. In this case, the catalyst is by aging the mixture of components at a

Yield 21.4%

[η] 3.29

cis-1,4-shares 96.8%

trans-1,4-shares 1.3%

1.2 shares ... "1.9%

Examples

Butadiene is polymerized as in Example 1 with the difference that all catalyst

7 8

components reduced by half and that it was obtained for 10 minutes, only traces of polymerized for 2 hours are obtained. The following is obtained ER of polymer when the polymerization result: 5 hours at 40 ⁰ C is carried out.

Yield 64.8% ₅ Be is ρ i el e 7 to 10 M ········ 5.68 Instead of the nickel used in example 1

cis-1,4-parts 98.2% naphthenate are used in these examples

trans-1,4-parts ..... '0.7% below named nickel compounds. The other

. 1.2 parts 1.1% of their catalyst components, the manufacturing

lo conditions for the catalyst, the solvent

With a catalyst that does not contain butadiene and the amount of monomers, the polymerization temperature catalyst component and the addition and the polymerization time are the same as bringing together triethylaluminum with the Re- in Example 1. The catalyst solutions are yellowish-action mixture of nickel naphthenate and boron tri-orange colored and clear. The results are given in fluoride etherate at 10 ⁰ C over a period of 15 Table II:

Nickel connection
(mg atom) 0.01
0.01
0.01
0.01 table H M. cis-1.4
V trans-1,4
% 1.2
7th example Nickel stearate
Nickel acetylacetone
Nickel acetoacetate
Nickel carbonyl yield
° /. 2.81
3.43
2.98
3.39 97.2
98.3
96.1
96.8 1.5
0.5
1.1
2.5 1.3
1.2
2.8
0.7 7th
8th
9
10 65.1
78.4
59.1
77.3

Example 11

Nickel octenate (0.05 mg atoms Ni), dissolved in 5 ml of toluene, and 0.25 mmol of boron trifluoride etherate, dissolved in 5 ml of toluene, are poured into a pressure-tight reaction vessel. The mixture is reacted at a temperature of 20 ^° C. for 10 minutes. Then 2.5 mmol of butadiene, dissolved in 5 ml of toluene, and 0.25 mmol of butyllithium, dissolved in 5 ml of toluene, are added in the order given and the mixture is aged for 15 minutes at a temperature of 50 ^° C. The thus prepared The catalyst is colored yellow.

7.5 g of butadiene in 16 ml of toluene are polymerized at 40 ° C. for 30 minutes in the presence of the catalyst.

The following result is obtained:

Yield 6.08 g (81%) ₄ ,

M 2.03

cis-1,4-proportions 96.8%

trans-1,4-proportion ... 1.8%

1,2-shares ..... '. 1.4%

50

As a control, an experiment is carried out in which no butadiene is added as a catalyst component. The mixture of the catalyst components is reacted at 20 ° C. for 10 minutes. then it is polymerized for 60 minutes at a temperature of 40.degree.

The following results are obtained:

Yield 1.9 g (25%)

M 2.32

cis-l. ^ proportions 95.2%

trans-LA sharec 2.2%

1.2 shares 2.6%

Example 12 _6j

Butadiene is polymerized for 2 hours at 4O ³ C with a catalyst which is obtained by mixing nickel naphthenate (0.1 mg atom Ni), 0.5 mmol boron trifluoride etherate, 3.5 mmol of isoprene and 0.5 mmol of diethylzinc was obtained in the order indicated and by aging the resultant mixture at 6O ⁰ C over a period of 15 minutes. The catalyst solution is colored yellow. The following results are obtained:

Yield 6.38 g (85%)

M x 1.26

cis-1,4-proportions 95.5%

trans-1,4-proportion 3.2%

1.2 shares 1.3%

If the polymerization is carried out under the same conditions with the exception that one If no isoprene is used as a catalyst component, the following results are obtained:

Yield 2.12 g (28.3%)

W 1.05

cis-1,4-shares 95.2%

trans-1,4-shares 3.8%

1.2 shares 1.0%

Claims (4)

Patent claims: 1. A process for the preparation of cis-1,4-polybutadiene by stereoselective polymerization of butadiene in the liquid phase and in the presence of a catalyst system consisting of at least one nickel salt of a carboxylic acid or of an organic complex compound of nickel as the first component (A), from BF ₃ or its complex compounds as the second component (B) and from at least one organometallic compound of an alkali metal or a metal from group II or III of the periodic table as the third component (C), characterized in that the polymerization is carried out in the presence of a Catalyst carries out, too 009 624 104 whose preparation has been used as a fourth component (D) a conjugated aliphatic diolefin, wherein the component D to the catalyst system has been added prior to the implementation of the first with the third component and the product was subjected to an aging treatment formed at 20 to 100 ⁰ C. 2. The method according to claim 1, characterized in that there is as much per 100 g of butadiene Catalyst used that the first component contains 0.025 to 2.6 mg-atoms of nickel, with on 1 mole of the third component 0.02 to 2 moles of the first component, 0.2 to 10 moles of the second Component and 0.2 to 20 mol of the fourth component are omitted. 3. The method according to claim 1 and 2, characterized in that the polymerization at a temperature of 0 to +100 ⁰ C is carried out. 4. The method of claim 1 to 3, characterized in that one uses a catalyst mixture which has been aged at a temperature of 30 to 80 ⁰ C.