DD252378A1 - PROCESS FOR PREPARING POLYMERIC PERCARBOXY COMPOUNDS - Google Patents

Abstract

The invention relates to a process for the preparation of uncrosslinked polymer percarboxylates which show no tendency to explode over other polymer-aliphatic peroxides. The aim of the invention is to develop a new and at the same time simpler process for the preparation of polymer percarboxylates. According to the invention, the object is achieved by autocatalytically enriching hydrogen peroxide by vacuum removal of solvents and water of hydrogen peroxide as percarboxylate in a hydrophobic polymer carboxylic acid. The polymer percarboxylates are important for the detergent industry, for the epoxidation of monomers and as a bleach and disinfectant (Festozonisator).

Description

Field of application of the invention

The invention relates to a process for the preparation of polymeric percarboxy compounds as a solid product. Polymeric percarboxy compounds can be used in the detergent industry as well as being used as a disinfectant, bleach and for epoxidation.

Characteristic of the known technical solutions

For the epoxidation of olefins crosslinked, carboxy-substituted polystyrene resins are used, which are hydrogen peroxide with sulfur or. Sulfonic acid catalysis (Macromolecules 8,130 [1975] and J. Chem. Soc. 1,605 [1976] J. Chem. See, 1009 [1974]). This class of products (J. Chem. Soc., 1,2252 [1976] and Eur. Polymer J. 16,293 [1980]). Epoxidation with a polyacrylic acid-peracid type polymer is also known (J. Polym., Part B, 5.1031 [1967], J. Polym., 12.681 [1974], J. Appl. Polym. 19.1649 [1975]). In this case, a crosslinked polyacrylic acid resin is converted as a base polymer with hydrogen peroxide under sulfuric acid or sulfonic acid catalysis in the percarboxylate. The aliphatic compounds are explosive. This product is also used as a polymerization initiator (J. Polym., 9.2439 [1971]). Furthermore, bifunctional cation exchangers with percarboxylic and sulfonic acid groups have been used for the hydroxylation of olefin compounds to α-glycols (J. Appl Polym., Sci., 8, 2199 [1964]). Crosslinked polymer resins with percarboxylic groups, which were produced mainly by means of sulfuric acid and sulfonic acid catalysis with hydrogen peroxide use and of which the aliphatic per resins were explosive, were used so far.

Object of the invention

The aim of the invention is the easier production of polymeric, percaboxylgmppenhaltigen, uncrosslinked and non-explosive polymers as a soluble solid product with high Percaboxylgruppendichte.

Explanation of the essence of the invention Technical task

The object of the invention is to obtain percaboxylgruppenhaltige, uncrosslinked, soluble polymers of other starting materials, bypassing the foreign catalysis in the introduction of hydrogen peroxide.

Features of the invention

According to the invention, this object is achieved in that malein- and / or fumaric acid-containing, uncrosslinked polymers dissolved in an inert, difficult to oxidize solvent, hydrogen peroxide added, concentrated under reduced pressure at temperatures below 100 ° C and the polymer is eliminated as a solid product. As malein and / or fumaric acid containing, uncrosslinked polymers are used co-, Pfropfco-, Blockco- orTerpoymerisate of the general formula _f

ι ι

G * - G

Gooh,

wherein R ,, R _{2 is} H, alkyl, C _n -Ary!

R ₃ C _n -COOH, C _n -COOR ₄ , C _n -CONR ₄ R ₆ , C _n -COO Me

R ₄ , R _{5 is} H..alkyl, C _n -aryl

Me alkali and / or Erdalkalimeiallkation

η = 0 to 20 mean.

Hydrophobic or polymer-hydrophobic monomers of the norbornene type and / or monomers of the general formula can be used as the co- or monomer components

with R ₆ , R _{7 is} H, alkyl, C _n -aryl, alkoxy, cy, O-C _n -aryl, C _n -SO 3 H, Cn-halogen, C _n -CN, C _n -O-CO-R ₈ R ₈ alkyl, C _n -aryl η = Ο to 20,

preferably styrene and / or α-methylstyrene monomer units. It is advantageous, as the hydrophobic polymer, a hydrolyzed or partially hydrolyzed alternating Styrenmaleinsäureanhydridcopolymer and / or a- Methylstyrenmaleinsäureanhydridcopolymer or their ester, amide or salt derivatives in the molecular weight range of 1000 to 1,000,000, preferably with a maleic anhydride monomer concentration of 40 to 60% in the copolymer and the polymers in the molecular weight range of 5,000 to 50,000. Hydrogen peroxide solutions are used in the concentration range from 5 to 90% by volume of H ₂ O ₂ in H ₂ O and / or in solvents which are difficult or impossible to oxidize, for example acetone and / or halohydrocarbons. The hydrogen peroxide is diluted or undiluted in the homogeneous or heterogeneous polymer solution at temperatures below 100 ⁰ C, preferably less than 5O ⁰ C, under reduced pressure by separation of the polymer-solubilizing, preferably heavy or non-oxidizable solvent with agitation and / or stirring the polymer solution or - mass in the synthesis apparatus as a bound to the carboxyl group hydroperoxide enriched in the polymer. It is advantageous to use per mole of carboxyl group in the polymer 0.2 to 10 mol, preferably 1 to 3 mol of hydrogen peroxide.

The advantage of the preparation of polymeric percaboxylic compounds over the other processes and substances is the simplified, safe handling without danger of explosion as well as the solubility of the solid product obtained with high Percarboxylgmppendichte. Due to the simplified production are without foreign catalysis in the introduction of hydrogen peroxide percarboxylgruppenhaltige, uncrosslinked, d. H. obtained in the pH range of> 7 water-soluble polymers as a solid product in high yield of percarboxylic groups.

embodiments

The invention will be explained in more detail below with reference to several exemplary embodiments.

0.1 mole partial hydrolyzed or hydrolyzed a-methylstyrene-maleic anhydride copolymer is dissolved in a 500 ml round bottom flask in a little acetone (about 200 ml) with the addition of water. After addition of 0.2 mol of H ₂ O ₂ , the solvent and the excess water under concentration of H ₂ O ₂ in the copolymer under vacuum at room temperature while moving the copolymer H ₂ O ₂ solution, ie concentrated to dryness on a vacuum rotary evaporator , Depending on the degree of drying and temperature, peroxide contents of 40 to 90% peroxide per carboxyl group are obtained. According to the above reaction, the ratios of maleic acid copolymeric base unit and H ₂ O ₂ can be safely varied up to about 1:10; Preferably, the ratio of 1: 2 to 1: 4 is used. ·

In analogy to the above provision, the following maleic acid copolymers are converted to percarboxylates and subsequent elimination to the solid product:

polymer maleic acid Yield to H ₂ O _{2 use} Percarboxylate to COOH a-Methylstyrenmaleinsäure-Cp. 1: 1 40 = 45% 1: 2 80-90% 1: 3 85-90% 1: 4 90-95% 1: 5 90-95% a-Methylstyrenmaleinsäure-n-butyl amide-Cp. 1: 2 85% a-Methylstyren- maleate-Cp. 1: 2 80% Styrene-maleic acid-Cp. 1: 3 85% Styrene-maleic acid-n-butyl amide-Cp. 1: 2 80% Styrene-maleic acid ethyl ester Cp. 1: 2 75% Vinyl butyl ether-maleic acid-Cp. 1: 3 70% Stearate-maleic acid-Cp. 1: 3 60%

Analogous results were obtained with the fumaric acid copolymers and their derivatives.

Claims (7)

1. Process for the preparation of polymeric percarboxy compounds ,. in which polymers are activated with hydrogen peroxide, characterized in that malein- and / or fumaric acid-containing, uncrosslinked polymers dissolved in an inert, hardly oxidizable solvent, added hydrogen peroxide; concentrated under reduced pressure at temperatures below 100 ⁰ C and the polymer is eliminated as a solid product. 2. The method according to item 1, characterized in that ais malein- and / or fumaric acid-containing, non-crosslinkable polymers Co, Pfropfco-, Blockco- or terpolymers of the general formula. R ₁ R ₉ I I _ - " C '**" C 300H be used, where R ₁ , R _{2 is} H, alkyl, C _n -aryl R ₃ C _n -COOH, C _n -COOR ₄ , C _n -CONR ₄ R ₅ , C _n -COO Me R _{4 /} R _{B is} H, alkyl, C _n -aryl Me alkali and / or alkaline earth metal cation
n = 0 to 20 mean. " 3. The method according to item 1 and 2, characterized in that as co- or Termonomerkomponenten hydrophobic or polymer hydrophobizing monomers of the norbornene type and / or monomers of the general formula * T '6 CH ₂ - R ₇ be used with R ₆ , R _{7 are} H, alkyl, C _n -ArYl, alkoxy, OC _n -aryl, C _n -SO ₃ H, C _n -halogen, C _n -CN, C _n -O-CO-R ₈ R ₈ alkyl , C-Ary! n = 0 to 20 preferably styrene and / or α-methylstyrene monomer units. 4. The method according to item 1 to 3, characterized in that the co-, Pfropfco-, Blockco- or terpolymers with maleic and / or fumaric monomer units in a concentration of 10 to 90% and the polymers in the molecular weight range of 1000 to 1,000,000 , preferably in a concentration of 40 to 60%, and the polymers in the molecular weight range of 5,000 to 50,000. 5. The method according to item 1 to 4, characterized in that the hydrophobic polymer is a hydrolyzed or partially hydrolyzed, alternating Styrenmaleinsäureanhydridcopolymer and / or a-Methyistyrenmaleinsäureanhydridcopolymer or their ester, amide or salt derivatives are used. 6. The method according to item 1, characterized in that hydrogen peroxide solutions in the concentration range of 5 to 90 vol .-% of H ₂ O ₂ in H ₂ O and / or in difficult or non-oxidizable solvents, for example acetone and / or halogenated hydrocarbons are used. 7. The method according to item 1 to 6, characterized in that per primer carboxyl group with polymer 0.2 to 10 mol, preferably 1 to 3 mol. Hydrogen peroxide can be used.