DE1239099B - Process for the production of stable aldehyde polymers - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C08g

German KL: 39 C-19

Number: 1239 099

File number: Z 9874 IV d / 39 c

Filing date: January 25, 1963

Open date: April 20, 1967

It is already known to produce Aldehydpolymerisate by polymerization of aldehydes using coordination complexes of elements of the I. to m. Group of the Periodic Table at a temperature below -40 ⁰ C.

It is also known that complexes or reaction products formed by adding halides of the elements of groups IV to VIa of the periodic table to form organometallic compounds of the elements of groups I to III of the periodic table are produced, polymerize olefins.

The invention relates to a process for the preparation of stable aldehyde polymers by polymerizing saturated aliphatic aldehydes having 2 to 4 carbon atoms at temperatures below -40 ° C in the presence of inert solvents and catalysts, which is characterized in that catalysts are used which react of organometallic compounds of the elements of groups I to III of the periodic table with metal halides of the elements of groups IV to VI of the periodic table and α-olefins in inert solvents at temperatures of -78 to +150 ⁰ C have been prepared.

The aldehyde polymers obtained in this way contain a polyolefin chain blockage at the end, which is likely causes the stabilizing effect.

The catalysts used according to the invention are complexes or reaction products between organometallic compounds of the elements of groups I to III of the Periodic Table of the Elements with metal halides of the elements of groups IV to VI of the periodic table and α-olefins.

Examples of organometallic compounds of the elements of groups I to III of the periodic Systems from which the catalyst used according to the invention has been prepared are butyllithium, Amyl sodium, phenyl sodium, dimethyl magnesium, diethyl magnesium, dimethyl zinc, dibutyl zinc, Diethyl mercury, butyl magnesium chloride, phenyl magnesium bromide, triethyl aluminum, Tributyl aluminum, trihexyl aluminum, diethyl aluminum monochloride, diethyl aluminum monobromide, Dibutyl aluminum monochloride, ethyl aluminum dichloride, butyl aluminum dichloride, diethyl aluminum ethoxide, Dibutyl aluminum ethoxide, diethyl aluminum isopropoxide and dibutyl aluminum isopropoxide.

Examples of metal halides of the elements of groups IV to VI of the periodic table are Process for the production of stable aldehyde polymers

Applicant:

Zaidan Hojin Nihon Kagaku Seni Kenkyushi,

Kyoto (Japan)

Representative:

Dr.-Ing. E. Hoffmann, Dipl.-Ing. W. Vain
and Dr. rer. nat. K. Hoffmann, patent attorneys,
Munich 8, Maria-Theresia-Str. 6th

Named as inventor:
Junji Furukawa,
Takeo Saegusa, Kyoto;
Shigeyasu Ohta, Takatsuki (Japan)

Claimed priority:

Japan January 27, 1962 (2356)

Titanium tetrachloride, titanium trichloride, zirconium tetrachloride, vanadium tetra- or trichloride, vanadium oxychloride or chromium trichloride. Even the combination of more than two of these chlorides sometimes results a higher activity catalyst. The molar ratio of chlorides to organometallic compounds is usually 0.01 to 2.0, but it can sometimes be outside of these values.

The α-olefins used to prepare the catalyst are, for example, ethylene, propylene, n-butene-1, n-pentene-1, n-hexene-1, styrene, butadiene or isoprene. The molar ratio of the olefins to the organometallic compounds is between 1 and 100 or above.

The catalysts are produced by the organometallic compounds in an inert Solvents are added. The aforementioned metal halides become this mixture given. An olefin is then absorbed on the reaction product to form the catalyst. But it can also change the catalyst components in the inert solvent Order to be added. Furthermore, an olefin can be absorbed on the catalyst under pressure, when the rate of absorption of the olefin is slow. The temperature at which the catalysts are made lies in a temperature range between

709 550/349

-78 and +150 ⁰ C. The optimum temperature varies depending on the selected catalyst component. For example, when using titanium tetrachloride, triethylaluminum and propylene, a temperature of -78 to -r 100 ° C is used for the preparation of the catalyst, while when using chromium trichloride instead of titanium tetrachloride, an advantageous catalyst by using a high temperature of 100 to 140 ° C and an increased pressure of the propylene exceeding a few atmospheres can be obtained. The catalysts are prepared in an inert solvent under a nitrogen atmosphere. Aromatic or aliphatic hydrocarbons such as benzene, toluene, heptane and hexane can be used as the solvent.

The polymerization is carried out by introducing the aldehydes used according to the invention in the gaseous or liquid phase into the solvent containing the catalyst. The poly ao merisationstemperatur here is below - 40 ⁰ C. Stirring is not necessary in particular; however, agitation generally gives a more favorable result.

Examples of aliphatically saturated aldehydes are acetaldehyde, propionaldehyde and butyraldehyde in question.

The following examples serve to illustrate the invention. Unexpected technical advantages of the Process according to the invention compared to the known processes are from the example 1 subsequent comparison test can be seen.

a) Preparation of the catalyst

^{0.1 cm 3 of} TiCl ₄ and 0.25 cm ^{3 of} A1 (C ₂ H _S ) _{3 were} added to an amount of 50 cm ^{3 of} n-heptane. The reaction mixture was stirred thoroughly and then allowed to stand to give a black precipitate. This was separated from the supernatant liquid and ^{washed three times with 50 cm 3 of} n-heptane each time in order to remove the excess of Al (C ₂ H ₃ ) _g and the soluble product. The sediment was ^{suspended in 50 cm s of} n-heptane and about 500 cm ^{3 of} gaseous propylene was added to the suspension at room temperature.

example 1

The catalyst prepared under a) was added 10 cm ^{3 of} acetaldehyde as a liquid by distillation and the temperature was cooled to -78 ° C.

The polymerization was carried out at -78 ° C for 48 hours. The yield of polymer! The product was 31.2 ⁰ zo, which is composed of 11.8% of a methanol-soluble portion, 6.3% of a chloroform-soluble portion and 13.1% of a chloroform-insoluble portion. This experiment was carried out with a system of A1 (C ₂ H ₃ ) ₃ -TiCl ₄ -propylene and the stability of the polymer was compared with that of polymers produced with a known catalytic system of A1 (C ₂ H ₅ ) ₃ alone. The percentage of decomposition in air was measured at 100 ° C for 1 hour. The values obtained are shown in the following table:

Unstabilized
Polymer *

Stabilized
Polymer ** ...

CH ₃ OH-

more soluble
proportion of

Insoluble part

94

41

90

34
better known

* Made with Al (C ₂ H ₅ ) ₃ catalyst

Way.

** Made with the catalytic system from
Al (C ₂ H ₅ ) _s -TiCl ₄ -propylene according to the invention.

From this experiment it is clear that the _{polymer obtained by Al (C 2} H ₅ ) ₃ -TiCl ₄ -propylene was more stable than that obtained only by A1 (C ₂ H ₅ ) _S.

b) Preparation of the catalyst

1.0 millimole of TiCl ₄ and 1.5 millimole of C ₄ H ₉ Li were added to an amount of 100 cm ^{3 of η-hexane.} The mixture, to which 1 cm ^{8 of} liquid propylene was added, was cooled to -78 ° C.

Example 2

0.3 mol of acetaldehyde was added to the catalyst prepared under b) by distillation and the polymerization was carried out at -78 ° C for 50 hours. The yield of polymeric product was 39.5%, the methanol-soluble portion 8.7%, the chloroform-soluble portion 19.1% and the insoluble portion was 11.7%. The percentage of decomposition was under the same conditions as in Example 1 52%, 34% and 30%, from which the stabilizing effect can be clearly seen.

Claims (1)

Claim: Process for the preparation of stable aldehyde polymers by polymerizing saturated aliphatic aldehydes having 2 to 4 carbon atoms at temperatures below -40 ° C in the presence of inert solvents and catalysts, characterized in that catalysts are used which are obtained by reacting organometallic compounds of the elements of the groups I to ΙΠ of the periodic system with metal halides of the elements of groups IV to VI of the periodic system and «-olefins in inert solvents at temperatures of -78 to +150 ⁰ C have been prepared. Considered publications:
French patent specification No. 1275 561. 709 550/349 4.67 © Bundesdruckerei Berlin