DE665197C - Process for the production of high-polymer, halogen-containing, organic compounds - Google Patents

Description

Process for the preparation of highly polymeric, halogen-containing, organic compounds It has been found that valuable high-polymeric, halogen-containing, organic compounds are obtained if practically saturated, highly polymeric, aliphatic hydrocarbons with a long carbon chain which, in addition to hydrogen, also carry alkyl groups with greater than treated the amounts of halogen required for the saturation of the double bonds still present. It is expedient to use, as starting materials, those high-polymer hydrocarbons whose molecular weight is higher than 100,000, up to about 20,000 or even up to 250,000 . Such substances are, for example, polyisobutylene or other polymeric isoolefins, e.g. B. Polyiso, amylene, which are obtained by polymerizing their monomers at low temperature, for example with borofluoride at temperatures below 0 "up to 100 °. High-polymer hydrocarbons obtained by complete hydrogenation of rubbers are also used These high-polymer hydrocarbons are practically completely saturated, and consequently have only an extremely low iodine number, up to about 7, and the higher their molecular weight, the more they are chemically inert, for example to hydrogen, concentrated sulfuric acid, oxidizing agents, etc. In contrast to rubber, they are no longer vulcanizable and soluble in any proportion in petroleum hydrocarbons, such as heavy gasoline, luminous oil and lubricating oils, with an increase in the viscosity of these agents, while rubber: in these liquids only swells and forms gels.

The treatment of the cited h, o, ch-polymeric, practically saturated aliphatic hydrocarbons with halogen can be carried out in the presence or absence of solvents. Suitable solvents are preferably those which are not attacked by halogen, or also those which are capable of reacting with halogen but which have no harmful effect on the high-polymer hydrocarbon. Carbon tetrachloride is particularly suitable. However, other solvents, such as carbon disulfide, sulfur halides, etc., can also be used. It is advantageous to use solvents which, with the high-polymer hydrocarbon, do not provide solutions that are too highly viscous. Fluorine, chlorine or bromine as well as iodine can be used for halogenation. The greatest practical importance, however, falls to chlorine, if only because it is the cheapest. The Ha.logenierung can at room temperature or higher temperatures, z. B. at 50 ° or up to 100 °; are executed. Djp_ However, the temperature must not be too high,; g = - be chosen because otherwise one more or v; 2 strong degradation of the highly volatile IiiS "`, hydrogen enters. You can at Atmd = -sphere pressure or, when using low temperature, at elevated pressure, z. B. 5 to 50, 100 or more atm. Pressure, work. You can optionally in the Halogenierun: g also peroxides, z. B. Benzoyl peroxide, add to let the halogen atoms attack preferentially on the u (terminal) carbon atoms of the molecules.

The halogen content of the products obtained can vary within wide limits. In general it is favorable. only i o to 2o o; 'o introduce halogen, but can the halogenation also considerably further, up to a chlorine content of, for example 5o%, to be continued.

You can use the halogen, e.g. B. in the case of chlorine, by a carbon tetrachloride solution of the high molecular weight hydrocarbon or you can use this solution in fine distribution of a chlorine atmosphere. Alkaline substances, e.g. B. Calcium or magnesium oxide or carbün.at, sodium carbonate or bicarbonate, can also be added during the halogenation, or the halogenation can in the presence of water and a carbonate insoluble therein, e.g. B. Calcium or magnesium carb, o: nat, can be made in order to reduce that which is split off during the halogenation To bind chlorine hydrogen. You can also, instead of solutions of the finished high polymers Run out of hydrocarbons, e.g. B. in the case of the use of polyisobutylene, the polymerization of the monomeric iso: butylene in the presence of that for the halogenation run the intended solvent and then act on the solution the halogen permit.

After the end of the halogen treatment, air or another inert gas, such as nitrogen or hydrogen, is blown through the solution at a slightly elevated temperature, if possible below 100 °, in order to remove the hydrogen halide formed. The small residue of hydrogen halide still remaining in the solution can be bound by further bubbling through with ammonia or volatile amines or mixtures of these gases, which are moderately inert with air, at normal or slightly elevated temperatures. But you can also the product with dilute alkali, z. B. Sod.aläsung, wash to remove the hydrogen halide. Appropriately, you can the halogenation product at low temperature with solutions of alkaline substances, such. B., alcoholic potassium hydroxide solution, lime What > aqueous soda or bicarbonate solution v., treat to remove unstably bound hair To split off Xgen - and thus to be particularly stable bil products. Hardly volatile basic compounds, especially aromatic amines, such as fonoethylaniline or methylnaphthylamine or phenoxypropene oxide, can be added to the end product as stabilizers in amounts of about 0.1 to 10.0. The chlorination products are obtained in a particularly pure form by precipitation from their solutions using alcohols, e.g. B. methanol, or by blowing off the solvent with steam or pouring the solutions into boiling water.

The products obtained are depending on the nature of the starting materials and treatment with halogen either highly viscous liquids or solids or represent more or less soft to hard plastic masses. They differentiate differs from chlorinated rubber in that it is generally somewhat more stable and softer are as this. Also, unlike chlorinated rubber, they are made with most resins not compatible, but can be mixed well with paraffin. They can be used for a wide variety of Purposes are used, for example in the form of their reaction products with aromatic Hydrogen or with alkali sulfides or sulfhydrates as additives to lubricants, e.g. B. for lowering the piece point or for high-pressure lubricating oils of high viscosity index. You can also do it on your own or with appropriate ones Soft resins, p pments, solvents and possibly linseed oil are used as varnishes that are particularly resistant to chemical and mechanical influences and are non-flammable. You can also use some resins, for example those which can be produced from petroleum hydrocarbons in a known manner, can be added to improve their properties.

Another area of application of the products obtained lies in their Also used in the preservation of wood by impregnation with wax. In Wood that is usually impregnated with wax is easily stained by water. Will however, the wax a small amount of a .chlorinated polyisobutylene with 5 to 10% chlorine content, for example 1/2 to 100%, mixed in, so the spots will become stained of the wood either completely prevented or greatly reduced. The halogen-containing, High polymer material can also be used as an impregnation agent for making the fire resistant various porous or fibrous materials such as wood, textiles, Paper and a wide variety of building materials.

The products, especially the @ veicllen @@ '' are also suitable as Plasticizers. You can use for matting rayon, e.g. B. in mixture with inert, organic oily or waxy substances, such as oily, s: a.Iben-like and solid petroleum hydrocarbons can be used. These blends will be added to the spinning solutions. Example r polyisobutyls @ n that - by polymerization of isobutylene with boron fluoride at -2o ° and a molecular weight of about 8,000 is dissolved in four times the amount of carbon tetrachloride. Finely divided chlorine gas is passed into this solution at room temperature. When the chlorine content of the polyisobutylene is about 200,000, the chlorination occurs canceled. The solution is washed with water and the carbon tetrachloride removed by distillation.

When using low molecular weight polyisobutylene, about 3ooo, it is not necessary to dissolve the product beforehand, but rather the chlorine can go directly into the viscous mass in the presence of very small quantities Iodine can be introduced as a catalyst. You then only need the reaction product To remove the hydrogen chloride, wash with a little sodium: m@carbonatlösu.ng. Example 2 Chlorine gas is fed under pressure from below into a tower with broken porcelain or other filling bodies. As soon as there is enough chlorine in the tower is a solution of polyisobutylene in carbon tetrachloride in the top Part of the tower let in. The solution then runs in a finely divided form bis, to the bottom of the tower and comes into close contact with the chlorine gas. Then it is either directed again through the same tower moder other similar towers, until the polyisobutylene has the desired chlorine content. .

The: from, building up the tower above. Gas mixture becomes liberation of hydrogen chloride over solid caustic soda and then passed back into the tower. The Rea; ctions; solution is freed from hydrogen chloride by washing with soda solution and removing the carbon tetrachloride by distillation.

Usually, by distilling off the tetra: chlorocarbon solution the remaining chlorinated isobutylene under ordinary or reduced pressure obtained in a fairly solvent-free form. The last traces of the solvent can by dissolving in a gasoline with narrow boiling limits that are close to the boiling point of carbon tetrachloride (76 °), and subsequent distillation: removed will.

It can use the high polymer, saturated, aliphatic, chen hydrocarbons before treatment with halogen also wax, resins, mineral or vegetable oils, aromatic Chlorine compounds or esters are added.

Claims (2)

PATLNTA NSPRÜettr: r. Process for the production of high polymer, halogen-containing organic compounds, characterized in that one practically saturated, high polymer, aliphatic hydrocarbons with a long carbon chain, which carries alkyl groups in addition to hydrogen, with larger groups than those for saturation of the remaining double bonds, the required amounts of halogen are handled. 2. Embodiment of the method according to claim z, characterized in that the Halogenation in the presence of waxes, resins, mineral or vegetable oils, aromatic Chlorine compounds or esters is made.