DE1172856B - Process for the production of phosphorus-containing polymers - Google Patents

Description

Process for the Production of Phosphorus-Containing Polymers The invention relates to processes for the production of polymers of the general formulas (R = monofunctional aliphatic, aromatic, heterocyclic hydrocarbon radical or substituted such radical X = divalent aliphatic, alicyclic, aromatic, heterocyclic hydrocarbon radical or substituted such radical; Y = oxygen or sulfur or absent; n = integer from 3) is characterized in that one or more organometallic compounds which contain two Na or Li atoms in the molecule or a Di-Grignard compound of the formula M - N - M (M = MgCl, - MgBr, or - MgI) with one or more dihalophosphines , Dihalophosphine oxides or dihalophosphine sulfides in which the chlorine, bromine or iodine atoms are bonded directly to the phosphorus atom and / or condensed with phosphorus compounds which contain more than two Cl, Br or I atoms.

Numerous processes are already known which are also known lead to products containing phosphorus. In the method according to the invention arise however, compounds in which there is an immediate P-C bond. These products also differ from a technical point of view due to their considerably greater stability of the products obtainable by the known processes.

The organometallic compounds can be a dilithium, a disodium or Di-Grignard compound of the formula M - X - M (X = divalent aliphatic, alicyclic, aromatic, heterocyclic hydrocarbon radical or substituted such remainder; M = MgCl, - MgBr or - MgJ residue). The latter is preferably used.

Phenyldichlorophosphine is preferably used as the phosphorus compound. The phosphorus compound containing two halogen atoms can be wholly or partially through an equivalent amount of a phosphorus compound attached directly to the phosphorus atom bound contains more than two halogen atoms. Such are phosphorus trihalides, Phosphoryl trihalides or thiophosphorus trihalides, fluorine-containing phosphorus compounds are not used.

As the organometallic compound is preferably a phenylene-l ,; or -1,3-bimetal compound used.

The condensation can be represented by the following equation: Here, X, Y and n have the same meaning as above; Z is a chlorine, bromine or iodine atom, M a lithium or sodium atom or - MgCl, - MgBr or - MgI.

The condensation can be carried out in such a way that one Equivalent of the difunctional organometallic compound with 0.8 to 1.2 equivalents of the phosphorus compound containing two halogen atoms. Preferably be equivalent amounts of both reagents are used. The condensation can take place in a suitable Solution medium in a temperature range from -4o up to 150 ° C. When the condensation is complete, the mixture is hydrolyzed and the polymer is isolated.

If the present invention is carried out with phosphorus compounds, which contain more than two halogen atoms bonded directly to the phosphorus atom, then crosslinked polymers are obtained.

Example 1 A solution of 15.5g phenyldichlorophosphine oxide in 50 ml of tetrahydrofuran was added dropwise to a well-stirred solution of an equimolecular Amount of phenylene-1,44ilithium in tetrahydrofuran added at -400C. To After the addition, the reaction mixture was allowed to reach room temperature and hydrolyzed with water.

The solvent was distilled off with steam.

The polymer was separated from the aqueous phase and dried at 300 "C in a vacuum.

It is a light yellow polymer which softens at 1500C, dissolves in ethyl alcohol and is stable at temperatures of around 300 "C.

This novel polymeric substance has good solubility in common volatile solvents Example 2 A mixture of 4.8 g of phenyldichlorophosphine oxide and 3.7 g of phosphorus oxychloride was dissolved in 50 ml of a mixture of tetrahydrofuran and ether dissolved in equal parts. The solution was added dropwise to one Suspension of the disodium compounds, prepared from 19.6 g of 4,4'-dibromodiphenyl ether in 100 ml of the same solvent.

After the addition, the mixture was stirred for 2 hours treated at reflux. The mixture was then hydrolyzed with water and steam distilled, to remove the volatiles. A light brown, crosslinked, resinous one was obtained Product which is stable in the air at temperatures of about 300 "C.

Example 3 A solution of 7.9 g of phenyldichlorophosphine in 50 ml of tetrahydrofuran was added dropwise to a suspension of the dilithium compound prepared from 13.3 g of 1, 10-dibromodecane, also in tetrahydrofuran, added. The mixture was then stirred for 3 hours at room temperature and hydrolyzed with water. After removing the solvent by steam distillation, the polymer was separated off and washed with water; it was soluble in hot aromatic solvents and softened at about 100 ° C.

Example 4 A solution of 4.4 g of phosphorus oxychloride in 50 ml of diethyl ether was added dropwise to a suspension of the di-Grignard compound prepared from 10 g 1,5-dibrompentene, added. The mixture was then at room temperature 2 Stirred for hours and hydrolyzed with water. After removing the solvent the polymer was separated off by steam distillation and washed with water.

This crosslinked polymer was white in color and organic Solvent insoluble.

EXAMPLE 5 5 g of phenylthiophosphoryid dichloride and an equimolar amount of dilithiwnbenzene were dissolved in tetrahydrofuran at -40 ° C. The mixture was stirred for 1 1/2 hour at this temperature; then it was allowed to warm to the cold temperature until the reaction had ended. The mixture was hydrolverted, the tetrahydrofuran was drawn off and the sand was washed with water and then dissolved in benzene The polymer was isolated by evaporating the benzene solution and dried in vacuo at about 200 ° C. The product was a yellow polymer with a softening point of about 120 ° C.

Claims (3)

Claims: 1. Process for the preparation of phosphorous-containing polymers of the general formulas tR = monovalent aliphatic, alicyclic, aromatic, heterocyclic hydrocarbon radical or substituted such radical; X = divalent aliphatic, alicyclic, aromatic, heterocyclic hydrocarbon radical or substituted such radical; Y = oxygen or sulfur or absent; n = integer from 3), characterized in that one or more organometallic compounds which contain two Na or Li atoms in the molecule, or a Di-Grignard compound of the formula MXM (M -MgCl, -MgBr or -MgBr or -MgJ) with one or more dihalophosphines, dihalophosphine oxides or dihalophosphine sulfides, in which the chlorine, bromine or iodine atoms are bonded directly to the phosphorus atom, and / or with phosphorus compounds which contain more than two Cl, Br or iodine atoms bonded directly to the phosphorus atom, condensed. 2. The method according to claim 1, characterized in that as Phosphorus compound phenyldichlorophosphine is used. 3. The method according to claim 1, characterized in that as Organometallic compound is a phenylene-1,4 or 1,3-dimetal compound used. References contemplated: U.S. Patents No. 2,616 873, 2,636,020, 2682522, 2743258; Swiss patent specification No. 285 782.