DE1495101A1 - Process for the modification of polymerization products of alpha-methylstyrene - Google Patents

Description

BADISCHE ANILIN- & SODA-PABBIK AG 1 A 9 5101

Our reference: O.Z. 21 977 Br / Dck / Dr Ludwigshafen am Rhein, July 23, 1962

Process for the modification of polymerization products of Λ-methy! Styrenes

Addition to DBP 1 073 742

The subject of patent 1,073,742 is a process for the modification of compounds prepared with alkali metals, alkylihydrides or organic alkali metal compounds in the presence of ethers Polymers or copolymers of ^ -Methylstyrene, in which the primarily formed polymers are reacted with such compounds immediately after the polymerization in the absence of oxygen and of compounds containing acidic hydrogen, those under C-C linkage with an organometallic compound able to react without polymerizing.

This process gives technically interesting polymerization products which essentially have the physical properties of the polymeric * / - methylstyrene.

It has now been found that following the procedure of the patent 1,073,742 leads to particularly advantageous polymers if

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the disodium or potassium compound of oligomers of the .. oCrMethylstyrene, the 2 to 8 .- ^ - methylstyrene units in the chain. contain, with ti- or polyfunctional compounds that under C-C linkage with the end members of the oligomericχ -methylstyrene able to react.

The disodium or di-potassium compounds of the oligomers dee οζ, -Me thy le ty ro le with about 2 to 8oC-methylstyrene units in the chain are known compounds that are formed by reacting ^ -methyl styrene under anhydrous conditions with sodium or potassium can be obtained. In this reaction, the oligomers are obtained in which the two alkali atoms are bonded to the ends of the chain. According to the invention, these sodium or potassium compounds of the oligomers of C-methylstyrene are reacted with those bifunctional or polyfunctional compounds which are capable of reacting with C — C linkage with organometallic end groups of the oligomeric C-methylstyrene. Examples of such compounds are dihalogen compounds, dicyano compounds, diisocyanates, diketones, dicarboxylic acid esters, bischlorocarbonic acid esters, dialdehydes or dicarboxylic acid halides.

Suitable compounds of this type are, for example, 1,2-dichloroethane, 1,2- or 1,3-dichloropropane, 2,2-dichloropropane, 1,4-dichlorobutane, 1,1,2-trichloroethane, 1,4-dichlorobutene or the corresponding Bromine compounds as well as the cyclohexane dichlorides, xylylene dichlorides, Adipic acid dinitrile, methylene chloride, benzal chloride, glutanic acid dichloride, phosgene, succinic acid diethyl ester, hexamethylene diocyanate, Malondinitrile, maleic acid diethyleter,

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Phenylene diisocyanate and bis-chlorocarbonic acid ester of butanediol, Butenediol, di-p-oxyphenyl-dibutyl-methane and 2,2 di-p-oxyphenylpropane.

The implementation conditions correspond to those mentioned in the main patent. All solvents are ethers, in which the alkali compounds of the oligomers of ⁵ ^ -methyl-styrene dissolve. Particularly suitable ethers are dioxane or tetrahydrofuran. Because of the violence of the reaction of the oligomeric 00 -Methyletyrole it is necessary to work at low temperatures, ie at temperatures between about -80 and +50 ⁰ C. At these low temperatures, particularly secondary reactions are largely avoided. It is expedient to work in such a way that the disodium or di-potassium compounds are prepared in an ether suitable for this purpose, the solution is cooled and the compounds are then added to the cooled receiver as the reaction takes place. It is often expedient to add the bifunctional compound diluted in a solvent such as tetrahydrofuran. The polycondensation occurs immediately and the conversion is practically complete. It is therefore not necessary to use one of the reactants in excess. The reaction is practically complete when 1 mole of the biifunctional compound has been added dropwise to 1 mole of the dialkali compound and the deep dark colored solution of the alkali metal compounds of the oligomeric O-methylstyrene has been decolorized permit.

The production of allyal compounds of the oligomeric O ^ -methylatyrene must be in carefully purified solvents under total

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ORIGINAL INSPECTED

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Exclusion of air, carbon dioxide or moisture can be carried out. Likewise, the bifunctional compounds used must also be very clean and be added to the reaction partner with the exclusion of air and moisture. However, the manufacture of the starting products is not the subject of the invention.

The new plastics dissolved in the ethers can, after having passed through the salts formed during the reaction. Filtration or washing with a little water can be obtained directly in solid form by evaporating the solvent . You can also precipitate the plastic by adding a lot of water or methanol and dry it after being spun off.

The new polycondensation products prepared according to the invention are macromolecular thermoplastic products. In most cases they are crystal clear. They can be processed on the usual processing machines with shaping or can be used as paint raw material. They are special because of their 'good electrical properties.

The parts mentioned in the examples are parts by weight, the K values were determined by the Fikentscher method in "Celluloeechemie ¹¹ , Volume 13, 1932, page 58.

example 1

In Figure 1, 300 parts of tetrahydrofuran purified 472 parts Qk-Me thylstyrol with 23 parts of finely divided sodium are stirred for 3 hours at 45 to 5O ⁰ C under purified nitrogen. After this time

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has custody solved all the sodium and the deep dark red solution of the disodium of octameric ^ methylstyrene is cooled to about -50 ⁰ C. At this temperature, 89 parts of 1,4-Eichlorbutan are dissolved in 400 parts of tetrahydrofuran were added dropwise rapidly to the solution that the temperature does not exceed -40 ⁰ C increases. Towards the end of the reaction, when a slight lightening of the color can already be seen, the remainder of the dichlorobutane is added particularly slowly.

After all of the dichlorobutane has been added, the solution is almost discolored.

The decolorized solution is slowly added dropwise to 10,000 parts of water at room temperature with vigorous stirring, the plastic precipitating in solid form and the sodium chloride formed dissolving . The precipitate is filtered off with suction and washed with water and methanol.

After drying at 80 ^° C. in vacuo, a fine white powder is obtained. The product has a K value of 38 and can be processed into clear press plates.

Example 2

472 TelleoC-methylstyrene, and 6000 parts of tetrahydrofuran are stirred with 50 parts of sodium powder under nitrogen for 2 hours at 20 ⁰ C. A deep red solution of the disodium compound of the tetrameric Ä — methylstyrenes forms, which will filter off the excess sodium. The solution is cooled to -60 ⁰ C and

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a solution of 187 parts of ethylene glycol dichloroate in 300 parts of tetrahydrofuran was gradually added with stirring. An almost colorless, viscous solution is obtained from which sodium chloride has separated out. By adding methanol becomes the polymeric reaction product precipitated and then washed with waeeer. 427 parts of a polyester are obtained K value 17.8.

Carrying out the condensation at -10 ⁰ C instead of -60 ⁰ C, the yield increased to 490 parts.

Example 3

As the disodium the tetrameric oC-methyl styrene prepared in Example 1 and stored at -20 ⁰ C 100 parts of phosgene are added gradually. After the addition is complete, the mixture is stirred for a further 2 hours at room temperature and then worked up as in Example 1. 490 parts of a polyketone with a K value of 32.5

Example 4

As the disodium the tetrameric oC-methyl styrene prepared in Example 1, and at -40 ⁰ C 215 parts of butanediol-bie-chlorkohlensäureester gradually added, finally enters discoloration. After working up, parts of a polyester with a K value of 30.5 are obtained.

If the reaction at ⁰ ° C instead of at -40 ⁰ C, we obtain 440 parts of the polyester with a K value of 20.5. '

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Example 5

As in Example 1, the disodium compound of the tetrameric cO-methylstyrene is prepared and ^{reacted at 0} ° C. with 175 parts of p-xylylene dichloride. 550 parts of a polymer with a K value of 26 are obtained.

Example 6

The disodium compound of tetrameric methylstyrene in tetrahydrofuran, which was prepared according to Example 2, is added with stirring to a solution of 213 parts of the dichlorocarbonic acid ester of 1,4-butenediol. The mixture is stirred at a temperature from -30 to -50 ⁰ C. The sodium chloride formed is washed out with a little water and the remaining solution is immediately evaporated.

A polyester with a K value of 27.8 is obtained, which is used for the production of Casting resins is suitable.

Claims (1)

Claim Further development of the process for modifying polymerization products dee oC * -Methylstyrols ^ according to Patent 1 073 742, in which one prepared primarily with alkali metals, alkali hydrides or organic alkali metal compounds in the presence of ethers Polymers or copolymers of ^ -Methylstyrene directly following the polymerization in the absence of oxygen and of compounds containing azldem hydrogen with such compounds 909810/0762 * ⁸ - U95101 - 8 - O.Z. 21 977 reacting, capable of reacting with CC linkage with an organometallic compound without polymerize it, characterized in that the di-sodium for the reaction or di-potassium compounds of oligomers of ^ methylstyrenes, 2 to 8 ^ - Containing methyletyrene units in the chain, and bifunctional or polyfunctional compounds that are able to react under CC linkage with the end members of the oligomeric C'-MethyIetyrols , used. BADIAN ANILINE & SODA FACTORY 909810 / 07B2