DE1137428B - Process for the production of plasticizers - Google Patents

Description

Process for Making Plasticizers The invention relates to a process for the production of plasticizers, which is characterized in that that one 4,4-bis (4-oxyphenyl) valeric acid or an ester of this acid with ammonia or a monoamine, on whose nitrogen atom at least one hydrogen atom and at least one aliphatic, aromatic or araliphatic radical is bonded, condensed in a manner known per se.

The process for producing the plasticizers according to the invention changes somewhat depending on the properties of the reactants used and the properties of the amide obtained. For example, the ammonia or the amine directly with 4,4Bis (4 oxyphenyl) valeric acid or it can with the Esters of the acid are reacted and the amide formation through the application of temperatures up to about 225 to 250 "C. When ammonia or low-boiling amines Lower temperatures can be beneficial, and often is desirable to replace the ammonia lost through evaporation or the Carry out the reaction in a closed vessel to avoid volatilization of the amine to prevent.

This can happen when high-boiling amines are reacted with the acid Water formed during the amide formation expediently immediately after formation by azeotropic distillation with a hydrocarbon solvent or by Passing through an inert gas stream while heating the reaction mixture removed.

If an ester is used, they can be released during the reaction volatile alcohols also removed by distillation immediately after formation will. The alcohols not removed by distillation can often be easily removed Way to be washed out.

Among those involved in the amide formation of 4,4-bis- (4-oxyphenyl) -valeric acid Usable monoamines include a large number of aliphatic, aromatic or araliphatic amines, e.g. B. methylamine, laurylamine, stearylamine, allylamine, Diallylamine, octadecadienylamine, aniline and naphthylamine. The ones from simpler aliphatic Amines produced amides, e.g. B. those substituted methyl, ethyl and Contain butyl groups, have different miscibility towards the reactants, with which they are mixed. As the number of carbon atoms in the Substituents located on the amide nitrogen can be used in the amides according to the invention one considerable plasticizing effect can be achieved; the plasticizing effect becomes particularly valuable when the substituents have eight or more carbon atoms contain. The use of these amides for the plasticization of resin compositions has advantages over the processes usually used, since the plasticizing Groups chemically bonded to the reactants used in the conversion are. Such plasticizing groups cannot be leached out and evaporate not from the surfaces, but cause greater flexibility and toughness and chemical resistance of the end products.

The following examples serve to illustrate the invention.

Unless otherwise stated, the stated amounts relate to on weight. The acid numbers give the number of milligrams of potassium hydroxide again, necessary to neutralize a 1 g sample. The amine numbers indicate the number of milligrams of hydrochloric acid required for neutralization a sample of 1 g are required. The amine and acid numbers were determined by electrometric Titration determined. The softening points were determined by the mercury method according to Durrans (Journal of Oil and Color Chemists' Association, Vol. 12, 1929, p. 173 to 175).

Example 1 In a three-necked flask fitted with a thermometer, a mechanical stirrer and a reflux condenser connected via a water separator was provided, a mixture of 286 parts of 4,4-bis (4-oxyphenyl) valeric acid and 97 parts of diallylamine. With continuous stirring, the mixture became 4 hours heated to 148 to 158 "C. The temperature of the mixture was then within from 40 minutes gradually to 195 "C and then over 80 minutes to 235" C elevated. The mixture was then held at this temperature for 10 minutes.

During the heating from 195 to 235 "C, these were not reacted Diallylamine and the condensation water by evaporation into the water separator removed. The product obtained in an amount of 351 parts had a softening point of 111 "C, an amine number of 9.1 and an acid number of 31.7.

Example 2 Using the apparatus given in Example 1 became a mixture of 286 parts of 4,4-bis- (4-oxyphenyl) -valeric acid and 57 parts Allylamine heated to 120 to 140 "C for 33/4 hours, then the temperature was within of 50 minutes gradually increased to 207 "C. Additional 57 parts of allylamine were added and the mixture was kept at 105-108 ° C. for 2 hours. The temperature was then gradually increased to 2300 C over 35 minutes, whereby volatile material was collected in the water separator. That in a lot The product obtained from 321 parts had a softening point of 98 ° C., an amine number of 3.2 and an acid number of 31.1.

Example 3 Using the apparatus of Example 1, a mixture of 286 parts of 4,4-bis (4-oxyphenyl) valeric acid and 317 parts of »rosin Amine D «produced. "Rosin Amine D", a derivative of specially treated resins, is a technical grade dehydroabietylamine made by the Herkules Powder Company is distributed. (The properties of this amine are in a publication entitled "Rosin Amine D and Its Derivatives", 1953 edition, published 1952 by Hercules Powder Company.) This mixture was allowed to take 1 hour Heated at 1750 C. The temperature was then increased to 220 "C and within 20 minutes then heated to 250 ° C. within 15 minutes. The condensation water was removed by distillation throughout the reaction. That in one The amount of 577 parts of the product obtained had a softening point of 131 "C, a Amine number of 1.6 and an acid number of 10.7.

Example 4 In a three-necked flask fitted with a thermometer and a mechanical stirrer was provided, a mixture of 286 parts of 4,4-bis- (4-oxyphenyl) -valeric acid and given 274 parts of "armies" to SD. This unsaturated monoamine composition is a distillation grade primary amine available from Armor & Company on the Market and 200/0 hexadecyl amine, 170% octadecylamine, 26% octadecenylamine and 37% octadecadienylamine. (The characteristics of this "army" and others "Armies" described in the following examples are in a publication described in 1954 under the title "Armeens, High Molecular Weight Aliphatic Amines "published by the Armor Chemical Division, Armor & Company.) This mixture was heated to 155 "C; the temperature with continuous stirring was then to 1900 C within 1 hour and then within 18 minutes increased to 224 "C. The water of condensation was allowed to evaporate during the reaction. The product obtained in an amount of 536 parts had a softening point of 118 "C, an amine number of 6 and an acid number of 16.

Example 5 Using the apparatus of Example 4, a mixture of 72 parts of 4,4-bis (4-oxyphenyl) valeric acid and 135 parts of »Armeen 2 S «produced. Armeen 2 S is a secondary amine available from Armor & Company is put on the market and its alkyl chains to 200 / o from hexadecyl, to 200 / o consist of octaceyl, 250in of octadecenyl and 350in of octadecadienyl residues. This mixture was heated to 130 "C.

Then the temperature rose to 158 "C and. Within 21/2 hours then increased to 203 ° C. within 31/2 hours. The water was left during evaporate from the reaction. The product obtained in the amount of 198 parts was a viscous liquid with an amine number of 14.2 and an acid number of 0.9.

Example 6 Using the apparatus of Example 4, a mixture of 72 parts of 4,4-bis (4-oxyphenyl) valeric acid and 135 parts of »Armeen 2 T «produced. Armeen 2 T is a secondary amine available from Armor & Company is put on the market and its alkyl chains to 300/0 from hexadecyl, to 250 / o Octadecyl and 45% octadecenyl residues. This mixture was within heated from 30 minutes to 2000 C and held at 190 to 220 "C for 53/4 hours. The The water of reaction was allowed to evaporate. That obtained in an amount of 187 parts The product was a viscous liquid with an amine number of 15 and an acid number of 0.

Example 7 Using the apparatus of Example 1, a mixture of 1145 parts of 4,4-bis (4-oxyphenyl) valeric acid and 585 parts of octylamine Heated for 15 hours to 190 ° to 210 ° C. The reaction mixture was admixed with a further 7 parts Octylamine was added and heating to 1909C continued for an additional 12 hours. The low molecular weight substances were then vacuum distilled at one pressure of 20mm with heating of the reaction mixture to 190 "C. The in a The amount of 1329 parts of the product obtained had a softening point of 65 "C, a Amine number of 2.2 and an acid number of 0.

Example 8 Using the apparatus of Example 1, a mixture of 573 parts of 4,4-bis (4-oxyphenyl) valeric acid and 315 parts of decylamine Heated to 170 "C for 32 hours. During the final 30 minutes of heating the pressure to remove the volatile, unreacted amine is reduced to 60 mm. The product obtained in an amount of 750 parts had an acid number of 1.1, an amine number of 1.0 and a softening point of 142 "C.

Example 9 Using the apparatus of Example 1, a mixture of 429 parts of 4,4-bis (4-oxyphenyl) valeric acid and 278 parts Dodecylamine heated to 190 ° C. for 21 hours. A further 20 parts were added to the reaction mixture Dodecylamine was added and heating continued at 190 "C for a further 2 hours. During the last 30 minutes of heating, pressure was released to remove the volatile, unreacted amine reduced to 60 mm. That in a quantity of 680 parts obtained product had an acid number of 31.1, an amine number of 1.8 and a Softening point of 138 "C.

Example 10 Using the apparatus of Example 1, a mixture of 573 parts of 4,4-bis (4-oxyphenyl) valeric acid and 540 parts of octadecylamine Heated to 150 to 1700C for 25 hours. An additional 37 parts were added to the reaction mixture Octadecylamine was added and heating to 150-170 "C was continued for 8 hours continued. During the last 30 minutes of the heat, the pressure became 60mm degraded. The product obtained in an amount of 1087 parts had an acid number of 3.2, an amine number of 1.1 and a softening point of 142 "C.

Example 11 In an autoclave with a mechanical stirrer and a thermometer, a mixture of 1145 parts of 4,4-bis (4-oxyphenyl) valeric acid and 585 parts of n-butylamine. The autoclave was closed and the mixture heated to 170 to 180 ° C. for 2 hours with continuous stirring. Then one left cool the reaction mixture. The unreacted butylamine and the water were distilled off, the reaction mixture being heated to 173 "C. at a pressure of 20 mm became. The product obtained in an amount of 1090 parts had an acid value of 0, an amine number of 1.1 and a softening point of 175 "C.

Example 12 In an autoclave with a mechanical stirrer and a thermometer, a mixture of 573 parts of 4,4-bis (4-oxyphenyl) valeric acid and 323 parts of di-n-butylamine. The autoclave was closed and the reaction mixture heated to 150 to 170 ° C. for 13 hours with continuous stirring. Then the mixture was left cool the reaction mixture to room temperature. The fleeting, unconverted Di-n-butyl amine was distilled off, whereby the reaction mixture at a pressure heated from 20mm to 170 "C. The product obtained in an amount of 655 parts had an acid number of 0, an amine number of 1.0 and a softening point of 70 "C.

Example 13 Using the apparatus given in Example 1 was a mixture of 573 parts of 4,4-bis (4-oxyphenyl) valeric acid and 205 parts Aniline heated to 1800C for 12.9 hours. The temperature then rose within 1 hour gradually increased to 190 ". The water separator was filled with cyclohexane and the reaction mixture then with removal of the water of reaction for 2 hours refluxed at 170 to 180 "C. The final purification of the reaction mixture was carried out by heating at 180 "C for 1 hour at a pressure of 60 mm; 701 parts of the anilide of 4,4-bis- (4-oxyphenyl) -valeric acid with one softening point of 107 "C, an amine number of 0 and an acid number of 7.75.

Example 14 In a pressure bottle was added 100 parts of the methyl ester the 4,4-bis (4-oxyphenyl) valeric acid added 80 parts of anhydrous ammonia. The pressure bottle was capped and shaking continuously the temperature is increased to 100 "C and held at this value for 4 hours.

After removing the anhydrous ammonia, the solid product became pulverized and unreacted with 200 parts of diethyl ether to remove traces Washed methyl ester, with 85 parts of the desired valeric acid amide remaining, which is insoluble in ether. This product was made by dissolving in methanol and precipitating cleaned with water. The purified product had a melting point of 185.5 to 187.5 "C; the analysis for nitrogen gave 4.88% (theory 4,900 / 0) and an equivalent weight the phenolic hydroxyl of 139.6 (theory 142.5).

To demonstrate the superior softening effect of the after Amides which can be prepared by the method of the invention versus known amides were comparative experiments with a urea-formaldehyde and a phenol-formaldehyde condensation product carried out.

The following compounds served as plasticizers: I. 4,4-bis (4-oxyphenyl) valeric acid amide (Example 14); II. The amide from 4,4-bis (4-oxyphenyl) valeric acid and 200 / o hexadecylamine, 170 / o octadecylamine, 26% octadecenylamine and 370/0 octadecadienylamine (example 4); III. Acetamide (Examples 17 and 19 of U.S. Patent 2,589,245); IV. Amide from linseed oil fatty acid and diethylenetriamine (Example 23 of US Pat. No. 2,589 245); V. abietic acid amide; VI. The amide from soy fatty acids and ammonia (example 26 of U.S. Patent 2,589,245).

The experiments showed that the known amides, especially the under IV, V and VI mentioned, in contrast to those according to the procedure of invention preparable amides not as plasticizers for thermosetting urea-formaldehyde and Phenol-formaldehyde condensation products are suitable. They lead, whether in lesser or less larger amounts used, only to inelastic films in the case of the compound IV are also discontinuous. Their emollient effect is, if anything present, only slightly. The films made using compound III were a little better, but stuck in the warmth.

In contrast, those which can be produced by the method of the invention are produced Amides are particularly good plasticizers for urea-formaldehyde condensation products which, applied in larger and smaller quantities, are consistently elastic and result in continuous films.

Claims (1)

PATENT CLAIM: Process for the production of plasticizers, thereby characterized in that one has 4, bis (4-oxyphenyl) valeric acid or an ester thereof Acid with ammonia or a monoamine whose amine nitrogen atom has at least one Hydrogen atom and at least one aliphatic, aromatic or araliphatic The remainder is condensed in a manner known per se. Publications considered: German Patent No. 863 411; U.S. Patent No. 2,589,245; Karrer, Textbook of Organic Chemistry, 11 edition, 1950, p. 253.