DE1162563B - Process for the polymerization of aldehydes - Google Patents

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FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Boarding school Class: C 08 g

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German class: 39 c-18

M 47003 IVd / 39 c
November 2, 1960
February 6, 1964

High molecular weight homopolymers of formaldehyde or acetaldehydes of the acetal type are known (cf. French Patent 1,131,940) and have been produced using very different catalysts and processes. For example, catalysts such as organometallic compounds, boron trifluoride, nickel carbonyl, triphenylphosphine and ferrocene were used for the polymerization of formaldehyde. 50 ⁰ C proposed - for the polymerization of acetaldehyde was ammonium persulfate as catalysts, boron trifluoride and aluminum oxide at temperatures between -100 and.

Of higher aldehydes than acetaldehydes, e.g. B. n-butyraldehyde, iso-butyraldehyde, n-valeric aldehyde, So far, only unstable polymers are known that under difficult conditions, which in practice with great cost can be obtained.

C o η a η t and Peterson (J. Am. Chem. Soc, 52, p. 1668 [1930]; 54, p. 628 [1932] obtained solid amorphous polymers of these aldehydes, which are unstable at room temperature, using pressures of the order of 12, 000 atm and in the presence of Peroxydkatalysatoren. these authors write the polymers a Polyacetalstruktur to and expressly state that these polymers are completely decomposed after 24 hours at room temperature and even more rapidly at temperatures of about 50 to 70 ⁰ C. In the publication from 1952 (B e ν i η gt ο n, Quaterly Reviews, 6, p. 152 [1952]) it was predicted that polymers of aldehydes higher than acetaldehyde would be very unstable at room temperature.

High polymers of higher aldehydes than acetaldehyde, which are stable in practice and therefore usable were previously unknown.

The invention relates to a process for the polymerization of aldehydes at temperatures from -40 to - 100 ⁰ C in the liquid phase, under anhydrous conditions in wesentliehen means of catalysts of the general formula

MeX _n R _m

Process for the polymerization of aldehydes

Applicant:

Montecatini Societä Generale per l'Industria

Mineraria e Chitnica, Milan (Italy)

Representative:

Dr.-Ing. A. v. Kreisler, Dr.-Ing. K. Schönwald
and Dr.-Ing. Th. Meyer, patent attorneys,
Cologne 1, Deichmannhaus

Named as inventor:

Giulio Natta,

Giorgio Mazzanti,

Paolo Chini, Milan (Italy)

Claimed priority:

Italy of November 6, 1959 (No. 18 497)

Italy of December 16, 1959 (No. 20 976)

indicates that aldehydes of the general formula _

R -c;

in which R is an alkyl radical with 2 to 10 carbon atoms, a cycloalkyl or an arylalkyl radical means polymerized alone or with one another. The polymers and copolymers prepared according to the invention are characterized in that they have an essentially linear main chain which has a polyacetal structure of the following type: HHHH

C — Ο — C — Ο — C — Ο — C — Ο—

in the Me an element of II. or III. Group of the Periodic Table, X halogen or hydrogen atoms, R alkyl, aryl, alkoxy or acyl radicals, m and η denote an integer or O and the sum of η and m is equal to the valency of Me, or their addition complexes with Ethers, optionally in the presence of solvents, which thereby ge-RRRR

The following connections are e.g. B. suitable as catalysts in the process according to the invention: Be (C ₂ H ₅ ); Mg (C ₆ H ₅ ), -O (C ₂ H ₅ ) ₂ ; (C ₄ H ₉ ) ₂ Mg; (C ₄ He) ₂ Zn; C ₄ H ₆ ZnJ; ZnCl ₂ ; BF ₃ ;

BF ₃ -O (C ₂ H ₅ ) ₂ ; AlCl ₃ ; AlBr ₃ ; AlCl (C _a H ₅ ) ₂ ; A1 (C ₄ H ₉ ) ₃ ; Al (C _a H ₆ ) ₈ • O (C ₂ H ₆ ) ₂ ; AlCl ₂ (C ₂ H ₅ ); AlCl ₂ (C ₄ H ₉ ); AlCl ₂ OCH ₃ ; A1C1 (OC ₈ H ₇ ) ₂ ;

A1 (C ₄ H ₉ ) ₂ H.

409 507/473

3 4

All of the above listed catalysts need boiling ether. They have a molecular weight

under substantially anhydrous conditions used in the order of 10 ~. ⁵

will. The homopolymers obtained contain high

The amounts of catalyst used are generally proportions of crystallizable eutactic macromolecules

mean very little and depend mainly on the 5 külen, at least one over long chain sections

The type of catalyst used and the purely regular steric structure of the isotactic type

unit of the monomers. In general, it can be said to sit. The regularity of the steric structure

that a minimum ^{concentration of 10 ~ e} moles of these macromolecules gives these polymers mechanical

Catalyst per mole of monomer is desirable. The niche properties required for polymers of higher

Polymerization temperature is -40 to - not anticipated 10O ⁰ C, io aldehydes as acetaldehyde

could be preferably from -60 to -80 C. ^0th The presence of macromolecules

The formation of high polymers with the pre- with regular structure, the presence of the mentioned catalysts is surprising, if crystalline fractions are required, it can even be considered with what is known about the chemical behavior of crude polymerization products in powdered aldehydes. In fact, it emerges from this stand by X-ray analysis with the aid of literature related to Geiger that the aforementioned counters are determined. The diffraction spectra obtained when using a compound with aldehydes according to a mechanism copper anticathode react which is completely different from that which is necessary for a polymerization in general to show a very sharp diffraction. For example, the maximum intensity for angle 2 Θ (the character-reducing magnesium alkyls which are aldehydes to Aiko- 20 ristic for each aldehyde and get from the size, and a similar reaction will also depend on R) in the range between 6 and 11 ⁰ C causes aluminum trialkylene. This is typical for polymeric substances with considerable

The polymerization can take place in bulk without any degree of order.

The exact position of this maximum corresponds to each

means that with the monomer or the catalyst 25 according to the starting monomer different Beu-

under the polymerization conditions, as shown in Table 1, do not react. and not at the temperatures used

solidify, be carried out. For example, labeile can propane, pentane, n-heptane, isooctane, toluene,

Ethyl chloride, methyl chloride, methylene chloride, di- 30 polymer

ethyl ether and diisopropyl ether as solvents

be used.

Polypropionaldehyde

10.25 9.80 9.00 8.50

In general, it is preferred to use the cata- poly-iso-butyraldehyde ". '.'. '.'. '.'. '.'. '.'. '.'. '.

capacitors, or the solution of the monomer or p _o j _n butvraldehyd a monomer solution to the polymerization 35 poly-iso-valeriomaldehyd '.'. '.'. Υ. '.'. '.'. '.,', ''

temperature were cooled, add the polyheptaldehyde i 6 70

The additional speed of the catalyst depends on the

The values of the angle 2 Θ are approximately within, half ¹ F 3 °. The first inflection is a regular one

Of course, the polymerization can also be carried out in a continuous chain arrangement normal to the chain axis.

to be carried out naturally; for example can write. In numerous cases, such as

the catalyst solutions and the aldehyde (or, in the case of crude polymers of propionaldehyde, valerian

Solution), both pre-cooled, continuously in an aldehyde and heptaldehyde (see the following examples 6,

Reaction apparatus are supplied, for example 8 and 13 and Figs. 1, 3 and 4) can be in the

in a tubular reactor, the apparatus 45 diffraction spectrum due to crystallinity also other

is cooled in such a way that the temperature is observed during the maxima which are necessary for a clear three-dimensional

sional order are characteristic of the entire passage in the desired area. This crystalline

remain. In a few hours a high level of umnity can only be achieved through a regular steric structure

sets of monomers to high molecular weight polymers are caused along the chain axis, can be achieved. 50 This regularity is particularly good due to the

At the end of the polymerization, the polymer can be seen by examining the spectra that are oriented towards

Determined by physical methods from reaction mes- Fibers made from raw polymers

dium separated, were obtained with small amounts of a base.

treated to remove all acid residues (e.g. with For example, in the case of fibers made from raw iso-

an amine), and then dried. The invention 55 butyraldehyde polymer the presence of an identity

according to the polymers obtained are activity period along the chain axis at room temperature, accordingly

stable and generally remain up to temperatures of about 5 Å as determined by X-ray analysis

stable from about 60 to 7O ⁰ C. The thermal stability will be.

These polymers can in all cases by addition There is the possibility by extraction with

of suitable amine compounds and, by addition, suitable solvents from the crude polymers

usually used for the stabilization of polymers to isolate fractions that have a different crystalline

used antioxidants considerably increased nity and a different degree of regularity in

will. A higher thermal stability can also contain the macromolecules, as well as essentially

by appropriate chemical treatments, alkylating amorphous non-crystallizable fractions that result from

or acetylation of the end groups. 65 atactic macromolecules exist. The solution

The aldehyde homopolymers produced according to the invention, which can be used for this purpose,

mers are solid products, generally in boil- are depending on the type of poly-

Insoluble in acetone, mostly only partially soluble in several different ways. For example, through

Extraction of a crude n-Butyraldehydpolymeren (prepared at -78 ⁰ C by means of Aluminiumäthyldichlorid as a catalyst) with Acetondiisopropyläther and benzene at their boiling point in that order the following four fractions obtained:

an acetone extract having an oily appearance in an amount of 4%;

a Diisopropylätherextrakt in an amount of 59 ° / _0, consisting of a plastic solid that turns out as in X-ray analysis only partially oriented;

a benzene extract in an amount of 6%> its properties those of the previous fraction correspond;

a residue after benzene extraction in an amount of 31 ⁰ I ₀ , which according to X-ray analysis with a Geiger counter (Cu Ka) has a high degree of crystallinity and consists essentially of isotactic macromolecules (see FIG. 2).

The spectrum of an oriented one prepared from this fraction not extractable with benzene Fiber shows a high crystallinity and enables the determination of an identity period along the Chain axis of about 5 Å.

The infrared analysis of the polymers produced according to the invention confirms a polyacetal structure of the main chains according to the formula Mass immediately becomes gelatinous. After 24 hours, 50 ml of acetone and 1 ml of triethylamine are added and the mass is brought to room temperature. After filtering and drying in vacuo, 18.1 g of a solid white polymer are obtained. If this is heated under vacuum, it only begins to decompose noticeably above 80 ° C. The X-ray diffraction spectrum (Cu K «) of this polymer has a main peak at 2 Θ = 9 ° 80.

If you put 5.0 g of this polymer in a Kumagawa extractor under nitrogen with boiling Extracted solvents, the following results are obtained:

solvent Extraction
Time
hours extract
Vo Crystallinity
of
Extract acetone
ao diisopropyl ether
benzene 15th
40
10 5
18th
11 low
low

HC - O - CH - O - CH - O

30th

By using the method according to the invention, copolymers of higher Aldehydes are produced together as acetaldehyde.

For example, by copolymerization, the residue after extraction is 66% and is highly crystalline. If it is heated under vacuum at 90 ° C for 450 minutes, it only loses 3% Weight.

2.15 g of this polymer obtained as a residue after the extraction are heated for 3 hours with 10 ml of pyridine and 10 ml acetic anhydride under nitrogen at 81.5 ⁰ C. The polymer is then filtered off, washed with n-heptane and methanol and dried. The weight of the polymer thus obtained is equal to that of the starting polymer.

However, the thermal stability of the polymer treated in this way is higher than that of the starting polymer.

Example 2 25 ml of isobutyr-

an equimolar mixture of n- and isobutyraldehyde introduced and ^{cooled to -78 0} C, an-

aldehyde obtained a solid plastic copolymerization product that is insoluble in acetone, while im In contrast, the homopolymers of the same monomers with boiling diisopropyl ether almost are fully extractable.

The polymers produced according to the invention can (especially after improving their thermal Stability) using the usual casting and shaping processes as plastics will.

The amorphous fractions and the amorphous copolymers show elastomeric properties and can be used for the production of elastic special rubbers. The more crystalline Fractions of the homopolymers are more suitable for the production of films and textile fibers.

The invention is illustrated in the following examples. The fractionation of the products is carried out in the Not claimed within the scope of this invention.

a measuring pipette are keyed 0.25 ml of a 2 ° / ₀ solution of BF ₃ · (C ₂ H _{5) 2} O solution is added in diethyl ether using. The polymerization takes place immediately. After 1 hour the temperature is increased to room temperature. The polymer represents a compact block. There is a transparent polymer film on the wall of the sample tube. The turnover is almost quantitative. When working under the same conditions, but using anhydrous zinc chloride instead of the boron fluoride etherate, a slow polymerization takes place with the formation of a polymer similar to that mentioned above.

Example 3 example 1

A mixture of 25 ml of anhydrous diethyl ether and 25 ml of isobutyraldehyde is introduced into a large test-tube, maintained under nitrogen and carbon dioxide-acetone mixture is cooled to -78 ⁰ C by means of a.

Using a measuring pipette, 2 ml of aluminum ethyl dichloride solution in diethyl ether are then added. A mixture of 25 ml of isobutyraldehyde and 25 ml of n-heptane is placed in a large test tube and cooled to -78 ° C; then 0.15 ml of a 23% AlBr ₃ solution in toluene are added using a measuring pipette. After 27 hours, 25 ml of acetone and 1 ml of triethylamine are added and the mixture is allowed to warm to room temperature. After filtering, washing with acetone and drying in vacuo, 3.7 g of polymer are obtained in the form of a fine powder. The thermal stability and the X-ray diffraction spectrum of this polymer are similar to those of the polymer prepared according to Example 1.

Example 4

A mixture of 25 ml of isobutyraldehyde and 50 ml of anhydrous diethyl ether is placed under nitrogen in a large test tube and cooled to -78 ° C; then 0.9 ml of a 2% A1 (C ₂ H ₅ ) ₂ -Cl solution in diethyl ether are added using a graduated pipette. After 14 hours, 25 ml of acetone and 0.25 ml of concentrated NH _{3 are} added and the temperature is allowed to rise to room temperature. After filtering, washing and drying 1.25 g of solid polymer are obtained.

When using 0.01 ml

Al (C ₂ H ₅ ) Cl ₂ ■ (C ₂ H ₅ ) ₂ O

as a catalyst and when working under the same conditions, 3.3 g of solid polymer with a density D ™ = 0.987 are obtained after 7 hours.

The polymers thus obtained have a thermal stability and an X-ray diffraction spectrum similar the product of example 1.

trum (Cu Ka) has a main peak of 2 Θ = 9 ° 10. When 5 g of the polymer is extracted with boiling solvents in a Cumagawa extractor under nitrogen, the following results are obtained.

solvent Extraction
Time
hours extract
7o Crystallinity
of
Extract acetone
Diisopropyl ether
benzene 15th
40
19th 4th
59
6th low

The extraction residue corresponds to 30% of the original weight and is highly crystalline (see Fig. 2). _

The extracted with ether product has an intrinsic viscosity (in toluene at 30 ⁰ C) of 1.15 corresponding to a molecular weight in the order of 10. ⁵

B e i s ρ i e 1 7

Example 5

A mixture of 45 ml of propionaldehyde, and 50 ml of diethyl ether is placed in a large test tube and cooled to -78 ⁰ C; then a mixture (1.15 ml) of Al (C ₂ Hg) ₂ Cl, Al (C ₂ H ₅ ) Cl ₂ and BF ₃ · (C ₂ H ₅ ) ₂ O in a volume ratio of 100:10 is made using a graduated pipette : 2 added. The polymerization takes place immediately. After 5 hours, 50 ml of diethyl ether and 2 ml of concentrated ammonia are added and the temperature is increased to room temperature. _

The ether is evaporated in vacuo, 150 ml of methanol are added and the mixture is filtered. After washing and drying in vacuo, 8 g of a pale yellow solid powdery polymer are obtained. The polymer begins only about 80 ⁰ C to decompose.

The X-ray diffraction spectrum (Cu Ka) has a main peak at 2 Θ = 10 ° 25 (see FIG. 1, in which the recording is given with the aid of a Geiger counter of X-ray diffraction [Cu Ka] measured on powdered polymer; the diffraction angles are at the The abscissa and the intensities plotted on the ordinate on a relative scale).

After extraction for 24 hours under nitrogen with boiling diisopropyl ether, the residue is 45% of the original weight and is highly crystalline.

Example 6

A mixture of 25 ml of n-butyraldehyde and 25 mL of anhydrous ether is placed in a large test tube and cooled to -78 ⁰ C; then (C ₂ H ₅₎ C1 ₂ solution in diethyl ether are added dropwise within 45 minutes 3 ml of a 1% ^en A1. A large amount of a gelatinous polymer forms immediately. After 16 hours, 50 ml of acetone and 1 ml of triethylamine are added and the temperature is allowed to rise to room temperature. After filtering, washing and drying in vacuo, 12 g of solid white polymer are obtained.

The polymer begins to decompose at temperatures above 80 ⁰ C. The X-ray diffraction spec- A mixture of 32 ml of isovaleric aldehyde (3-methylbutyraldehyde) and 25 ml of diethyl ether is placed in a large test tube and cooled to -78 ° C.

Then 0.7 ml of a mixture of A1 (C ₂ H ₅ ) ₂ C1 and Al (C ₂ H ₅ ) Cl ₂ in a volume ratio of 13: 1 are added using a graduated pipette. The polymerization takes place immediately. After 2 hours, 50 ml of acetone and 2 ml of triethylamine are added and the temperature is increased to room temperature.

After filtering, washing with acetone and drying in vacuo, 7.7 g of a pale yellow powdery product are obtained solid polymers obtained.

This polymer begins to decompose at temperatures above 8O ⁰ C. The X-ray diffraction spectrum (Cu Ka) has a main peak at 2 Θ = 8 ° 5 (see Fig. 3). After extraction for 24 hours with boiling diisopropyl ether under nitrogen, a residue corresponding to 57% of the original weight is obtained, which is highly crystalline.

45

Example 8

A mixture of 10 ml of n-butyraldehyde, 10 ml of isobutyraldehyde and 25 ml of anhydrous diethyl ether is placed in a large test tube and cooled to -78 ° C. Then 3 ml of a 1% A1 (C ₂ H ₅ ) C1 ₂ solution in diethyl ether are added dropwise over the course of 15 minutes. The solution becomes more and more viscous and eventually gels.

After 3 hours, 75 ml of acetone and 2 ml of triethylamine are added and the temperature is allowed to rise to room temperature. After filtering, washing with acetone and drying in vacuo, 10.5 g of a solid polymer are obtained. This polymer begins to decompose at temperatures above 8O ⁰ C.

5 g of this polymer can under nitrogen in a Kumagawa extractor with boiling solvents extracted. From comparing the results of this extraction with the results that for the corresponding homopolymers, it can be seen that a true copolymer is present.

solvent Extraction time
hours n-butyraldehyde
homopolymer Extract, ° / "
i-butyraldehyde
homopolymer n-butyraldehyde
iso-butyraldehyde
copolymer acetone 15th
40 5
18th 4th
59 7th
90 Diisopropyl ether

The extracted with ether product has an intrinsic viscosity (in toluene at 30 ⁰ C) of 0.87 corresponding to a molecular weight in the order of 10. ⁵

Example 9

A mixture of 10 ml of n-heptaldehyde and 25 ml of toluene is introduced into a large test tube and cooled to -78 ⁰ C. Then 0.5 ml of a 33% A1 (C ₂ H ₆ ) ₂ C1 solution in n-heptane is added using a graduated pipette. The mixture becomes more and more viscous and is completely gelled after 1 hour.

After 20 hours, 0.5 ml of triethylamine are added and the mixture is allowed to warm to room temperature. A further 200 ml of acetone are then added, the product is filtered and washed with acetone. After drying in vacuo, 0.8 g of a plastic white polymer are obtained. The X-ray diffraction spectrum (Cu Ka) has two main peaks at 2 Θ = 6 ° 70 and 7 ° 50 and confirms that this product is a high polymer (see FIG. 4). The polymer melts between 84 and 94 ° C.

Example 10

35

25 ml of isobutyraldehyde are diluted with 25 ml of diethyl ether and under nitrogen to - 78 ⁰ C cooled. After addition of 1 ml of 10.4 ° / ₀ hydrochloric Al (C ₂ Hs) ₃ solution in n-heptane immediately starts the polymerization and proceeds very quickly away. After about 3 hours the contents of the reactor appear as a solid white mass. After 12 hours, the reaction mixture is brought to room temperature, the polymer is suspended in acetone and filtered.

After drying under reduced pressure, 15 g of a white solid are obtained X-ray analysis proves to be crystalline. The extraction of this polymer, carried out under nitrogen in a Cumagawa apparatus shows that 81% of the Product can be extracted with boiling diisopropyl ether and are highly crystalline.

When working under the same conditions, but taking the polymerization in the absence of Solvents is carried out, 17 g of a polymer with similar properties as above described, received.

Example 11

25 ml of n-butyraldehyde are diluted with 25 ml toluene and cooled to -78 ⁰ C, operating under nitrogen. Then 1 ml of a 20% solution of Zn (C ₄ H ₉ ) ₂ in n-heptane is added. The liquid slowly becomes more and more viscous. After 20 hours, 10 ml of butanol are added; the mixture is brought to room temperature; the toluene is removed under reduced pressure.

The residue is taken up in methanol and filtered. After drying under reduced 0.8 g of an n-butyraldehyde polymer are obtained under pressure, which is highly crystalline on X-ray analysis proves.

Example 12

10 ml of n-butyraldehyde are diluted with 10 ml of diethyl ether and - cooled 70 ⁰ C, operating under nitrogen. After the addition of 1 of a lO ° / oig ^e n Be (C ₂ H _{5) 2} ml of solution in n-heptane occurs a slow polymerization.

After 24 hours the temperature is brought to room temperature and the polymer is then dissolved in acetone suspended, filtered and washed with acetone. After drying under reduced pressure, 0.9 g obtained a highly crystalline white polymer.

Example 13

0.32 g of A1 (C ₂ H ₅ ) ₃ and 25 ml of toluene are placed under nitrogen in a three-necked flask equipped with a stirrer and a dropping funnel. Is added dropwise to this cooled to -78 ⁰ C. A solution of 15 ml of phenylacetaldehyde in

15 ml of toluene added. After a few minutes it starts the polymerization and proceeds rapidly. To

16 hours the polymer, a solid compact Mass, purified by suspending in butanol and then washing with methanol.

After drying under reduced pressure, 11.1 g of solid white product are obtained. An extraction of the polymer in a Cumagawa hot solvent extractor shows 6% of the polymer extractable with acetone and 3% with benzene. Both the benzene extract and the extraction residue turn out to be crystalline in X-ray analysis. A stability test carried out by Heating the polymer for 4 hours under vacuum (0.1 mm) shows that it is extremely stable because no change in weight was found.

Example 14

5 ml of phenylacetaldehyde are slowly added under nitrogen to 30 ml of a 0.09 molar solution of C ₆ H ₆ MgBr in ethyl ether cooled to -78 ° C. After 16 hours, 0.99 g of a white polymer are obtained, the procedure being as described in the previous example. 90.8% of this polymer are insoluble in ethyl ether and are found to be crystalline on X-ray analysis.

Example 15

8 ml of phenylacetaldehyde are diluted with 40 ml of toluene and then cooled to -78 ⁰ C, operating under nitrogen. Then a 5% ig i Be (C ₂ H _{5) 2} solution in toluene ^he added 6 ml. After 20 hours the catalyst is decomposed with butanol and hydrochloric acid, and 0.9 g of a white powdery polymer is obtained.

17.8 and 25.4% of this polymer can be extracted with acetone and benzene, respectively. This frac-

409 507/473

The X-ray analysis shows that the ions and the extraction residue are crystalline.

Example 16

15 ml ß-phenylpropionaldehyde, diluted with 25 ml of toluene, are placed in a equipped with a stirrer and dropping funnel and then cooled to -78 ⁰ C, operating under nitrogen.

7 ml of a 3% strength A1 (C ₂ H ₅ ) ₃ solution in toluene are then added dropwise with stirring. After a few minutes, an increase in the viscosity of the solution is observed. After 22 hours, the catalyst is decomposed with butanol and, after purification with methanol and drying under vacuum, 8.94 g of white polymer are isolated. 20% of the polymer is extracted with hot acetone and 21% with boiling benzene. The acetone extract proves on the X-ray analysis to be amorphous and has an intrinsic viscosity (determined in toluene at 30 ⁰ C) of 0.74. ao

The benzene extract with an intrinsic viscosity of 0.7 and the extraction residue are found in the X-ray analysis as amorphous.

The polymer is completely soluble in hot chlorobenzene, o-dichlorobenzene and anisole. During the stability test, carried out by heating for 4 hours at 90 ° C. under vacuum (0.1 mm Hg) shows the polymer a weight loss of 1.25%.

B is ρ ie 1 17 _on

15 ml / J-phenylpropionaldehyde, diluted with 10 ml ethyl ether and cooled to -78 ⁰ C, is added dropwise under nitrogen, to 20 ml of a 0,07molaren C ₆ H ₅ Br Mg solution in ethyl ether was added. After a process lasting three hours, as described in the previous example, 3.54 g of a white polymer are isolated. 20% of this polymer can be extracted with hot acetone and 50% with benzene.

Both the acetone and benzene extracts and the residue are revealed by X-ray analysis as crystalline. The acetone extract has an intrinsic viscosity (in toluene at 30 ° C) of 0.11 and the Benzene extract of 0.46.

Example 18

5 ml / S-phenylpropionaldehyde are diluted with 10 ml toluene and cooled to -78 ⁰ C. Then are slowly added under nitrogen 2 ml of a 1% ^en A1 (C ₂ H _{5) 2} C1-solution in toluene. After 20 hours, 1.5 g of solid polymer are isolated. During the extraction with hot solvents, 67% of this polymer is dissolved in acetone and 1% ^m ethyl ether. The residue is crystalline according to X-ray analysis.

Example 19

4 ml of a 5% Al (C ₂ H ₅ ) ₃ solution in toluene are placed under nitrogen in a flask equipped with a stirrer and dropping funnel. After cooling to -78 ° C., a solution of 5 ml / I-phenylbutyraldehyde in 3 ml toluene is added dropwise. After 20 hours, 1.5 g of a white powdery polymer are isolated. ^{1% m} acetone and 12.6% ^m benzene dissolve from this polymer during extraction with hot solvents. The benzene extract and the extraction residue are crystalline according to X-ray analysis. In a stability test, carried out by heating for 1 hour under a vacuum of 0.1 mm Hg at 140 ^° C., the polymer showed a weight decrease of 2.94%.

Claims (1)

Claim: Process for the polymerization of aldehydes at temperatures from -40 to -100 ° C in liquid Phase under essentially anhydrous conditions by means of catalysts of the general formula MeX "R _m in the Me an element of II. or III. Group of the Periodic Table, X halogen or hydrogen atoms, R alkyl, aryl, alkoxy or acyl radicals, nt and η denote an integer or O and the sum of η and m is equal to the valency of Me, or their addition complexes with Ethers, if appropriate in the presence of inert solvents, characterized in that aldehydes of the general formula R —c: in which R is an alkyl radical with 2 to 10 carbon atoms, a cycloalkyl or an arylalkyl radical means polymerized alone or with one another. Considered publications:
French Patent No. 1,131,940;
Comptes rendues, 241, 1955, pp. 1765-1766. When the registration was announced, two priority documents were displayed. For this purpose 2 sheets of drawings 409 507/473 1.64 © Bundesdruckerei Berlin