DE1229735B - Process for the production of an organic polymer containing phosphorus and nitrogen - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C 08 g

German class: 39 c - 30

Number: 1 229 735

File number: A 28446 IV d / 39 c

Filing date: December 4, 1957

Opening day: December 1st, 1966

There is already a method for producing a phosphorus-containing polymer known therein consists that at least one Äthyleniminphosphinoxyd or sulfide with at least two optionally substituted ethyleneimine groups bonded directly to the pentavalent phosphorus atom or their mixtures heated or reactive with compounds with at least one, at least two Compounds containing hydrogen atoms or hydroxyl radicals, optionally with heating, are reacted.

The invention relates to a process for the production of an organic containing phosphorus and nitrogen Polymers by reacting an Äthyleniminphosphorverbindungen with at least two optionally substituted ethyleneimine groups bonded directly to a pentavalent phosphorus atom are, with an organic compound with reactive hydrogen atoms, which is characterized is that a di- or triethylenimine phosphine sulfide is used as the ethyleneimine phosphorus compound or Di- or Triäthyleniminphosphinoxyd and containing as reactive hydrogen organic compound a monohydric phenol and / or a carboxylic acid is used.

Tris (ethyleneimine) phosphine oxide or tris (ethyleneimine) phosphine sulfide is preferably used. Diethylenimine phosphine oxide and sulfide are also suitable in accordance with the general formula

Y-P-Y

in which X is an oxygen or sulfur atom, Y is an ethyleneimine group and Z is a monoalkyl or dralkylamine radical, ζ. Β.

/ CH ₃

■ n ( or - '

^X CH ₃

/ CH ₂ - CH ₂ N

) 0

or an alkyl, alkylene or aryl radical. The Älhylenimineruppe can optionally, for. B. be substituted by an alkyl group.

Suitable monohydric phenols are e.g. B. phenol, o-, m- and p-cresol, ρ - bromophenol, ο-nitrophenol, m - fluorophenol, pentachlorophenol, 3 η - pentadecylphenol, ρ - hydroxydiphenyl and HO - C ₆ H ₄ (CH ₂ ) Ii - CH ₃ .

Process for the production of a phosphorus and
nitrogen-containing organic polymers

Applicant:

Albright & Wilson Limited,

Birmingham, Warwickshire (UK)

Representative:

Dr.-Ing. F. Wuesthoff, Dipl.-Ing. G. Pulse
and Dr. E. v. Pechmann, patent attorneys,
Munich 9, Schweigerstr. 2

Named as inventor:
Wilson Alvin Reeves,
Leon Howard Chance
George Lenton Drake Jr.,
John Daulton Guthrie,
New Orleans, La. (V. St. A.)

Claimed priority:

V. St. v. America December 4th 1956

(626 271, 626 272, 626 273)

Suitable carboxylic acids are, for. B. acetic acid, perfiuoroacetic acid, propionic acid, / 3-bromopropionic acid, stearic acid, oxalic acid, adipic acid, malonic acid, succinic acid, vinyl acetic acid, benzoic acid, bromobenzoic acid, terephthalic acid and 1,4,5,6,7, - hexachlorbicyclo-S-hepten ^^ - dicarboxylic acid.
Perfluorocarboxylic acids are particularly suitable when flame-resistant and oil-resistant polymers are to be produced.

The starting materials are preferably reacted in such amounts that no more than one phenolic Hydroxyl group or one carboxyl group is used per ethyleneimine group, the monovalent ones Phenols and carboxylic acids react almost quantitatively.

The reaction can be carried out with or without a solvent. If the starting materials are solids the reactants can be melted together. If any of the components is liquid at room temperature, the

609 729/410

solid component can be dissolved in the liquid component. In some cases it is preferable to run the reaction in a solvent. Suitable solvents are water or the usual organic solvents. Water and benzene are particularly good solvents; Acetone and ethanol are also suitable. In general, method of the invention between 10 and 150 ⁰ C is allowed to proceed.

According to the invention, mixtures of the starting materials can also be used, e.g. B. a mixture of Diethylenimine phosphine oxide and sulfide, a mixture of two or more monohydric phenols or Carboxylic acids or a mixture of a monohydric phenol with a carboxylic acid.

The polymers obtained according to the invention can be used as flame retardants for the treatment of Textiles are used.

In the following examples, the quantities are given as parts by weight and percentages by weight.

example 1

Implementation of p-bromophenol with
Tris (ethyleneimine) phosphine sulfide

2 parts of p-bromophenol were dissolved in 7 parts of benzene and then 2 parts of tris (ethyleneimine) phosphine sulfide were dissolved in this solution. The resulting clear solution was heated in an open beaker on a funnel evaporated to about 70 ⁰ C to give a water-clear, highly viscous mass was obtained after 4 hours of heating. Polymerization was then continued as follows:

A. One tenth of this viscous polymeric mass was ^{heated to 150 °} C. for 5 minutes, a hard, tough, slightly flexible, water-clear resin being obtained. When this resin was heated an additional 10 minutes at 150 ⁰ C was the polymers at 15O ⁰ C still pliable; however, the flexibility decreased on cooling, and before 27 ⁰ C was reached, it became brittle.

B. The remainder of the viscous product was ^{heated to 110 °} C. for 30 minutes, a tough, water-clear polymer being obtained.

The total weight of the resin obtained according to A and B corresponded to a monomer conversion of more than 90%. The product obtained according to B contained 8.5% phosphorus, 22.58% bromine, 8.68% sulfur and 10.64% nitrogen. The resin is not flammable.

Example 2

Polymerization of acetic acid with
Tris (ethyleneimine) phosphine sulfide

5 parts of tris (ethyleneimine) -phosphinsulfid were dissolved in 25 parts of water, then were added to this solution at 30 ⁰ C with stirring, 3 parts of acetic acid. The initially clear solution became cloudy after about a minute, and finally a floury, white, insoluble resin settled. The amount of resin almost corresponded to the amount of sulfide and acetic acid used. The resin does not sustain the combustion.

A similar resin was obtained when / 3-bromopropionic acid was used in place of acetic acid.

Example 3

Implementation of adipic acid with
Tris (ethyleneimine) phosphine sulfide or oxide

A solution of 4 parts was added to a solution of 4 parts of adipic acid in 25 parts of acetone Tris (ethyleneimine) phosphine sulfide given in 10 parts of acetone. This mixed solution was on heated in a steam bath. The temperature of the

ίο The solution was kept at about 65 ° C until about 80 to 90% of the acetone had distilled off within about 10 minutes. The temperature then rose slowly. At 70 ⁰ C the steam was throttled in such a way that a temperature of about 70 ⁰ C was not exceeded. The mixture was kept at this temperature for about 2 to 3 minutes and then cooled ^{to 27 ° C.} The reaction product was a water-white, highly viscous syrup. A sample of this mass was placed in a thin layer on a glass plate and ^{heated to about 70 to 80 °} C. on a steam funnel for 10 minutes, a clear oil being formed.

The remainder of the syrup was allowed to stand at 27 ° C. for 16 hours, during which time a clear, viscous, in water and acetone formed insoluble resin. This resin was pulverized and mixed with water and ethanol extracted. After this treatment the resin contained 7.56% phosphorus and 10.23% nitrogen. the The yield was 91% based on the amount of starting materials. The resin maintains the combustion not.

In the same way as described above, an experiment with tris (ethylene imine) phosphine oxide was set up, the solvent and procedure being the same. The end product was the same as above described similarly. After standing for 16 hours, a clear, tough polymer in 96% strength was obtained Yield. The resin contained 8.33% phosphorus and 11.0% nitrogen. This resin was also flame retardant.

Example 4

Implementation of terephthalic acid with
Tris (ethyleneimine) phosphine sulfide

About 3 parts of terephthalic acid were dissolved at 40 ⁰ C in dimethylcyanamide and then 3 parts of tris- (ethyleneimine) -phosphinsulfid placed in this warm solution. The resulting solution was then heated in a thin layer in a watch glass on a steam funnel. A clear, viscous reaction product was obtained after 40 minutes; after heating at about 80 ° C. for 2 hours, a hard and tough polymer had formed. This polymer contained phosphorus and sulfur and was flame-swept. Tris (ethylene imine) phosphine oxide does not react with dimethyl cyanamide.

Example 5

Implementation of stearic acid with
Tris (ethyleneimine) phosphine sulfide

First 4 parts of stearic acid were dissolved in 35 parts of ethanol and then 2 parts of tris (ethyleneimine) phosphine sulfide dissolved in this ethanol solution. 5 parts of this solution were placed on a watch glass and on a steam funnel for 1 hour heated, being a waxy, in water

and ethanol insoluble, polymeric, phosphorus and sulfur containing product was formed.

Claims (1)

Claim: Process for the production of an organic polymer containing phosphorus and nitrogen by reacting an ethyleneimine phosphorus compound with at least two optionally substituted ethyleneimine groups that are bonded directly to a pentavalent phosphorus atom, with an organic compound with reactive hydrogen atoms, characterized in that that a di- or triethylenimine phosphine oxide is used as the ethylene imine phosphorus compound or di- or triethylenimine phosphine sulfide and organic compound containing reactive hydrogen a monohydric phenol and / or a carboxylic acid is used. Considered publications:
German patent specification No. 854 651. 6Ο9 72Ϊ / 4-1Ο 11.66 © Bundesdruckerei Berlin