DE1148749B - Process for the polymerization of alkylene oxides - Google Patents

Description

GERMAN

PATENT OFFICE

G 28806 IVd / 39 c

REGISTRATION DATE: JANUARY 14, 1960

NOTICE THE REGISTRATION AND ISSUE OF EDITORIAL: MAY 16, 1963

The invention relates to a process for the polymerization of one or more alkylene oxides in Presence of an organometallic compound of the general formula

MeRRV ₁

(Me = metal of valence χ from groups I. to III of the periodic table; R = hydrocarbon radical; R '= hydrogen, halogen, hydrocarbon radical or alkoxy or secondary amino radical) and a mixed catalyst, characterized in that that the polymerization in the presence of a catalytic amount of a mixture or the reaction product of the organometallic compound with a or more metal oxides of groups II to IV of the Periodic Table.

Numerous catalysts for the polymerization of alkylene oxides are known which consist of either organometallic compounds alone or additional certain metal halides. For example, British patent 785 229 and US Pat. No. 2,870,100 describe the polymerization of ethylene oxide and propylene oxide with organometallic compounds of aluminum, zinc and maignesium. British Patent 793 065 describes the copolymerization of two or more alkylene oxides with the aid of an organometallic compound. Organometallic compounds along with other catalysts are used in the triethylaluminum and iron ⁱⁿ chloride system described by S. Kambara and M. Hatano, Journal of Polymer Science, Vol. 27, p. 584 (1958), and in the trialkylaluminum and system Sodium fluoride (vs. British Patent 799 955).

Even if the polymerization of alkylene oxides is induced by organometallic compounds alone can be, however, it is strengthened if this is combined with aluminum oxide or a other acidic oxide can be used. In addition, in this case, the polymerization goes very well much further.

Alumina alone can also polymerize alkylene oxides, such as ethylene oxide or propylene oxide (see German patent specification 821 349).

However, high molecular weight polymers are not obtained with alumina alone.

It has now been found that when the catalysts according to the invention are used, solid polymers with a very high molecular weight can be produced in high yields. If If silicic acid-aluminum oxide mixtures are used, this effect is particularly remarkable.

Polymerization process
of alkylene oxides

Applicant:

The General Tire & Rubber Company,
Akron, Ohio (V. St. A.)

ίο Representative: Dipl.-Ing. W. Meissner, Berlin 33,
and Dipl.-Ing. H. Tischer, Munich 2, Tal 71,
Patent attorneys

Junji Furukawa, Teiji Tsuruta,

Takeo Saegusa, Kyoto,

and Genjiro Kakogawa, Osaka (Japan),

have been named as inventors

With silica-aluminum oxide mixtures alone, alkylene oxides only polymerize to low molecular weight liquid polymers.

The organometallic compound to be used in the invention is an organic compound of one Metal of Groups I to III of the Periodic Table and is represented by the general formula

MeRR '

x-l

reproduced, where Me is a metal with the valency x, R is a hydrocarbon radical and R 'is a radical which can be hydrogen, a hydrocarbon radical, an alkoxy group or a secondary amine radical.

As for the amount of the organometallic compounds to be used, there is no particular one Limit, but one usually uses 0.01 to 100 mole percent organometallic compound, based on on the alkylene oxide monomer. Mixtures of two or more organometallic compounds can also be used or the so-called "Ate complex", which is said to consist of two organometallic compounds, be used.

The other catalyst component consists of metal oxides, such as aluminum oxide, and the so-called acidic oxide mixtures of aluminum oxide and one or more oxides of metals Groups II to IV of the periodic table.

Examples of such oxide mixtures are silica - ^ aluminum oxide, Aluminum oxide - boron oxide,

309 580/447

Aluminum oxide — thorium oxide, aluminum oxide— Magnesium oxide, aluminum oxide - zirconium oxide, silicic acid - aluminum oxide - zirconium oxide, silicic acid! - aluminum oxide - thorium oxide and similar oxides with aluminum oxide.

The amount of oxide catalyst can be varied widely, but usually from 0.01 to 1000 percent by weight of the oxide catalyst based on the alkylene oxide monomer is used. Mixtures of diethyl zinc and silica-aluminum oxide powder (SiO ₂ : Al ₂ O ₃ = 87: calcined for 13.15 hours at 500 to 600 ° C.) are also produced.

5 g of silica-alumina was placed in a pressure bottle and 20 cc of hexane was added. Then 0.0125 moles of di- were - äthylzink added under nitrogen atmosphere and the mixture heated for 1 hour at 80 ⁰ C.

After cooling, 10.1 ecm (0.25 mol)

from two or more oxides, propylene oxide monomers can be used and added. The polymers. was then carried out in 65 hours at room temperature.

Solvents are carried out when the poly rature is carried out. The polymer was not always necessary in a merization, but using a mixture of methanol and acetone (7: 3) can facilitate the reaction. Usable dissolved, insoluble substances were removed by centrifugation Solvents are aliphatic hydrocarbons, 15 removed, the polymer precipitated with water and like hexane and heptane, aromatic hydrocarbons - finally dried in vacuo at room temperature. The percentage conversion was 60% and the [η] of the polymer was 3.1.

If only silica-alumina as a catalyst under the same conditions (without inventive When diethyl zinc was used, only a liquid polymer was used obtained with a low molecular weight and a conversion of 3%.

If only diethyl zinc as a catalyst under the same conditions (under a nitrogen atmosphere) was used without using silica-aluminum oxide according to the invention, no polymer was obtained.

Thus the use of silica-alumina and diethylzinc together goes a long way

substances, such as benzene and toluene, and other organic solvents, such as ether and others Reactants, in particular towards the organometallic compound, are inert.

The metal oxide and the organometallic compound are mixed and before or after the addition of the Brought monomers to reaction. The pressure and the reaction time are not particularly limited.

The polymerization temperature can be varied within a wide range, e.g. B. between -70 and 200 ^° C. However, it is preferable to carry out ^{the polymerization between approximately 0 and 100 ° C.}

In general, the metal oxide is placed in a hydrocarbon solvent and the organostars are added Effect than either of these catalysts alone. Example 2

metal compound directly or as a solution in one
inert solvent is added to heat the catalyst
and the additional catalyst for a certain time
to a certain temperature, then adds the mono- 35 In the polymerization of propylene oxide under mere (sometimes excess organo- Use of 0.0125 mol of triethylaluminum metal compound before the addition of the monomer
removed by washing with an inert solvent), the monomer polymerizes, removed
hold unreacted monomer after the polymer 40,
sation by distillation, the polymer is extracted
with a solvent, e.g. B. with benzene or
Acetone, the polymer falls with a different solution during the polymerization of propylene oxide

solvent, e.g. with petroleum ether or water, from the use of 5 g aluminum oxide grains (15 hours and finally dries it, e.g. B. in a vacuum at 45 to calcined at 500 to 600 ° C) in place of the Room temperature. Silicic acid-aluminum oxide in Example 1, but

For the polymers produced in this way, the viscosity of their solutions in benzene at various concentrations of polymer is determined at 35 ° C., and the intrinsic viscosity [η] (dl / g) is determined by extrapolation.

The polymers obtained according to the invention can be used as additives for lubricants and greases, as a plasticizer and in the manufacture of

Shoe heels, shoe soles, sportswear, driving 55 yield. Along with alumina, the belts, tires, inner tubes and coated effects of diethyl zinc are also evident, and fabrics will be used. They can be vulcanized with combinations of peroxides and sulfur
and if they contain unsaturated olefinic carbon-carbon double bonds, 60
they are supplied with sulfur and sulfur-supplying masses

Place of diethyl zinc and processing as in Example 1 were 3.3 g of polymer with an internal Viscosity of 0.4 and a yield of 23% er

Example 3

Otherwise the same procedure as in Example 1, 3.9 g non-sticky, colorless, elastic mass with an [η] = 2.3 were obtained.

If propylene oxide under the same conditions but using aluminum oxide is polymerized alone as a catalyst without using diethyl zinc according to the invention one 3.4 g sticky semi-solid mass at 24%

obtained a polymer with a high degree of polymerization (high viscosity).

working or being vulcanized. These polymers can also be mixed with rubber and plastic additives be mixed.

example 1

9.0 g of non-sticky, colorless, elastic solid mass were obtained with the aid of a catalyst system Examples 4 to 12

The polymerization of propylene oxide was carried out as in Examples 1 to 3 using of 5 g of aluminum oxide or silicic acid-aluminum oxide as an acidic mixed oxide catalyst and tributylborane, triethylaluminum, diethylcadmium, Ethylmagnesium bromide and butyllithium carried out as the organometallic compounds. The conditions were: monomer 0.25 mole, aluminum

oxide or silicic acid-aluminum oxide 5 g, organometallic compound 0.0125 moles, room temperature

and 65 hours under nitrogen. The results are given in Table 1 below:

Table 1

Polymerization of propylene oxide using a mixed catalyst of aluminum oxide or silica-aluminum oxide and organometallic compound

example catalyst solvent
in ecm sales
° / o [η] W 4th Alumina - Cd (C ₂ H _s ) ₂ Benzene 15 38 4.2 5 Alumina - C ₄ H ₉ Li Hexane
+ Benzene *) 8th 0.9 6th Alumina - A1 (C, H ₅ ) ₃ Hexane 20 21 1.3 7th Alumina - C ₂ H ₅ MgBr ether
+ Benzene W 9 0.5 8th Alumina — B (nC ₄ H ₉ ) ₃ Benzene 15 10 (d) 9 Silicic acid / aluminum oxide - Cd (C ₂ H ₅ ) ₂ Benzene 15 1 0.6 10 Silicic acid / aluminum oxide - C ₂ H _{5 MgBr} ether
+ Benzene ^<c > 20th (d) 11 Silicic acid / aluminum oxide - C ₄ H ₉ Li Hexane
+ Benzene ») 1 (e) 12th Silicic acid / aluminum oxide - B (nC ₄ H ₉ ) ₃ Benzene 15 32 (e) B (nC ₄ H ₉ ) ₃ alone Benzene 15 0 A1 (C ₂ H ₅ ) ₃ alone Hexane 20 13th 1.4 Cd (C ₂ H ₅ ) ₂ alone Benzene 15 0 C ₄ H ₉ Li alone Hexane
+ Benzene 0

(a) In benzene at 35 ° C (dl / g).

(t>) 11 ecm hexane + 9 ecm benzene.

(<0 11 ecm ether (Grignard solution) + 9 ecm benzene.

Examples 13-15

(d) Sticky semi-solid mass.

(e) liquid.

and diethyl zinc varied. The other conditions

Propylene oxide was at 75 to 80 ° C for 4 hours 40 were: propylene oxide 0.25 mol, hexane 20 ecm,

polymerized under nitrogen as in Example 1, only the amounts of aluminum oxide were

Nitrogen. The results obtained are shown in Table 2:

Table 2
Polymerization of propylene oxide with a mixed catalyst of aluminum oxide and diethyl zinc

example Alumina Diethyl zinc Polymer implementation M. G Mole ■ 10 G ° / o 13-1 1 0.25 0.47 3.23 0.49 13-2 1 1.25 1.24 8.53 1.25 13-3 1 2.50 2.01 13.8 3.26 13-4 1 5.00 2.59 17.8 3.58 13-5 1 12.50 0.78 5.37 0.76 13-6 1 25.00 0.44 3.03 0.67 14-1 2 0.25 0.81 5.57 0.36 14-2 2 1.25 1.04 7.16 0.67 14-3 2 2.50 1.96 14.5 1.18 14-4 2 5.00 6.15 42.3 4.30 14-5 2 12.50 1.87 12.8 1.19 14-6 2 25.00 1.74 12.0 1.10 15-1 5 0.25 3.81 26.2 0.40 15-2 5 1.25 3.52 24.2 0.42 15-3 5 2.50 3.69 25.4 0.92 15-4 5 5.00 5.39 37.1 2.29 15-5 5 12.50 9.86 68.0 4.08 15-6 5 25.00 3.69 25.4 1.15

Example 16

gave polymers with a high degree of polymerization in high yield, while the fourth and fifth The polymerization can also be carried out in the manner by- catalyst samples approximately the same results be led to bring the acidic oxide with it like the use of aluminum oxide Organometallic compound converts, free organo- 5 alone that has not yet been treated with diethylzinc metal compound removed and then the monomer became.

admits. Table 3

5 g of aluminum oxide were added to 25 ecm of hexane, for which 0.025 mol of diethyl zinc was added under polymerization of propylene oxide in an aluminum-nitrogen atmosphere added. The mixture of io oxide and diethyl zinc

was heated to 80 ° C. for 1 hour. Excess

Diethyl zinc was made by washing with hexane among number of treatments

Nitrogen removed. 0.25 moles of propylene oxide became alumina with diethyl zinc

added to the catalyst prepared in this way and

held at 80 ° C. for 4 hours for the purpose of polymerization. 15th

7 g of high polymer were obtained with an internal - * ■ ·

Viscosity of [η] = 2.9. ²

Example 17 4> j

The polymerization was carried out by adding 5 g of 20 5

Aluminum oxide and 0.025 mol of diethyl zinc to untreated aluminum oxide

25 ecm hexane, heating for 1 hour at 80 ° C,

Removal of the hexane solution by means of a syringe, Examples 18 to 23

Add the solution to a second sample of 5 g

Aluminum oxide (which has not yet been treated), 35 ethylene oxide was made in the same way as in

Renewed heating, repeated use of Examples 1 to 12 polymerized. In this case, too

0.025MoI diethylzinc, up to five aluminum oxide, resulted in the organometallic catalyst system

Samples (5 g each) were obtained, and binding and acid oxide gave excellent results.

finally polymerization of propylene oxide Polyethylene oxide was isolated and extracted by

Purified (0.25 mol) with the aluminum oxide thus obtained with benzene and precipitation in petroleum ether.

rehearse. The results are shown in Table 3. The results are shown in Table 4 below.

The first, second, and third catalyst samples passed.

sales M. »/ 0 70 3.6 67 3.8 75 3.8 27 0.7 31 0.4 28 0.4

Table 4

Polymerization of ethylene oxide with a mixed catalyst made of aluminum oxide or silica-alumina and an organometallic compound

(0.25 mol of ethylene oxide, 5 g of aluminum oxide or silica-aluminum oxide, 0.0125 mol of an organometallic compound, Room temperature, 20 hours under nitrogen)

example catalyst solvent Poly
merisat sales M ' ^a) in ecm G »/ 0 18th Aluminum oxide + Zn (C ₂ H ₅ ) ₂ Benzene 15 9.6 87 4.1 19th Alumina 4- Cd (C ₂ H ₅ ) ₂ Benzene 15 3.7 34 9.4 20th Alumina + C ₂ H ₅ MgBr ether
+ Benzene ^(b) 3.2 29 3.4 21 Aluminum oxide + C ₄ H ₉ Li Benzene 15 - 3.0 27 3.5 22nd Silicic acid / aluminum oxide + Zn (C ₂ H ₅ ) ₂ Benzene 15 2.9 26th 2.9 23 Silicic acid / aluminum oxide + C ₂ H _{5 MgBr} ether
-1- benzene W 4.8 44 1.7 Alumina alone Benzene 15 6.2 56 1.0 Silica / aluminum oxide alone Benzene 15 - ■ - (C) Zn (C ₂ H ₅ ) ₂ alone Benzene 15 0 0 Cd (C ₂ H ₅ ) ₂ alone Benzene 15 0 0 C ₂ H ₅ MgBr alone ether
+ Benzene 2 9.5 C ₄ H ₉ Li alone Benzene 15 traces

(a) In benzene at 35 ° C (dl / g).

W 11 ecm Grignard solution + 14 ecm benzene.

Cc) liquid.

Example 24

1.12 g of slightly sticky polymer (9.3%) soluble in acetone and 0.70 g of non-sticky polymer in acetone insoluble polymer (5.8%), but which is soluble in benzene, were obtained by adding a mixed catalyst from 5 g of aluminum oxide and 0.0125 mole of diethyl zinc to 0.25 mole of butadiene monoxide, the same as in Example 1 above, and left to stand at room temperature for 98 hours to achieve the Polymerization obtained.

Example 25

0.735 g of copolymer were obtained by adding 2 g of aluminum oxide to 20 ecm of benzene, as follows Addition of 0.005 mol of diethyl zinc, heating to 80 ° C for 1 hour, addition of propylene oxide and ethylene oxide in amounts of 0.125 mol each and allowing to stand for 9 hours at -5 to 0 ° C to achieve the polymerization.

20 Example 26

0.78 g of copolymer were using the same catalyst system as in the above Example 25 and by copolymerization of 0.150 mol of propylene oxide and 0.10 mol of ethylene oxide manufactured under the same conditions.

Claims (6)

PATENT CLAIMS: 1. Process for the polymerization of one or more alkylene oxides in the presence of a Organometallic compound of the general formula (Me MeRR ^ _-1
= Metal of valence χ from groups I to III of the periodic system; R = hydrocarbon radical; R '= hydrogen, halogen, hydrocarbon radical or alkoxy or secondary amino radical) and a mixed catalyst, characterized in that the polymerization is carried out in the presence of a catalytic amount of a mixture or the reaction product of the organometallic compound with one or more metal oxides of groups I to IV of the periodic Systems performs. 2. The method according to claim 1, characterized in that there is aluminum oxide as the metal oxides or an acidic mixed oxide of aluminum oxide and one or more oxides used by metals of groups II to IV of the periodic table. 3. The method according to claim 1, characterized in that the polymerization at at a temperature between -70 and + 200 ° C. 4. The method according to claim 1, characterized in that the polymerization in Carries out the presence of an inert solvent. 5. The method according to claim 1, characterized in that the alkylene oxide is at least one from the group of ethylene oxide, propylene oxide and butadiene monoxide is used. 6. The method according to claim 1, characterized in that the organometallic compound used is diethylzmk, diethylcadmium, butyllithium, triethylaluminum, ethylmagnesium bromide or tributylboron and the metal oxide used is aluminum oxide or silicic acid-aluminum oxide. © 309 580/447 5.