FR2510578A1 - SUBSTITUTED 1-PHENYL-1-PHOSPHONIC ACIDS AND THEIR USE - Google Patents

Abstract

THE INVENTION CONCERNS 1-PHENYL-VINYL-1-PHOSPHONIC ACIDS CONTAINING A SUBSTITUTE R ON THE RADICAL PHENYL, R BEING MADE FOR A POSSIBLY SUBSTITUTE RADICAL ALKYL, POSSIBLY RAMIFIED, CONTAINING 3 TO 20 ATOMES OF CARBON, AS WELL AS SELS, SEMI-ESTERS, SALTS OF SEMI-ESTERS AND DIESTERS DERIVED THEREOF, A PROCESS FOR THEIR PREPARATION AND THEIR USE.

Description

Phosphonic acids which have polymeric units

  risables, as well as their salts, semi-esters and esters, are interesting as monomers, because homo or copolymers built from them find numerous uses in the art, for example as flame retardants, as resistant coatings corrosion for metals, such as

  ion exchangers, as dispersants, as adhesion promoters

  rence, etc. Copolymers of l-phenyl-vinyl-l-phosphor Lique acid have been recommended for example for the subsequent treatment of phosphated metal surfaces (German patent applications

no 26 15 489, 24 55 624).

  For the industrial synthesis of l-phenyl-vinyl acid

  phosphonic, we know a process that starts from acetophenone.

  According to this process, acetophenone is reacted with phosphorus trichloride, for example in the presence of glacial acetic acid. The product initially formed is attributed the structure of a cyclic phosphonic acid By causing water or hydrochloric acid, we obtain,

  from this product, l-hydroxy acid or l-chloro-l-

phenylethane-1-phosphonic.

  When thermal energy is added, these compounds react

  smells while giving, with elimination of water or hydrochloric acid

  that, 1-phenyl-vinyl-1-phosphonic acid (Ph VP).

  The phosphonic acids of the state of the art, with l-phenylvinyl-l-phosphonic acid as a typical representative, are not able to meet all the requirements of the art in the various fields of use. so

  for example that the solubility of Ph VP in organic solvents

  that non-polar and, in particular, in interesting comonomers of another type, is insufficient. Furthermore, they lack the activity of an emulsifier, required for certain fields of application, etc. However, it has been discovered that substituted l-phenyl-vinyl-1-phosphonic acids of formula I

R CH 2

2 P 03 H 2

  in which R is put for a substituted alkyl radical, optionally branched, containing at 20 carbon atoms, preferably 6 to 12 carbon atoms, fill in a large

  measures the requirements of the technique.

  The protection claimed by the present application relates to lphenyl-vinyl-1-phosphonic acids of formula I, as well as a process for their preparation according to which, starting from an acetophenone of formula II

R O

  it (II) CCH 3 in which R is taken for a substituted, optionally branched, alkyl radical containing 3 to 20 carbon atoms, preferably 6 to 12 carbon atoms, this is reacted with phosphorus trichloride, preferably in the presence of glacial acetic acid, the reaction product formed is reacted with a compound of formula III

EX ((II)

  in which R represents OH or Cl, to obtain the compound of formula IV

R CH 3

X {P 032 (IV)

  X in which R and X have the meanings given above, then the compound of formula V is thermally eliminated

* EXI (V)

  in which X 'has the meaning of the symbol X appearing in formula IV, and a subsequent treatment known per se is carried out. The substitution of the radicals R in formula I, provided by definition, preferably includes substituents which are stable in the reaction conditions, such as

  alkyl, aryl, ether, amino, alkylamino radicals.

  The reaction of substituted acetophenone of formula II

  preferably carried out with at least stoichiometric amounts

  metrics of phosphorus trichloride and glacial acetic acid, generally below 350 C, preferably in the range between room temperature and 3550 Under these conditions, it is advantageous to keep the concentration of acetic acid in the mixture

  reaction, i.e. acetic acid is added slowly

  drop by drop to the mixture of acetophenone / phosphorus trichloride previously introduced. Preferably, the following is added:

  in total 2 mol of acetic acid per mol of phos trichloride

phore used.

  Then the compound of general formula IV, in which X is put for OH, can be prepared by hydrolysis of the reaction mixture with an amount of water at least equimolar to the amount of acetic acid added, preferably with a small excess. preparation of the compound of formula IV, in which X represents Cl, the reaction mixture resulting from

  the reaction of the compound of formula II with stoichiometric amounts

  metrics of phosphorus trichloride and glacial acetic acid, may be saturated with hydrochloric acid, also at

  a temperature of around 3520 C maximum.

  The raw products of the two process variants can

  be used, without further purification, for the elimination

  thermal tion of compound EX '. The thermal removal of HX ′ in compound IV can advantageously be carried out based on the method of German patent application No. 20 60 218, for example by heating the compound IV in a suitable inert solvent, such as 1.1 , 2, 2-tetrachloroethane, at temperatures of the order of

   C to 1402 C The elimination reaction is preferably obtained

  by suspending compound IV, preferably in 3 to 5 times its volume of 1,1,2,2-tetrachloroethane and by

  heating to reaction temperature with simultaneous stirring.

  With a strong release of water or HC 1, the suspensions are transformed into solutions, from which the compounds of formula I can be recovered in a manner known per se, by

  example by crystallization (if necessary after concentration).

  Compounds of formula I are generally substances

  but the tendency to crystallize decreases-

  when the chain length is increased From the substituted 1-phenyl-vinyll-phosphonic acids of formula 1, their salts, semi-esters, salts of semi-esters and diesters can be prepared in a manner known per se (cf. K Sasse, in Houben-Weyl, vol. XII / l, pp 383 sqq, Georg-Thieme-Verlag, Stuttgart 1963) Examples of alkali, alkaline earth and

heavy metals.

  Alkaline salts can be prepared, for example,

  from aqueous solutions of acids, by adding quan-

  monomolar or bimolar tites of the corresponding hydroxides or carbonates and they are isolated if necessary by extraction

with a solvent.

  Alkaline earth salts can be obtained in an analogous manner, for example by reaction of the free acids of formula I with alkaline earth hydroxides or carbonates. They are

  relatively poorly soluble in water.

  Cupric and zinc salts are formed, for example, from aqueous solutions, by addition of copper or zinc carbonate to the free acids of formula I The bivalent lead salts are preferably prepared using bivalent lead acetate; the monovalent silver salts are obtained by reaction with silver oxide, the divalent silver salts precipitate from ammoniacal solutions of

  acids of formula I with silver nitrate.

  The salts of the phosphonic acids of the form can be obtained.

  I with amines, for example with aromatic amines, by heating these elements in solvents, for example

an alcohol or benzene.

  Direct esterification of phosphonic acids of form

  mule I can be carried out according to general methods

  ques, by treatment of divalent silver or lead salts with alkyl halides of formula VI,

R 1 Z (VI)

  in which R 1 is set for an alkyl radical, preferably containing 1 to 8 carbon atoms, or a benzyl radical and Z is set for a halogen such as chlorine, bromine or iodine, to obtain the esters of formula IA R t-Cz O // f CH 2

C O

p OR,

  in which R 1 has the meaning given above By sapo-

  nification of the diesters of formula IA in basic medium under rather rigorous reaction conditions, the salts of monoalkyl esters of phosphonic acid of

formula IB.

  R -C \ Il X J 1 (D) p 0 k in which R and 1 have the meanings given above

  and A is set for the cation corresponding to the base AOH used.

  By acidification of the aqueous solution of formula IB, it is possible to obtain the free acids (A replaced by H) which deposit

in most of the cases.

  Suitable, for example, as a basis for the preparation

  ration of the compounds of formula LB, aqueous washing soda

  ses, barite water or alcoholic alkalis.

  The metal salts of formula IB can also be prepared by cleavage of the diesters of formula IA with salts

  neutral metal at high temperature.

  When R 1 in formula IB is put for a benzyl; these compounds are also suitable for the preparation of acids

  free derivatives of IB or for the preparation of compound I itself

even.

  Substituted l-phenyl-vinyl-l-phosphonic acids of -

  formula I 1 according to the invention and the derivatives derived therefrom

  suitable for example very well as monomers or comonomè-

  res for the manufacture of synthetic resins.

  Mention will be made, for example, of copolymers with acrylic and methacrylic acids, as well as with acid esters.

  (meth) acrylic, styrene vinyl acetate, vinyvl-

  imidazole and combinations of these compounds.

  Both in the form of free acids and in the form of

  salts, phosphonic acids have an emulsifying activity

amazing.

7 _

  Another interesting aspect of use should be mentioned

  emulsifiers made using l-phenyl-

  vinyl-phosphonic substituted according to the invention or their

  salts, the fact that these emulsifiers are fixed in poly-

  mother in the latex particles during polymerization.

  The following examples are intended to illustrate the preparation

  ration of the compounds of formula I according to the invention, without there being any need to limit them to these embodiments

EXAMPLES

  Examples 1 to 4 Preparation of substituted acetophenones

  2.4 mol of pulverized aluminum trichloride are introduced.

  in 500 ml of 1,2-dichloroethane and mixed, with stirring and cooling, with 2.1 mol of acetyl chloride Then

  2 mol of the alkyl- are added dropwise to 10 20-0

  appropriate benzene and stirring is continued for 1 to 2 hours at room temperature The reaction mixture is carefully poured over 900 g of ice, the organic phase is separated and

  the aqueous phase is extracted with dichloroethane Organic phases

  The combined dishes are washed with water, with 2% sodium hydroxide solution and again with water, dried with potassium carbonate and

  subjected to fractional vacuum distillation.

  Yield of substituted acetophenones: Example N 2 Substituted acetophenone Yield (% of theory) 1 Methylacetophenone 78 2 nhexylacetophenone 89 3 n-nonylacetophenone 82 4 n-dodecylac etophenone 68 Examples 5 to 8 Preparation of l-phenvl-vinrv acids 1-1- substituted phosphonics The substituted acetophenone and the phosphorus trichloride are preloaded, subjected to an intense mixture for min at room temperature, then slowly added, drop by drop, the acetic acid. charge becomes cloudy and the temperature begins to rise By intermittent cooling, the reaction temperature is maintained at 2320 Then the stirring is continued for 1 h and, under these conditions, the charge becomes clear and the temperature rises to approximately 2820 The acetyl chloride and excess Pm 13 are extracted under vacuum to a temperature of 432 o C at the bottom of the column and the mass similar to honey which

  rest is mixed with ice After adding 1,1,2,2-

  tetrachlorethand, the charge is heated in a separator

  of water and the theoretical amount of water is extracted by circulation

  When cooled or after concentration, the desired substituted 1-phenyl-vinyll-phosphonic acid separates out in the crystalline state. Example Alkylacetophenone n 2 alkyl = (mol) Pol -Acetic acid (mulol (mol)

  Ice Yield of 1-alkylphenyl acid

  (mol) virnyl-1-phosphonic (% of theory) pf (2 C) methyl 6 hexyl 7 nonyl 8 dodecyl 1.5 0.5 1.12 O, 3 d 1.875 0.625 1.5 0, e 375, 75 1.25 3.0 È 0.75 4.5 1.5 3.6 0.9 r%). -Ij

2.5 10578

Example 9

  Polymer dispersion with l- (hexylphenyl) -vinyl-l- acid

  phosphonic as a comonomer In a polykerization vessel, equipped with a stirrer, a reflux condenser and a thermometer, a solution of

  0.5 g sodium salt of l- (hexylphenyl) -vinyl-l- acid

  phosphonic acid and 0.5 g of potassium peroxobisulfate in 400 g of distilled water and the mixture is heated to 8020 C. In this preliminary charge, an emulsion prepared at drop temperature is introduced over 4 hours at 802 ° C. from 500 g of methyl methacrylate 500 g of butyl acrylate g of sodium salt of 1- (hexylphenyl) -vinyl-1- phosphonic acid 1.5 g of potassium peroxobisulfate and

600 g of water.

  After the end of the addition, the mixture is left at 800 ° C. for a further 2 hours. After cooling to room temperature, a well-filterable dispersion is obtained, devoid of

coagulated masses.

  Dry matter content: 49.2% Viscosity: 10 m Pa s I s 5 10578

Claims (2)

  1 1-Phenyl-vinyl-1-phosphonic acids le I R \ VS p DCH 2 o G 2 P 03 H 2 form substituted   (I) in which R is put for an alkyl radical vented 3 Jst sabmented, optionally branched, containing 3 to 20 carbon atoms, and salts, semi-esters, salts of semi-esters and diesters which derive from it.   2 Substituted 1-phenyl-vinyl-1-phosphonic acids of the formu-   the I according to claim 1, characterized in that R is taken for an optionally substituted alkyl radical, optionally   branched, containing 6 to 12 carbon atoms.   d, Process for the preparation of l-phenyl-vinyl-l- acids   substituted phosphonics of formula I R CH 2 (I) PO 3 H 2   in which R is taken to be an optionally substituted, optionally branched alkyl radical containing 3 to 20 carbon atoms, preferably 6 to 12 carbon atoms, and salts, semi-esters, salts of semi-esters and diesters derived therefrom , characterized in that, starting from Itacetophenone of formula II R O O -C CH 3 '   in which R is used for an optionally substituted, optionally branched alkyl radical containing 3 to 20 carbon atoms, preferably 6 to 12 carbon atoms, the latter is reacted with phosphorus trichloride, preferably in   presence of glacial acetic acid and the product is reacted   tional formed to react with a compound of formula III EX (III)   in which X is put for OH or C II, to obtain the compound of formula IV R CH   \ l 3 P 032 (iv) x in which R and X have the meanings given above, then the compound of formula V EX '(v) is thermally eliminated in which X' has the meaning of the symbol X appearing in formula IV , and we proceed to further processing   per se known, l-phenyl-, nyl-l-phosphonic acids subs-   of formula I thus obtained being converted, where appropriate, into the salts, semi-esters, salts of the semi-esters or diesters. 4 Use of the compounds of formula I according to claim 1 as monomers or comonomers in radical polymerization. 5 Use of the compounds of formula I according to claim 1 as polymerizable emulsifiers for products of dispersion polymerization.