DE1667275C - Process for the production of high molecular weight alkylene oxide polymers or alkylene oxide copolymers - Google Patents

Description

R ₁ O-Al-OR ₂ OR ₃

in which R ₁ , R ₂ and R _{3 have} the meaning mentioned. have, which is dissolved or dispersed in the liquid inert medium of aromatic and saturated hydrocarbons and / or ethers, has been prepared with 0.1 to 2.5 mol of water per mol of aluminum alkoxide at a temperature of 0 to 200 ⁰ C, and w At least one organometallic compound of the formulas

and

R ₄ -MR ₅

R ₄ -Al-R ₅

(D

(II)

and complexes of (I) and (I), (II) and (II) and (I) and (II), where R ₄ , R ₅ and R ^ are as defined and M is magnesium, zinc or cadmium, in represents an amount of 0.01 to 1.0 mol of organometallic compound per mol of aluminum in the partially hydrolyzed aluminum alkoxide at a temperature of 40 to 200 ° C.

3. The method according to any one of claims' and 2, characterized in that one is used as the catalyst component a partially hydrolyzed aluminum alkoxide is used in its manufacture by reacting with water an aliphatic alcohol with 1 to 6 carbon atoms, an aliphatic one Ketone with 3 to 13 carbon atoms, an amine with at least one hydrocarbon radical with 1 to 6 carbon atoms bonded to the nitrogen atom, or 1,4-dioxane, each in one Amount of 0.01 to 20 mol per mol of aluminum alkoxide, or mixture ** of these compounds is used have been.

4. The method according to any one of claims 1 to 3, characterized in that the organometallic catalyst ^ mponente a dialkylzinc compound with alkyl radicals with 1 to 6 carbon atoms used.

i>. Process according to one of Claims 1 to 4, characterized in that the polymerization carried out in the presence of at least one tertiary AiflinS !, the at least cincii hydrocarbon residue contains 1 to 6 carbon atoms bonded to the nitrogen atom.

6. The method according to claim 5, characterized in that that the tertiary amine is N, N-dimethylaniline, N.N-Djäthylanilm or triethylamine used.

7. The method according to any one of claims 1 to 6, characterized in that propylene oxide and AHylglycidyl ether (»are polymerized.

Aikylenoxydpoiymerisatc can be used as a dispersant for the production of paper, as Vef thickening

medium, small suspended as flocculant door Particles, as water-soluble films and as a finisher for fibers hence great commercial utility. Especially alkylene oxide polymers with a high Degree of polymerization can generally very well be used in smaller amounts for this purpose, which is why their commercial value is high.

The term "intrinsic viscosity" or "[)?]," As used in the following as a measure of the degree of polymerization refers to the 35 ° C in an aqueous solution (at Äthylenoxydpolymerisaten) or at 30 ⁰ C in a benzene solution (for the other alkylene oxides) certain value.

Japanese patent specification 409 556 (Auslegeschrift rs 2748 63) describes the sole use of a partially hydrolyzed aluminum alkoxide, which Reaction product of an aluminum alkoxide with water in the production of Alkylenoxydpohnicfisaten; in U.S. Patent 2,870,100 it is stated that organometallic compounds of a metal of group II or III of the periodic table can be used in particular for the polymerization of alkylene oxides.

However, if ethylene oxide is only polymerized with a partially hydrolyzed aluminum oxide as a catalyst, so the polymer obtained only has an intrinsic viscosity of 5, even if the polymerization is carried out under optimal conditions over a long period of time; the Polymerisationsgeschwir. The speed is not high enough for the production of the polymer on an industrial scale. Becomes ethylene oxide only with an organometallic compound of a metal from group II or III of the periodic table polymerized as a catalyst, no polymers with intrinsic viscosities of more than 2 are obtained, except when using organomagnesium compounds, and the rate of polymerization is very low. The ethylene oxide polymer obtained often has organomagnesium compounds an inherent viscosity of more than 10, in some cases of 20. However, it takes a very long time to so that such a high degree of polymerization is achieved, which is why an organometallic compound is used alone is considered technically unsuitable.

In contrast, the invention is directed to a method for the production of alkylene oxide polymers and copolymers directed for -iie above cited purposes. The object of the invention is to provide such a method, with which the polymers at high speed on an industrial scale and with a very high degree of polymerisation and thus great usefulness can be produced.

This object is achieved according to the invention by a method in which one or more Alkylene oxides with the formula

drive is characterized in that the polymerization in the presence of a reaction product as a catalyst, which is obtained by reacting a partially hydrolyzed aluminum alkoxide obtained by reacting an aluminum alkoxide with the formula

R ₁ O-AI-OR ₂
OR ₃

in which R ₁ , R ₂ and R ₃ each represent saturated aliphatic hydrocarbon radicals with 1 to 6 carbon atoms that are dispersed or dissolved in a liquid inert medium of aromatic and saturated hydrocarbons and / or ethers, with 0.01 to 2.8 mol Water per mole of aluminum alkoxide ^{has been obtained at temperatures from -50 to +300 0} C, with at least one organometallic compound of the formulas

R. — M "—R,

R ₄ -M »'- R ₅

R ₇ HC-CH ₂

'V

60

wherein R _{7 represents} a hydrogen atom, a methyl, ethyl, phenyl, vinyl, chloromethyl, bromomethyl, methoxymethyl, allyloxymethyl or a phenoxymethyl group, polymerized or copolymerized in the presence of an organoaluminum compound-containing catalyst, this being interwoven with R ₄ , R ₅ and R _{6 are} each saturated hydrocarbon radicals with 1 to 6 carbon atoms or phenyl groups, M "is beryllium, magnesium, calcium, strontium, barium, zinc, cadmium or mercury and M ^{111 is} a metal of the 3rd main group of the periodic table, and complexes of these compounds in amounts of 0.001 to 2.5 mol of organometallic compound per mole of aluminum of the partially hydrolyzed Aluminiumalkoxyds obtained at a reaction temperature of -50 to +300 ⁰ C, is carried out, wherein the amount of catalyst from 0.0001 to 0.3 mole { »h aluminum, which is contained in the catalyst) amount per mole of alkylene oxide, and the polymerization temperatures from -50 to +150 ⁰ C.

Surprisingly, a high molecular weight alkylene oxide polymer can be obtained by the process according to the invention at a very high rate of polymerization, with the yield of polymer per unit amount of catalyst in comparison to the known ones given above Procedure is extremely high. It has also been found that in the inventive Process the use of a tertiary amine to a large increase in the degree of polymerization of the polymer obtained leads.

The partially hydrolyzed aluminum alkoxides, the al «first component of the invention Process used catalyst can usually be prepared as follows:

An aluminum alkoxide with the formula

RiO-Al-OR ₂
OR ₃

in which Rj, R ₂ and R ₃ each have saturated aliphatic hydrocarbon radicals having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl -, isopropyl, sec-butyl, tert-butyl, tert-pentyl, cyclohexyl and similar radicals, z. B. aluminum trimethoxide, aluminum triethoxide, aluminum triisopropoxide,

637 275

Aluminum mono-selc-butoxydüsopropoxide ^ aluminum tri-sec.-butoxide is dispersed or dissolved in a liquid, inert medium, whereupon water in amounts of 0.01 to 2.8 mol, preferably 0.1 to 2.5 mol, particularly preferred 0.4 to 2.0 mol, per mol of aluminum alkoxide is added, and the two components are then reacted at temperatures between -50 and + 30O ⁰ C, preferably between 0 and 200 ⁰ C, a partially hydrolyzed aluminum alkoxide being formed.

The inert medium used for the above reaction is at least one substance from the group of aromatic hydrocarbons, such as benzene, Tciuoi,. vl-il, mesitylea, ethylbenzene, diethylbenzoi or F-r ^ ylbenzol, the saturated aliphatic carbons, such as n-pentane, isopentane, n-hexa \ iiohexane, 3-methylpentane, 2,3-dimethylbuian u -Heptane, 2,2-dimethylpentane, 2-methylhe? -. i. 1-methylhexane, n-octane, isooctane, n-nonane, cyc. ^ Outane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cycloponane or decalin; the ethers, such as diethyl ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, diisobutyl ether, disec-butyl ether, ethyl isopropyl ether, diethylene glycol diethyl ether, anisole, phenetole, diphenylic acid, tetrahydrofuran, 1,3-dioxanuran, 1,3-dioxanuran , Ethyls; iglycol dimethyl ether, propylene glycol dimethyl ether, diethylene glycol diethyl ether or ethylene glycol diet; ther; the medium being liquid under the conditions used in the preparation of the partial hydrolyzate of the aluminum alkoxide.

The reaction of an aluminum alkoxide with water can be achieved by adding the two components to an inert medium, which in amounts of more than 0.1 times, preferably 1 to 200 times Volume of the aluminum alkoxide is present and caused by mixing the mixture formed will. In general, the water can be added to the medium in which the aluminum alkoxide is dissolved or dispersed while stirring the medium with stirring continued if necessary can be. The temperature for this reaction Hegt between -50 and 300 ° C, preferably between

0 to 200 ^° C. The reaction can be shortened by increasing the temperature. The time required for this reaction is generally 0.1 to 10 hours. Furthermore, the reaction can be carried out under pressure or under reduced pressure. The pressure is not critical.

In the case of partial hydrolysis, at least one additive from the group of aliphatic alcohols can be used with 1 to 6 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, n-pentanol, n-hexanol, allyl alcohol or ethylene glycol, the aliphatic ketones with 3 to 13 carbon atoms, such as acetone, Methyl ethyl ketone, diethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, diisopropyl ketone, di- -n-butyl ketone or di-n-hexyJketon, the amines with at least one hydrocarbon radical with

1 to 6 carbon atoms on the nitrogen atom, such as methylamine, dimethylamine, trimethylamine, ethyl amia, diethylamine, triethylamine, n-propylamine, din-propylamine, Tri-n-propylamine, isopropylamine, diisopropylamine, triisopropylamine, tri-n-hexylamine, AJlyiamine, N-methylaniline, N, N-dimethylaniline or Ν, Ν-diethylaniline can be added. Through this Additives, the polymerization effect of the catalyst obtained can be regulated. Wishes one for example in the polymerization of ethylene oxide in n-Hexai! in the presence of a catalyst, which is the reaction product of a partially hydrolyzed

sized aluminum triisopropoxide with diethyl zinc represents, an ethylene oxide polymer with a higher molecular weight, so one sets the medium for partial hydrolysis, preferably methanol. On the other hand, if one wishes for this polymerization

Ethylene oxide polymer with a somewhat lower molecular weight, acetone or isopropanol should be used be added; if in this polymerization an ethylene oxide polymer with a high or low If apparent density is desired, ethanol should be used

rs or A.cetone or isopropanol can be added. Furthermore, in the polymerization of propylene oxide, by adding the above-mentioned Additives change the crystallinity of the polymer obtained. If the above specified Hydrocarbon used as a medium for hydrolysis, s' can be that given above as a medium Ether can also be used as an additive. This additive and the water can can be added separately to the medium that contains the Alu

contains miniumalkoxide dispersed or dissolved; but often you can also add them as Gerrisch, since the most additives are compatible with water. If the inert medium is not hydrophilic (e.g. hydrocarbons), so it is difficult to mix the aluminum alkoxide in this medium evenly with water To bring touch. Therefore it is often beneficial the water gradually diluted with a water-miscible alcohol, ketone, amine or ether add to the medium or a mixture of water vapor or an inert gas such as nitrogen or argon, to be blown into the medium. The amount of additives used generally ranges from 0.01 to 20 moles per month! Aluminum alkoxide.

The partial hydrolyzate of the aluminum alkoxide obtained in this reaction is inert Medium containing the alcohol formed as a by-product, dispersed or dissolved; this can can also be added as an additive. The alcohol produced as a by-product and the alcohol

hol, the primary amine or the secondary amine, which are used as additives, can react with the organo-metal compound, which is used as the second component for the preparation of the catalyst, and adversely affect the polymerization of the alkylene oxide by the catalyst, which is, for example, in a Reduction in the rate of polymerization and the degree of polymerization of the polymer obtained expresses itself.
These secondary substances and the additives are usually distilled off from this syrup, together with part of the inert medium, immediately after the preparation of the partial hydrolyzate. The amount of the remaining. By-product or additive can be the amount / of the "AIu-

60-miniumalkoxyds be about equimolar, although they are is preferably as small as possible. The partial hydrolyzate of aluminum alkoxide thus obtained can in the reaction with an organometallic compound in the form of a solution or dispersion in the inert Medium or after removal of the inert medium.

It is believed that the partially hydrolyzed aluminum alkoxide in a sense an inorganic one

Polymer with> A1 — Ο — Al <bonds is, although its exact structure has not yet been confirmed. In either case, this is partial hydrolyzate something quite different from aluminum oxide, since ethylene oxide is alone with this partial hydrolyzate is polymerized under optimal conditions, the polymer obtained has an inherent viscosity of about 5 has, while when using aluminum oxide, even under the best conditions, only one polymer with an inherent viscosity of less than 1 is obtained.

The organometallic compound of a group II metal used in the process according to the invention or III is a compound of the formula

R ₄ -M "-R ₅ ' ⁵

R ₄ -M " ¹ -R ₅

20th

wherein M ".. a metal of group II of the periodic table, that is, beryllium, magnesium, calcium strontium, barium, zinc, cadmium or mercury; M" ^a a metal of group IfI of the Periodic Table, such as boron or aluminum, and R _4. R ₅ and R ₆ each represent hydrocarbon radicals having 1 to 6 carbon atoms, or a complex of these compounds. Typical examples of the above-mentioned organometallic compounds are dimethyl magnesium. jp diethyl magnesium, di-n-propyl magnesium. Diisopropyl magnesium, di-n-butyl magnesium. Diisobutyl magnesium. Ethyl-n-propylniagnesiuni. Afbytisopropylmagnesium, ethylisobulylmagnesium. Dicyclohexylmagnesium, diphenylmagnesium and corresponding compounds, m which the magnesium is replaced by other metals of Group II: and trimethylaluminum. Trietbyl aluminum. Tri-n-propyl aluminum, triisopropyl aluminum. Tri-n-butyl aluminum, triisotratyl aluminum, dimethyl ethyl aluminum. Methyl diethyl aluminum. Diethyl-n-propylaluminum, ethyldi-n-propylaluminum. Diethyl isobutyl aluminum, ethyl diisobutyl aluminum. MethyläthylisobatylaJuminitini.Tricyclohcxylalominium.Triphenylalummnnn and corresponding compounds. in which the aluminum is replaced by boron.

Examples of the complexes are Calchimtetra- meth'jhink, Calcromtetraäihylzini :. Calcium tetrapropylzirii. Calcium teirabatyl zinc. Calciumdimethyldi-eihylnaa, CaTciamdiathyldibaiylzink. Strontium tetraethyziak, Strontinmtelrabntylzrnk. Barium telraäthyJzinir Barinmtetrabutylzink and corresponding compounds, ia which the zinc is ααί through cadmium or mercury; Magnesite pentamethyl boron. Magnesine pentaethyl boron. Magnesiumpeniamethylalaminnnn, Magnesiumpen taäthylaluminium, Magnesrampeniaijntylalamiinhini and those compounds in which the magnesium is replaced by calcium. Strontium, zinc or cadmium replaces isL

The catalyst used in the process according to the invention is obtained by mixing the above-mentioned partial hydrolyzate of an aluminimalkoxide with at least one of the above-mentioned organometallic compounds, which are present in amounts from 0.001 to 25 mol, preferably from 0.01 to 1.0 Mc !, per month. Alnnimnnnalfcoxyd is used, produced in any amount, whereupon the resulting mixture of a reaction at temperatures from -50 to +300 ⁰ C over a period of 0.1 to 30 hours, preferably at 40 to 200 ⁰ C over a period of 0.1 to 10 hours. It is usually preferred and convenient to mix the two components together in a liquid, inert medium. In particular, it is often preferable to add the organometallic compound to the solution or dispersion of the partially hydrolyzed aluminum alkoxide in the inert medium that occurs during the preparation of the partial hydrolysis. B. at room temperature or at atmospheric pressure, proceeds relatively quickly, the two components can simply be mixed together with the monomer to be polymerized in a polymerization medium immediately before the polymerization, whereby the monomer can be polymerized. Furthermore, the two components can be mixed with one another in a monomeric alkylene oxide or directly. The catalyst prepared in this way is suitable for the bulk polymerization of alkylene oxides. The reaction of the two components can take place under pressure or under reduced pressure, ie. the pressure is not critical in this implementation. However, it is often advantageous to carry out the reaction under pressure if one wants to work at a high temperature in a low-boiling medium.

The medium that can be used to prepare the catalyst can be any medium which was used to prepare the partial hydrolyzate of aluminum alkoxide. The used The amount of medium can be practically the same as in the preparation of the partial hydrolyzate.

The activity of the catalyst prepared in this way can be increased by heating the partial hydrolyzate Temperatures of 40 to 300 ° C over a period of 0.1 to 30 seconds before mixing with the Organometallic compound can be improved. When using this preheated partial hydrolyzate the rate of polymerization and the degree of polymerization in the polymerization of alkylene oxides with the catalyst from this partial hydrolyzate and the organometallic compound improved. Furthermore, the crystallinity of the polymer can be varied in this way. the Preheating is preferably carried out with the dispersion or solution of the partial hydrolyzate in the inert Medium from which the substances that adversely affect the subsequent reactions, e.g. B. that alcoholic by-product, were distilled off. The higher the preheating temperature, the more the preheating time can be selected to be shorter. However, if the preheating is carried out at temperatures of is carried out more than 300 ° C, the rate of polymerization becomes less. On the other hand, less than 40 ° C is a very long time for this preheating necessary, which is why preheating under these conditions is technically not favorable, especially Preheating is preferably carried out at temperatures from 80 to 200.degree

In the method according to the invention was a Alkylene oxide usually in a medium with the catalyst thus prepared in a manner known per se Polymerized way, although the alkylene oxide also together with the catalyst of a block polymer

30 * 424/242

sation can be subjected to in the absence of this medium. As a polymerization medium, any of the media specified above for the preparation of the partial hydrolyzate can be used. Almost all media for polymerization can be divided into two groups, the first being Group is able to dissolve both the monomeric alkylene oxide and the polymer, while the other Group can only solve the monomer, but not the polymer. For example, fall during the polymerization of ethylene oxide, the aromatic hydrocarbons and ethers, with the exception of dialkyl ethers in the first group and the saturated aliphatic hydrocarbons and the dialkyl ethers in the second group.

In practicing the invention it is often preferable to use media related to the second Belong to the group, since the polymer is then obtained in granular form, which means that it can be separated and recovered can be facilitated. Of course, a mixture of the media of the two groups can also be used can be used, although it is desirable. that the media are combined so that the same effect as can be achieved with the media of the second group.

The polymerization reaction in the present process can be carried out in that given above inert medium in the presence of a catalyst in amounts of 0.0001 to 0.3 mol (as aluminum) each used mole of alkylene oxide monomer at temperatures of -50 to + 150C below any desired Printing can be carried out. In general, at a higher polymerization temperature the rate of polymerization is greater, while preferably lower temperatures used when using polymers with bonem molecular weight wants to receive. At a polymerization temperature of less than -50 ° C, the rate of polymerization is too low, and above 150 ° C. the polymer obtained tends to decompose.

In the polymerization of an alkylene oxide according to the invention, the presence of a tertiary Amine with at least one hydrocarbon radical with 1 to 6 carbon atoms on the nitrogen atom often leads to an increase in the degree of polymerization of the obtained polymer. Examples of these amines are

Trimethylamine. Triethylamine.
Tri-n-propylamine, triisopropylamine,
Tri-n-butylamine. Triisobutylamine.
Tri-sec-butylamine, tri-n-amylamine.
Triisoamylamine, triallylamine,
Methyl diethylamine. n-propyldimetfaylamine,
Cetyldimethylamine,
Methylethyl-n-propylamine.
Tricyclohexylamine, Methyldiyclohsxylamiri,
Dimethylcyclohexylamine,
Methylethylcyclohexylamine.
Diethylcyclohexylamine,
Ν, Ν-dimethylaniline,
Ν, Ν-diethylaniline, triphenylamine,
N-ethyl-N-benzylaniline,
Ν, Ν, Ν ', Ν'-Tetraäthyläthylendiaanii,
N, N, N \ N'-TetramethyIpkenylCTdiamm,
N, N, N ^ N'-Tetramethylbenzidm,
N-methylmorphon, Ν-ΑΛνίΐηοτρΒοιίπ *
N-phenylmorpholine,
N-methylphenotidazine or pyridine.

The tertiary amines mentioned are effective in amounts of only 0.001 mol per mol of aluminum in the catalyst. Even if the tertiary amine is used in amounts of more than 10 moles per mole of aluminum

is used, its effect is not improved any further. The most preferred amount of added tertiary amine is 0.01 to 5 moles per mole of aluminum. You can determine the degree of polymerization of the obtained polymer regulate that

ίο one varies the type and amount of tertiary amine. The addition of the tertiary amine to the polymerization system can before. simultaneously with or after the initiation of the polymerization take place. If desired, the tertiary amine can also be used in the manufacture

ij position of the partial hydrolyzate or in the preparation of the catalyst by reacting the partial hydrolyzate mi! can be added to the organometallic compound.
That used in the method of the invention

to alkylene oxide is a compound with the formula

C C

wherein R _{7 is} a hydrogen atom or a methyl. Ethyl-. Phenyl-. Vinyl-. Represents chloromethyl, bromomethyl methoxymethyl, AlJyloxymethyl or phenoxymethyl group. Examples of these AlkylenoAyde are ethylene oxide. Propylsnoxide. 1,2-epoxybutane. tpichlorohydrin. Epibromohydrin. Methyl glycidyl lather. Phenyl glycidyl ethers. Butadiene monoxide, allyl glycid} 1-ether or slyroloxide.

J5 According to the method according to the invention with success homopolymers or copolymers of at least one of the alkylene oxides mentioned getting produced. Not only the degree of polymerisation can be changed, but also the crystallinital of the alkylene oxide polymer obtained can be improved. Furthermore, compared with the known Polymerization process, the reaction time can be shortened, and in some cases can control the Polymerization reaction through a suitable

selection of the heating conditions in the preparation of the catalyst by an appropriate combination the starting materials for the catalyst and are facilitated by the tertiary amine, creating a Polymer with the desired polymerizatiofaa-

degree can be produced within a certain time.

It is extremely surprising that the catalyst combination from the partially hydrolyzed aluminum alkoxide and the organometallic compound

of a metal of group K or III of the period " systems, compared with the low polymerisation effect of the individual components in technically more advanced Way leads to an alkylene oxide polymer that acts as a flocculant. Thickener

and sizing agent is particularly suitable for an aluminum oxide polymer with a high molecular weight, so far with the separate use of the said catalyst components could not be established.

example 1

In an 800 ml glass vessel with a reflux condenser, The thermometer and stirrer turned the air through

Displaced nitrogen, whereupon a solution of 0.03 mol of aluminum triisopropoxide in 80 ml of decalin was poured into the vessel. The solution was gradually heated with stirring at 8O ⁰ C, after which 0.024 mole of water, which were diluted with 50 ml of isopropanol was slowly introduced over 2 Stunder with vigorous stirring in the vessel. The resulting mixture was then refluxed with stirring for 3 hours. To the system obtained, which contained the partial hydrolyzate of aluminum triisopropoxide formed by this reaction, 50 ml of n-heptane were added, and the mixture formed was heated up to the boiling point of heptene to produce the fractions with lower boiling points as n-heptane to distill off. The fractions distilled off insisted on n-heptane, which contained both the alcohol obtained as a by-product in this reaction and the added alcohol. To the remaining liquid, 0.03 mol of diethyl zinc and an amine (only No. 4 in Table 1) were added, and the resulting mixture was kept at 80 ° C for 1 hour

s touched. 400 ml of n-heptane were then added and the mixture was stirred at 70.degree. Ethylene oxide was then introduced into the vessel over a period of 4 hours polymerized. The rate of addition of the ethylene oxide was regulated so that it was always a small one Amount of it emanated from the compartment of the vessel, whereby the reaction system was always saturated with ethylene oxide under atmospheric pressure. The results obtained are shown in Table 1, which also contains the results when using Aluminum oxide instead of the partial hydrolyzate shows for comparison.

Partial hydrolyzate crowd table 1 crowd Additive crowd Received
Polymer St. Art (Mole) Organometallic compound (Mole) Art (Mole) Out
prey Γ. 0.03 Art 0.03 - _ _ (gl 4.0 Aluminum tri - 60 1 isopropoxide 0.03 Diethyl zinc - Triethylamine - 1.9 the same - 0.03 - 45 - 2 - 0.03 - 0.03 0.03 0 8.5 3 Aluminum tri Diethylz'nk 55 4th isopropoxide 0.03 the same 0.03 - Active 2 5 Aluminum oxide el 2 the same At s ρ i

The polymerization of ethylene oxide was carried out in the same manner as in Example 1, but with the following Deviations carried out: the water was diluted with 1.4-Dioran, the by-product Alcohol from the partial hydrolyzate of aluminum triisopropoxide was not removed, and di-n-butyl zinc was used instead of diethyl zinc. There were 42 g of a polymer with an inherent viscosity obtained from 3.1. If 0.01 mol of N, N-diethylaniline was added during the polymerization, 48 g of a polymer with an inherent viscosity of 5.7 were obtained in this way.

Example 3

This example shows that numerous aluminum alkoxides are used for the polymerization of ethylene oxide can be.

In a 300-ml four-necked flask mitRückfiußkühler, thermometer, dropping funnel and stirrer was filled by the displacement of the air with nitrogen, a solution of 0.045 mol of a Aluminiumalkoxyds in 150 ml rubber petrol (boiling point 80 to 12O ⁰ C), whereupon 0.045 moles of water, with 15 ml of isopropanol were diluted with. 3O ⁰ C were added dropwise within 10 minutes while stirring. D? S resulting mixture was for 2 hours at 30 ⁰ C overnight, then distilled to the ^TT in the IMPLEMENTATION of Aluminiumalkoxyds with water as a byproduct formed alcohol and the isopropanol added to remove. After the temperature reached in the apparatus 102 ⁰ C, the distillation was interrupted it immediately 0.0045 mole diethylzinc to the mixture for 1 hour at a temperature of 102 "C under total reflux and stirring was maintained, a white suspension being obtained would.

In another 500 ml flask with a stirrer, in After the air was first displaced with nitrogen, there was added 400 ml of η-hexane, the above Suspension as a catalyst in an amount corresponding to 0.015 mol of aluminum and 52 g of ethylene oxide The mixture formed was charged for 6 hours at room temperature stirred and then allowed to stand for 42 hours to complete the polymerization.

The results obtained are shown in Table 2.

Table 2

No.

1 2 3

Aluminum alkoxide

Aluminum trimethoxide

Aluminum triisopropoxide ...
Aluminum mono-sec-butoxy-

diisopropoxide

A! Uminium tri-sec.-butoxide ..

Polymer yield

(G)

41 40

39
38

Example 4

This example shows the effect of the partially hydrolyzed alumina in the preparation used additive on the polymer produced.

In a 1.5-1 four-necked flask with reflux condenser, thermometer, dropping funnel and stirrer, after replacing the air with nitrogen, 0.25 mol AIuminiuraisopropoxyd containing 130 ml of kerosene in a mixture of 470 ml rubber benzine (boiling range 80 to 12O ⁰ C) and (boiling range 158 to 23O ⁰ C) was dissolved was introduced, followed by 0.25 moles of water which were diluted with an additive, was added dropwise at 30 ⁰ C over one hour under vigorous stirring. The mixture was then ^{stirred at 30 °} C. for 1 hour. The alcohol formed as a by-product in the reaction of the aluminum propoxide with water and the added additive were distilled off. The distillation was stopped when the temperature reached in the apparatus 14O ⁰ C, immediately followed by 0.025 mol of diethylzinc were added and the mixture was heated for 1 hour under total reflux, with stirring, to a temperature of 140 ⁰ C. A white suspension was obtained.

In an enamelled vessel with a capacity of 101, equipped with a stirrer, in which the Air had been displaced by nitrogen, 8 liters of η-hexane, the suspension indicated above and 1100 g of ethylene oxide filled in in the order given. The resulting mixture was 40 hours polymerized with stirring at 25 ° C. The results obtained are shown in Table 3.

table Additive crowd 3 Out Olympus Apparent (ml) prey density No. Art 47 ig) ['/] <g / ml) 45 S90 0.29 Methanol 30th 950 17.8 0.36 1 Ethanol 30th 940 12.8 0.23 2 Ethanol 45 920 5.1 0.22 3 Isopropanol 47
20th 935 9.6 0.23 4th acetone 47
20th 890 12.5 0.29 5 ί methanol
(.Acetone 30th 1050 17.8 0.48 6th Γ methanol
(.Ethanol 50 950 18.4 0.25 7th Dioxane 50 910 8.5 0.23 8th Ethyl ether *) 850 6.0 0.30 9 n-butylamine 16.8 10

Table 4

Temperature of implementation Polymer 8.7 No. of aluminum alkoxide 9.5 with water yield 18.0 CC) (G) 1 3 to 4 6! 2 30th 66 3 93 40

At s ρ i e 1 6

This example relates to the heat treatment of the aluminum alkoxide after removal the additive and the alcohol formed as a by-product.

115 g of ethylene oxide were polymerized as in Example 5, but with the following differences: n-heptane was used instead of rubber gasoline, the amount of water was 0.036 mol, the hydrolysis temperature was 30 "C. The heat treatment was carried out after the distillation and before the addition of the diethyl zinc 107 ⁰ C using given in Table 5 periods performed. After addition of the Diäthylzinks no heat treatment was carried out, and the time during which the mixture was allowed to stand was 90 hours. the results obtained are shown in Table 5.

Table 5

- - No Duration of the heat treatment 7th St. Pll of the partial hydrolyzate (Stood) Polymer 15.8 1 3 yield 15.0 2 10 Jg) 15.0 3 20th 32 18.0 4th 24 33 example 34 35

Note: *) Added separately before adding the water.

Example 5

This example illustrates the influence of temperature in the reaction between an aluminum alkoxide and water.

Ethylene oxide was polymerized as in Example 3, but with the following differences: It was Alurainium propoxide used as aluminum alkoxide, the hydrolysis temperature was varied in the manner shown in Table 4, the reaction was carried out at 60 ° C after adding diethyl zinc, the amount of ethylene oxide was 88 g, N, N-dimethylaniline (0.015 mol) was added along with the catalyst during the polymerization, and the time the mixture was allowed to stand was 92 hours. The results obtained are in Table 4 given.

In the same reaction vessel as in Example 1

were after displacing the air with nitrogen, 80 ml decalin, 75 ml n-Hc, tan and 0.06 mole of aluminum alkoxide eingefüllL The formed mixture was heated under slow stirring to 8O ⁰ C, after which 0.048 MoI water, which, with 50 ml 1 4-dioxane

were diluted, were gradually added at a temperature of 80 to 90 ⁰ C within 2 hours with vigorous stirring. The resulting mixture was stirred under reflux for an additional 2 hours, whereupon the alcohol formed as a by-product

was distilled off. To complete the removal of the alcohol, the distillation was added Continued for 5 minutes after the temperature of the mixture reached the boiling point of the decalin The partial hydrolysates of the various AIu-

minmmalkoxides all fell in the form of white, translucent jelly. 240 ml of n-heptane was added to the jelly, and the mixture was shaken well, a uniform suspension was obtained.

The suspension of the partially hydrolyzed Alumininmalkoxyds was in an amount corresponding to 0.135 g (0.005 mol) of aluminum in the Compound, together with 20 ml of ethylene oxide, a

15th

667

16

Organometallic compound and a tertiary amine. Then the reaction mixture was in the under a nitrogen atmosphere in a 100 ml jar - the same manner as Method A for the polymer keg was poured in and the mixture was used well sation (this method is described below shakes, whereby a uniform mixture obtained is referred to as method B).

would. This was then 28 hours at −10 ^° C. The results obtained are given in table 6. Diethylmagseshim and dimethylmagnesium were used in the form of solutions in 0.3 ml of diethyl ether, while calcium tetraethyl

p yy y zinc and triethylaluminum in the form of dispersed

then 1 hour at 80 ⁰ C with a Organometallver- io emissions in 3 ml benzene and 0.3 ml of n-heptane compound reacted, whereupon it is mixed with n-heptane were spent.

left to stand, the ethylene oxide polymerizing (this method is hereinafter referred to as method A).

The partially hydrolyzed aluminum alkoxide became Sd bi

table

Aluminum alkoxide crowd Art (MoI) 0.005
0.005 Aluminum tri
isopropoxide
the same 0.005 the same 0.005
0.005 Aluminum tri
isopropoxide
the same 0.005 desgL 0.005 the same 0.005 desgL 0.005 the same 0.005 desgL OJ005 desgL 0.005
0.005 Aiumimumtri-
isopropoxide
desgL 0.005 the same

desgL desgL

Aluminum triethoxide

the same as Afuntiniumiri-

0.005

0.005

O ₁ OGS 0.005

Organometallic compound Tertiary amine

Art

Diethyl magnesium like

Diethyl magnesium desgL

desgL

Dimethylcadmium like.

Calchim tetraethyl zinc desgL

Triethylaluminum desgL

Triethylaluminum like.

Diethyl zinc desgi.

the same

Diethyl magnetic

sium

the same. Dimethylmagne-

Amount (Mo «

0.00125 0.00125

0.00125 OJOOl

Art

N _T N-DimethylanSine

0.00125 j N, N-pimethyI-

0.005

0JÖ05

0.001

OJOOl

0.001

0.001

0.00125

0.00125

0.0005

0.0005 0.00125

0.00125 0.00125

aniline

N, N-dimethylaniline

N.N-dimethylaniline

N.N-dimethylaniline

N, N-diethylaniline

diamine
Tri-n-propylamine

Triphenylamine

crowd IMoI)

0.0015

0.0015

0.0015

0.0015

0.0015

0.0030

Her-

sleflungsmelhode of the catalyst

0.0015

0.0005

B.
B.
A.
A.
A.
A.
A.
A.
B.
B.

B *)
B.

Polymer

yield

56 63

36 0

73 67

42 46 48 49 52 55 58 62

65

5?

47

55 64

10.3

24.0

8.6 15.5 IU 19.3 10.8 20.6

7.8 15.3

8.7 24.1

sec.-t> utoxyd sium

the same 0.005 the same 0.00125 triethylamine 0.0005 A ***) 58

* i The temperature during the preparation of the catalyst was 60 ^° C.
"I The tertiary amine was added during the preparation of the catalyst.
* · *) O. <? 7 mol of water were added without using 1,4-dioxane! was, and the polymerization was
Carried out at - 5 C for 24 hours.

Example 8

This example shows the influence of the temperature in the preparation of the catalysts on the polymerization.

309676/262

115 g of ethylene oxide were polymerized as in Example 3, but with the following differences: There were 0.03 mol of aluminum nitride isopropoxide as aluminum alkoxide, 0.03 mol of water, 10 ml of 1,4-dioxane instead of isopropanol, 150 ml of a mixture of n-heptane and decalin (the mixing ratio changed depending on the desired temperature) and 0.003 moles of diethylzinc used during the time which the mixture was left to stand was IS hours, and the temperature at which the distillation was stopped, i.e. the temperature at total reflux (the temperature of the preparation of the Catalyst) was changed as shown in Table 7 is specified. There were those in table? specified Get results. Furthermore, the same procedure as above was repeated, wherein however 0.015 mol Ν, Ν-dimethylaniline were added; the results obtained are also in the table? specified.

Table 7

Temperature of
Manufacture of the Polymer CD with N, N-Di- !aniline Catalyst without KN-Di- melhy
Out C '/ J ⁵ No. CQ melhylaniline 4.7 prey Room temperature Out
prey 9.2 (G)- 5.8 43 <g> 8.6 10 - 1 62 13th 9.1 - - ^IO 2 75 24 12.6 - 10.5 3 92 29 13.1 20th 14.2 4th 117 29 14.9 54 16.2 5 137 58 14.7 59 18.1 ¹ S 6 156 12 pounds 71 16.8 7th 174 65 72 15.2 8th 75 74 9 97

Example 9

A white catalyst suspension was formed in the ethylene oxide in the same manner as in Example 8 prepared in the same manner as in Example 8, 25 polymerizing with this catalyst suspension, wherein however 0.024 mol of water and other organometallic quantities of ethylene oxide and the polymerization compounds were used; Then the temperature was changed.

The results obtained are shown in Table 8.

Table 8

Organometal compound crowd temperature Amount of Polymerization Polymer 16.2 with N.N-Di- 18.5 (Mole) the production
of the catalyst Ethylene oxide length of time·) without N ₁ N-Di- methylaniline 19.7 0.0015 meihylaniline Out 24.1 No. Art 0.003 (E) (Hours} Out prey 22.4 0.0015 140 100 64 bump (G) Diethyl zinc 0.0015 128 Π5 72 (G) 97 1 Diethyl magnesium 132 115 72 31 2 Triethylaluminum 125 115 72 35 31 3 Diethyl zinc 72 **) 4th

Note *) Time during which the mixture was left to stand. **) 0.0075 mol of Ν, Ν-dimethylaniline were used.

Example iö

A white catalyst suspension was produced as in Example 8, but with the following differences: A 2-1 four-necked flask, 1.21 of a mixture of n-heptane and decalin, 1.2 mol of aluminum triisopropoxide, 0.72 mol of water, 100% were used ml of 1,4-dioxane and 0.12 mol of diethyl zinc were used. The partial hydrolysis product was subjected to distillation, to the by-produced alcohol, then subjected to distill off bsi 140 ⁰ C before the addition of diethylzinc a 1 hour heat treatment. The temperature during the catalyst production was 105 ^° C.

In an enamelled reactor of 301, which was versehea with a stirrer, the air 0.84 mole of N, N-Diinsih "were determined by the displacement by nitrogen 24 1 η-hexane, the above-mentioned Su ^r board,! IINI! In and 4 kg of ethylene oxide were charged in the order given, and the resulting mixture was stirred for 6 hours at room temperature and then allowed to stand for 94 hours to polymerize out the ethylene oxide, 3.93 kg of a polymer having an inherent viscosity of 22.1 being obtained.

Example 11

The polymerization was carried out as in Example 8, but with the following differences: The temperature of the catalyst production was 105 ⁰ C, there were equimolar amounts of other tertiary types? ine used instead of N, N-dimethylaniline and 88 g of ethylene oxide. The mixture was stirred for 6 hours and then allowed to stand for 42 hours. The results obtained are shown in Table 9.

Table 9 Example 14

Tertiary amine Polymer M. No. yield N.N-diethylaniline (G) 15.1 1 Diethylcyclohexylamine 65 14.2 2 Triethylamine 48 14.6 3 n-methylmorpholine 49 13.9 4th 55

Example 12

In the same reaction vessel as in Example 1, after displacing the air with nitrogen, 80 m! Decaun, 75 ml of n-Hepian, 0.06 mol of aluminum triisopropoxide and 0.005 mol of diisopropylamine filled. The mixture was heated to 80 ° C. with slow stirring, whereupon 0.048 mol of water diluted with 50 ml of 1,4-dioxane was gradually added to the mixture over a period of 2 hours with vigorous stirring. Then, the isopropyl alcohol formed as a by-product and the isopropylamine were distilled off. In order to complete the removal of the alcohol and the amine, the distillation was continued for an additional 5 minutes after the temperature had reached the boiling point of the De-CaIUr *. With the partial hydrolyzate of aluminum triisopropoxide thus prepared, ethylene oxide was polymerized without a tertiary amine in the same way as according to method A of Example 7, about 50% of the monomer being converted into a polymer with an inherent viscosity of 14.8. . . ,,
Example 13

The polymerization was as, but carried out according to Example 4 with the following differences: There were η-hexane used instead of rubber gasoline and kerosene and 30 ml of acetone as an additive, the distillation was stopped, reached when the temperature is au apparatus 71 ° C. The isopropyl alcohol by-product was distilled off at 91% of the mixture of the partial hydrolysates with diethylzinc was heated at 140 ⁰ C in a closed system under pressure, and 0.2 mol of N, N-Dimethyiani) in the catalyst during the polymerization added, 77O g of a polymer having an inherent viscosity of 18.6 were obtained.

The polymerization was carried out as in Example 13, but using a mixture of 45 ml

s methanol and 20 ml of acetone were used in place of the acetone; after the completion of the reaction, the solvent was distilled off after adding diethyl zinc, whereby a white powder was obtained. A mixture of ethylene oxide with this white powder as a catalyst, which was free from N ₁ N-dimethylaniline, was polymerized for 20 hours, 250 g of polymer being obtained.

Example 15

In a lOO-mi-Eeaktionsgeiäp, from which the loft was displaced by nitrogen, 40 ml of n-Hcxan and a catalyst suspension were introduced, which as according to Example 8, but with the following deviations

had been obtained: The temperature during the catalyst production was 128 ° C, the amount of the catalyst corresponded to 0.05 mol of aluminum in the compound. Then another 20 ml of propylene oxide were added, and the mixture formed was at room temperature Left for 30 hours. There were 5.2 g of a polymer with an inherent viscosity of 6.4 obtained.

In contrast, η-hexane, which was partially hydrolyzed Aluminum triisopropoxide (as prepared according to examples), Diethyl zinc and propylene oxide are poured into the same reaction vessel as above, without the If catalyst components were reacted beforehand, 1.9 g of polymer with an inherent viscosity were obtained obtained from only 3.0.

Example 16

Propylene oxide was polymerized as in method A of Example 7, but with the following deviations: Aluminum isopropoxide and 20 m! Propylene oxide was used, the polymerization was carried out at room temperature, the polymerization time was 72 hours, and the organometallic compound and the tertiary amines were varied as shown in Table 10, the results shown in Table 10 being obtained. The insoluble in cold acetone part is a measure of the crystallinity of the polymer produced (measured at 0 ⁰ C).

Table 10

Organometallic compound crowd Without Out 1 45 J tertiary amine in cold ί With tertiary amine crowd Out Polymer in cold I. prey 'olymerisat acetone i tertiary amine prey acetone (Mole) more insoluble I. (Mole) more insoluble No. Art 0.00125 <%) part 0.0015 <"/.) i'il part 32 M. (%) Art 31 (V.) 32 28 Diethy! Magnesium 0.00125 0.0006 8.4 ι (Diethyl ether 0.00025 - 5.4 Ν, Ν-Di- 0.0015 27 0.3 ml) - methyl- 37 - the same 0.001 aniline 7.4 2 Di-n-butyl zinc - Pyridine 9.1 3 (n-heptane 0.3 ml) N, N-Di- Diisopropyl 6.3 methyl- magnesium aniline (Diethyl ether)

In sample no. 1, 24% of the monomers used were converted into a polymer without a tertiary amine with a viscosity of 2.0 when diethyl magnesium was not used. Didn't become Suspension of the partial hydrolyzate of aluminum triisoproposide used in n-Hqrtas, no Obtained polymer.

Example 17

20 ml of propylene oxide were used as in Example 7, Method B, with no tertiary amine was polymerized, but with the following ^ "deviations: Aluminum triisopropoxide was used as the aliüsiniuBiali ·: .xyd and sts ^., 4-dioxane were 50ml other accessories wr.Ycuüet. Diethyl zinc was used as a Oigancnieiaiiver-iciung uses the temperature at the Her.5 * i «> mg of the catalyst was 140 ° C, the polymerization was carried out at room temperature, and the polymerization time was 72 hours. The results obtained are shown in Table II.

Table 11

additive Out Polymer in cold prey acetone No. (%) more insoluble Methanol 50 M. part Ethanol 63 38 1 Isopropanol 53 8.2 35 2 acetone 60 3.1 22nd 3 1,4-dioxane 56 5.0 25th 4th 5.4 27 5 4.6

Example 18

It was a white suspension of catalyst prepared as in Example 10, but using ^d: e the temperature of the partially hydrolyzed WärmebehandluEg Aluminiumtriisopropoxyds was varied before the addition of diethylzinc.

The suspension thus obtained was together with 20 ml of propylene oxide and 20 ml of η-hexane under a Filled nitrogen atmosphere in an amount corresponding to 0.005 mol of aluminum in an IOC ml glass vessel. The resulting mixture was allowed to stand at room temperature for 72 hours, with the in Results given in Table 12 were obtained.

table Out
prey ! 2 Polymer ui cold aa
more insoluble ' Temperature of (%) M. (%) ίο No. Heat treatment 27 21 CC) 45 3.5 26th 1 60 53 3.8 29 2 100 54 4.7 32 3 140 4.3 4th 180

Example 19

A mixture of 5? g ethylene oxide and 5 g of propylene oxide was as described in Example 3, but with the following differences polymerized: There are Aluminiumtriisopropoxyd as aluminum alkoxide, a mixture of 130 ml rubber petrol (boiling point 80 to 120 ⁰ C) and 30 ml of kerosene (boiling point 158-230 ° C ) used instead of 50 ml rubber gasoline and acetone instead of isopropanol. Water was added in amounts of 0.081 moles. The distillation was continued until the temperature reached 140 "C. The

Amount of diethylzinc was 0.0135 mol and the temperature at which the catalyst was kept under total reflux, was 140 ⁰ C. 40 g of a copolymer obtained, which was, ialyse identified by infrared analysis and thermal Diiierenüala. This copolymer was soluble in water and had an inherent viscosity of 3.3 (measured in aqueous solution at 35 ° C.).

Example 20

The polymerization was as in Example 15 carried out, but where a mixture of 15tnl Propylene oxide and 5 m! Ally! Glycidyl ether was used instead of 20 ml of propylene oxide. There were 3 g of one Polymer obtained, which can be vulcanized in the usual way.

Claims (3)

Patent claims: 1. Process for the production of hochmolekula Ren alkylene oxide polymers or copolymers! sowed by polymerization of at least one alkylene oxide with the formula R ₇ HC; -CH ₂ wherein R _{7 represents} a hydrogen atom, a methyl, ethyl, phenyl, vinyl, chloromethyl, bromomethyl, methoxymethyl, allyloxymethyl or a pheaoxymethyl group, in the presence of a catalyst containing an organoaluminum compound, characterized in that the polymerization in the presence of a reaction product as a catalyst, which is obtained by reacting a partially hydrolyzed aluminum alkoxide, which is obtained by reacting an aluminum alkoxide with the formula R ₁ O-Al-OR ₂ OR, in which R ₁ , R ₂ and R ₃ each represent saturated aliphatic hydrocarbon radicals with 1 to 6 carbon atoms, which is dispersed or dissolved in a liquid inert medium of aromatic and saturated hydrocarbons and / or ethers, with 0.01 to 2.8 mol Water per mole of aluminum alkoxide ^{has been obtained at temperatures from -50 to +300 0} C, with at least one organometallic compound of the formulas R ₄ - M ⁿ - K ₅ R ₄ -M ¹¹¹ -R ₅ R where R ₄ , R ₅ and R ₅ each represent saturated hydrocarbon radicals with 1 to 6 carbon atoms or phenyl groups, M "represents beryllium, magnesium. Calcium, strontium. Barium, zinc, cadmium or mercury and M ¹ " represents a metal from main group 3 of the periodic table , and complexes of these compounds in amounts of 0.001 to 2.5 moles of organometallic compound per mole of aluminum of the partially hydrolyzed aluminum ?? alkoxide has been obtained at a reaction temperature of -50 to + 30O ⁰ C, carried out, the amount of catalyst from 0.0001 to 0.3 mol (as aluminum contained in the catalyst) per mole of alkylene oxide and the polymerization temperatures from -50 to +150 ⁰ C. 2. The method according to claim 1, characterized in that the polymerization is m the presence a catalyst carries out the reaction product from the partially hydrolyzed Aluminum alkoxide obtained by reacting the aluminum alkoxide of the formula