DE1206585B - Process for the polymerization of A2-oxazolines - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

Number.
File number:
Registration date:
Display day:

COSg

German class: 39 c-15

1 206 585
C31966IVd / 39c
January 25, 1964
December 9, 1965

It is known that ^{I 2} -oxazolines can react with carboxylic acids, their anhydrides or halides or with dilute strong acids with ring opening.

It is also known that / isoxazolines form salt-like compounds of the monomeric I ^{2 -oxazoline with strong acids or alkyl halides.}

It has now been found that one can produce high molecular weight, nitrogen-containing, linear polymers ^{by polyaddition of I 2 -oxazolines, ι ο if one zl 2} -oxazolines of the general formula process for the polymerization of
^ I ² -oxazolines

Applicant:

Chemical works Hüls Aktiengesellschaft, Mari

Named as inventor:

Dr. Wolfgang Seeliger, Mari

in which Ri to R5 are hydrogen atoms, aliphatic or cycloaliphatic, aromatic or heterocyclic radicals, but at least two radicals hydrogen atoms represent, polymerized in the presence of cationic catalysts.

As the cationic catalysts are already suitable for the cationic polymerization of cationically polymerizable monomers, such as. B. styrene, known catalysts such. B. sulfuric acid, phosphoric acid, organic sulfonic acids, such as. B. p-toluenesulfonic acid, benzenesulfonic acid, 1- or 2-naphthalenesulfonic acid, perchloric acid, preferably in concentrated or anhydrous form, boron trifluoride or its addition compounds, e.g. B. ethers, hydrohalic acids, advantageously in anhydrous form, tin chloride, aluminum chloride, or elemental iodine. Also effective are esters of strong acids, such as. B. alkyl sulfates or alkyl sulfonates, alkyl halides, insofar as they can react with amines with quaternization, and compounds that, under the polymerization conditions, optionally partially, can convert into the substances mentioned, such as. B. p-nitrophenyl diazonium fluorate or ammonium sulfate. Salts or salt-like compounds of the ^{I 2} -oxazolines with the above substances, such as. B. 2-propyl-zI ² -oxazoline sulfate, 2-phenyl-zf ² -oxazoline-p-toluenesulfonate, methoiodide or perchlorate also prove to be effective catalysts.

zI ² -oxazolines can be known from alkylolamines and carboxylic acids or their derivatives, eg. B. esters or acid halides, or from carboxylic acid nitriles and epoxies or halohydrins (Chem. Reviews, 44 [1949], p. 447 ff .; Chem. Abstracts, 57, p. 12 453). For example, 2-methyl-, 2-n-propyl-, 2,4,4-trimethyl-, 2-phenyl-, 2-m-nitrophenyl-, 4- or 5-methyl- 2 - phenyl, 2 - cyclohexyl, 2 - cyclododecyl, 2- (3-tetrahydrofuryl) -I ² -oxazoline.

The cation-active catalysts are used in amounts of 0.001 to 5, preferably 0.001 to 1 percent by weight, based on the Δ ² -Οχ- azoline used.

The polymerization of the zl ² -oxazoIine with cation-active catalysts often takes place even at room temperature on prolonged standing. However, it is advantageous to work at an elevated temperature, preferably between 70 and 280 ^° C., in particular 90 and 200 ^° C.

In the case of low-boiling / 1 ² -oxazolines, it may be appropriate to polymerize under pressure. But it can also be advantageous to carry out the polymerization under reduced pressure, for. B. when higher-boiling zl ² -oxazolines are to be polymerized under reflux.

The polymerization is generally carried out in the absence of solvents. However the polymerization can also be carried out as a solution polymerization, using inert solvents with boiling points at or above the desired polymerization temperature, such as. B. toluene or Xylene, can be used.

The polymerization can be easily controlled by varying the amount of catalyst or by the polymerization temperature. By adding hydroxyl compounds, such as B. water, or amines, which have a chain-terminating effect, the degree of polymerization be reduced. The polymers can be purified, for example, by falling over will.

509 757/435

The nitrogen-containing polymerization products obtained by the process according to the invention are high molecular weight, thermoplastic, generally hard, transparent plastics. Depending on the molecular weight and the type, number and size of the substituents, they can be used for the production of films, foils and threads or thermoplastic molding compounds such as casting resins or injection-molded articles. Some polymers, such as. B. those of the 2-methyl- ^{I 2} -oxazolins, are water-soluble and can be used as a thickener or for the production of water-soluble films.

The polymers of the J ² oxazolines are in solvents such. B. chloroform, ethylene chloride, dimethylformamide, readily soluble and can be processed from it.

They are characterized by their thermal resistance. The polymers prevent as a rule an electrostatic charge. By adding to other plastics, such as. B. polystyrene, polyvinyl chloride, its stability, colorability or pigmentation ability can be improved, the static Charge can be reduced.

From German Patent 1,067,437 it is known that vinyl-substituted oxazolines can be used for radical Tend to polymerize, d. This means that only the vinyl group is used for the polymerization will. The polymerization inhibitors specified in this patent only prevent one radical Polymerization in the sense indicated, but not a cationic polymerization accordingly the method of the present invention.

example 1

100 parts by weight of 2-n-propyl-zl ² -oxazoline (boiling point 148 to 150 of ⁰ C) and 0.1 part by weight of p-nitrophenyl-diazoniumfluoborat heated under exclusion of moisture for 1 hour at 120 ⁰ C and 15 hours at 130 ⁰ C (Olbadtemperatur) . A hard, high molecular weight, thermoplastic material is created. Softening range, determined on a Kofler bench, 106 to 126 ⁰ C; relative viscosity, measured in 1% chloroform solution at 25 ° C., 1.66. The corresponding high polymers are obtained when iodine, dimethyl sulfate, diethyl sulfate, sulfuric acid, tin tetrachloride, boron trifluoride etherate or ethyl iodide are used as catalysts.

Example 2

25 parts by weight of 2-p-ToluyI ^J-2 -oxazoline (mp. 70 to 72 ° C) according to Example held and 0.02 parts by weight of dimethyl sulfate are 1 for 9 hours at 140 ⁰ C. A hard, high molecular weight plastic is obtained.

Example 3

100 parts by weight of ^2-phenyl-2 zJ -oxazoIin and 0.1 part by weight of p-toluene sulfonic acid (mp. 36 ° C) are heated in accordance with Example 1 for 3 hours at 120 ⁰ C and 4 hours at 130 ° C. 98.5 parts by weight of a hard, high molecular weight, thermoplastic material are obtained. Relative viscosity 1.84, softening range 178 to 184 ° C, each measured under the conditions specified in Example 1.

Example 4

a) 100 parts by weight at reduced pressure freshly distilled over sodium ^2-phenyl-2 J oxazoline (mp. 29 to 31 ⁰ C) and 0.05 parts by weight of p-ToIuolsulfonsäure (mp. 36 ° C) for 15 hours at 12O ⁰ C held. 99.5 parts by weight of a high molecular weight, hard, thermoplastic material are obtained. Relative viscosity 2.3, softening range 180 to 190 ⁰ C, measured under the conditions specified in Example 1.

b) To check the content of monomers! 41 parts by weight of the plastic obtained are dissolved in chloroform in the heat. This solution is then stirred into twice the volume of ligroin (boiling point 90 to 110 ^° C.), left to stand for 2 hours and the precipitated polymer is boiled with ligroin for 1 hour. The residue is separated off

■ 5 a porous plate first dried in air and then at 100 ⁰ C and 15 mm Hg. 40.5 parts by weight of the polymer are recovered.

c) The repetition of example 4, a) with 2-phenyl- ^{I 2} -oxazoline perchlorate, boron trifluoride etherate, p-nitrophenyl-diazonium fluorate, 2-phenyl- ^{I 2} -oxazoline-hydroiodide or -p-toluenesulfonate. Dimethyl sulfate, diethyl sulfate, iodine, ethyl iodide, methyl iodide, anhydrous sulfuric acid or anhydrous phosphoric acid mixture (made from aqueous orthophosphoric acid and phosphorus pentoxide) as catalysts lead to high molecular weight, thermoplastic plastics.

Example 5

50 parts by weight of ^2-phenyl-2 oxazoline and 0.25 J Gewrchtsteile 57% aqueous provide hydoriodic acid after 20 hours at 130 ⁰ C, a viscous, liquid polymer.

Example 6

100 parts by weight of 2-phenyl- ^{I 2} -oxazoline are placed in a flask with a reflux condenser in the vacuum of a water jet pump (nitrogen-perfused boiling capillary, calcium chloride drying tower between the water jet pump and the flask) with 0.29 parts by weight of a mixture of equal volumes of concentrated sulfuric acid and dimethyl sulfate, which before the use briefly warmed to 130 ⁰ C and was then cooled again heated to an internal temperature of 120 ° C. The pressure is reduced to 13 mm Hg and the contents of the flask are stirred. The heat released during the rapid polymerization is dissipated by reflux cooling. After 60 to 70 minutes, the viscosity has risen to such an extent that it is no longer possible to stir. The mixture is then heated to 140 to 150 ^° C. for a further 14 hours and then left to cool.

97 parts by weight of a hard, thermoplastic, high-polymer plastic are obtained. Relative viscosity 1.56, measured in 1% chloroform solution at 25 ^° C.

Example 7

14 parts by weight of 2-phenyl-I ² -oxazoline are dissolved in 50 parts by weight of freshly distilled xylene and 0.07 parts by weight of dimethyl sulfate are added. Then it is boiled for 7 hours with the reflux condenser attached. After the solvent has been distilled off under reduced pressure, 12 parts by weight of a high molecular weight, hard plastic remain.

Example 7 is repeated using 2-phenyl-zl ² -oxazoline perchlorate, boron trifluoride etherate, p-nitrophenyl diazonium fluorate, 2-phenyl-zl ² -oxazoline hydroiodide, dimethyl sulfate, diethyl sulfate, iodine, ethyl iodide, anhydrous, methyl iodide or an anhydrous phosphoric acid mixture, a corresponding plastic is obtained in yields between 12 and 14 parts by weight.

Claims (1)

Claim: Process for the polymerization of ^{I 2} -oxazolines to high molecular weight, nitrogen-containing, linear polymers, characterized by net that one / ^ - Oxazoline of the general formula R ₂ R ₃ -C in which Ri to R5 are hydrogen atoms, aliphatic or cycloaliphatic, aromatic or heterocyclic radicals, but at least two radicals Represent hydrogen atoms, polymerized in the presence of cationic catalysts.