DE1570605A1 - Hydrophilic, thermally stable polyester amides with sulfonic acid groups - Google Patents

Description

Hydrophilic, thermally stable polyester amides with sulfonic acid groups The invention relates to a process for the production of hydrophilic, thermal stable polyester amides with sulfonic acid groups.

It is known by melt condensation of polycarboxylic acids and Polyols polyester or polyester amides of polycarboxylic acids, polyols, and diamines to manufacture. However, both polyester and polyester amides only show a crack Water absorption capacity. However, there is often for certain areas of application the desire to use polycondensation products with increased hydrophilicity.

It is also known that the hydrophilicity of polyesters increases lets when higher molecular weight polyethylene glycols are used as polyoi component. Such but manufactured polyesters are particularly susceptible to Saponification and oxidative degradation.

It is also known that polyesters with increased hydrophilicity prevail Let win conversion of unsaturated maleic acid polyesters with bisulfites. These polyesters with sulfonic acid groups are thermally unstable and tend to be acidic pH range easy to split back.

There has now been a method of making hydrophilic and thermal stable polyester amides with sulfonic acid groups from polycarboxylic acids, polyols and Compounds containing sulfonic acid groups found, which is characterized is that, as compounds containing sulfonic acid groups, alkali salts of N - (# - aminoalkyl) aminoalkanesulfonic acids or of N, N'-alkylene-bis (# - aminoalkanesulfonic acids) can be used.

For example, compounds of the formula R1-NH- (CH2) x-NH y-SO3Me in which R1 is a hydrogen atom or the radical - (CH2) 7-SO3Me, x the numbers 2 to 12, y denotes the numbers 4 or 5 and Me denotes an alkali metal ion.

Of particular interest are compounds of the above formula in which R1 = hydrogen atom, x denotes the numbers 2, 4 or 6 and y denotes the number 4.

Among the alkali metal, lithium, sodium or potassium are preferred here Sodium or potassium understood.

The N (# - aminoalkyl) aminoalkanesulfonic acids to be used according to the invention are made by reacting alkylenediamines such as ethylene, propylene, tetramethylene, Pentamethylene-hexamethylene, octamethylene, decamethylene diamines or their on one or more carbon atoms through an alkyl radical. such as methyl, ethyl, propyl substituted Derivatives with one mole of butane-1,4-sultone or pentane-1,5-sultone or their on one or several carbon atoms substituted by alkyl radicals such as methyl, ethyl, propyl Detiraten, given @ all in a solvent such as benzene, toluene, chloroform, Chlorobenzene etc. produced in accordance with Deutsche Auslegeschrlft 1 200 318. she ammonium salts accumulate inside. For the production of the alkali salts the as internal ammonium salts of N - (- aminoalkyl) aminoalkanesulfonic acids in aqueous Solution reacted with the equivalent amount of lithium sodium or potassium hydroxide. The aqueous alkali salt solutions of the N (# - aminoalkyl aminoalkanesulfonic acids or the N, N'-alkylene-bis (# -aminoalkanesulfonic acids) are used directly or after neutralization with the equivalent amount of a polycarboxylic acid used for the condensation reaction. usually carbonic acids used for polyester production, as stated later, are in question.

The N, NL-alkylenebis («eaminoalkanesulfonic acids) to be used according to the invention are based on the German Auslegesehrift 1 200 318 as follows.

For one mole of the aliphatic diamine dissolved in water, in Presence of two moles of alkali metal hydroxide, two moles of alkane sultone at temperatures of 20-100 ° C, preferably at 40-60 ° C, was added dropwise. The reaction is more positive Heat tint. If necessary, the reaction is cured by occasional cooling carried out the desired reaction temperature. The reaction solutions obtained are directly or after neutralization with the equivalent amount of a polycarboxylic acid, such as already indicated above, used for the condensation reaction.

Should the Alkalisake of the mono- or dialkane sulfonic acid derivatives in solid form are used eo the reaction of the alkali hydroxide with the internal ammonium salts of the # -Aminoalkansulfonsäurederivate in methanol, ethanol or another lower alcohol with 1-6 carbon atoms, preferably 1-3 carbon atoms carried out and the salts after the addition of diethyl ether or benzene by filtration isolated.

All polyoarboxylic acids are suitable for the process according to the invention Aliphatic, aromatic or commonly used for polyester production hydroaromatic polybasic carboxylic acids, preferably aliphatic dicarboxylic acids with 4 to 10 carbon atoms. It is also possible to mix the individual Use polycarboxylic acids. Examples of polycarbanoic acids are: Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, Sebacic acid, isosebacic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, Terephthalic acid, hexahydroterephthalic acid.

Isophthalic acid and terephthalic acid are mostly taken simultaneously Use of common transesterification and condensation catalysts such as calcium acetate, Zinc acetate, cobalt acetate, antimony trioxide, etc., as methyl or phenyl esters of Subjected to condensation reaction. The catalysts mentioned are usually in amounts of opOs - 1 percent by weight} bent on the phthalic acids.

It is possible without any problems, including unsaturated polybasic carboxylic acids such as maleic acid and fumaric acid and / or monocarboxylic acids such as oleic acid and Fatty acids up to 30 mol percent, based on the saturated dicarboxylic acids used, to be used.

The polyhydric alcohols used in the process according to the invention preferred: ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6,2-hexanediol, 2-dimethylpropanediol-1,3, p-Hydroxymethyl-cyclohexane, trimethylclethane, trimethylolopropane, hexanetriol, glycerine and pentaerythritol or mixtures thereof.

To carry out the process according to the invention, the polycarboxylic acids, the polyols and the alkali salts of I -aminoalkyl) -aminoalkanesulphonic acids or N, N'-alkylenebis (# -aminoalkanesulfonic acids) mixed in the desired ratio and at temperatures from 150-3000 C, preferably 180-2300 C, condensed in the melt. To a To achieve the finest possible distribution of the aminoalkanesulfonic acids, it has to be Proven to be advantageous, these compounds in aqueous solution, which by adding the equivalent amount of polycarboxylic acids can be neutralized in the reaction mixture to add.

Depending on the choice of polycarboxylic acids, polyols and U-amino-. alkanesulfonic acid derivatives and the chosen proportions can be achieved through this condensation reaction linear or branched polyester amides with terminal hydroxyl or carboxyl groups and Generate pendant alkanesulfonic acid groups.

The molecular weight of the polyester amides can be adjusted to 8o, that both relatively low molecular weight products with a molecular weight of 500-5,000, preferably 800-3000, as well as higher molecular, stringy products are created. The molecular weights of the higher molecular weight products are above 5,000, preferably 10-50,000. Because of the sulfonic acid groups built into the polyester amide, they all stand out Products compared to comparable polyesters or polyester amides by an increased Hydrcphilien with simultaneous thermal stability.

The polyester amides produced by the process according to the invention can be 0.05 - 15 percent by weight, based on the end product, preferably 0.1 1-6 percent by weight, contain sulfonic acid groups.

The low molecular weight polyester amides containing sulfonic acid groups low melting point or oily or syrupy consistency are used as plasticizers and antistatic agents are suitable for plastics and are also used as intermediate products used in the paint and plastics sector, while the high molecular weight products with high melting points, e.g. B. from terephthalic acid, ethylene glycol, and N- (o aminoalkyl) alkanesulfonic acids for making threads and fibers with increased Hydrophilicity and improved affinity - used for basic dyes will.

The parts given below are parts by weight unless they are otherwise noted.

Production of N, N'-hexamethylene-bis (# -aminobutanesulfonic acid m sodium) as starting material for the process according to the invention 116 parts of hexamethylenediamine are dissolved in 400 parts of water. Then 80 parts of sodium hydroxide are added (solid) added in portions. At 40 - 60 ° C it takes 4 hours 272 parts of Butane @ ulton were added dropwise and then 8 hours at water bath temperature post-condensed. The aqueous solution obtained is essentially N, N'-hexamethylene-bis (# -aminobutanesulfonshures sodium) as a reaction product can be used directly for evaluate the method according to the invention used. b In a four-necked flask, the equipped with a thermometer, stirrer, gas feed pipe and an approx. 50 cm long column are adipic acid, diethylene glycol, 1,1,1-trimethylolpropane and a 50% aqueous solution of equimolar amounts of adipic acid and sodium N- (6-aminohexyl) -4-aminobutanesulfonic acid (Solution A) mixed in the desired ratio, nitrogen is passed over the reaction mixture and increases the temperature to 19,000, with the registered Water and part of the condensation water are distilled off. As soon as the temperature of the thermometer at the Kobnnenkopf falls below 95 ° C, the reaction temperature is increased for 2 - 3 hours at 230 ° C. The temperature is then allowed to drop back to 1900C and completes the condensation at 19,000 and a pressure of 12 to 20 torr.

Details of the polyester amides produced are given below Table I can be found.

Preparation of solution A: In 402.5 parts of distilled water 40 parts of caustic soda dissolved. One after the other then carries 252.4 parts with stirring N- (6-aminohexyl) -4-aminobutanesulfonic acid and 146.1 parts of adipic acid in the sodium hydroxide solution one, whereby the temperature may rise to 60 - 65 ° C. The 50% aqueous saline solution is then - possibly after adding a little activated charcoal - filtered and condensation of the polyesteramide used.

Table I (example 1) 1a 1b 1 c 1d 1e Adipic acid (Tle) 2321 1165 1132 1095 766.5 Diethylene glycol (Tle) 1733 885 865 840 585 1,1,1-trimethylol propane (Tle) 134 67 67 67 50.3 Solution a (Tle) 84 105 210 420 630 Condensation time b. 190 ° C (12-20 Torr) (Hours) approx. 4 approx. 6 approx. 10 approx. 12 approx. 12 OH number 53.3 57.5 67.2 65.8 84.0 Acid number 2.1 1.7 2.3 1.7 0.6 SO3Na content (mVal / kg) 27.3 67.5 135.0 262.0 500.0 SO3Na content (Wt%) 0.28 0.695 1.39 2.70 5.1 Example 2 In the apparatus described in Example 1, 1132 parts of adipic acid, 506 parts of ethylene glycol, 67 parts of 1,1,1-trimethylolpropane and 210 parts of solution A are condensed under nitrogen at 1900 ° C. until the thermometer at the top of the column has dropped to 850 ° C. The pressure is then slowly reduced and the condensation is completed in approx.

7 hours at 1900C and a pressure of 20 torr.

The polyester amide has an OH number of 55.2 and an acid number of 1.3. Of the The content of SO3Na groups is 165 mVal / kg, corresponding to 1.7 percent by weight.

Example 3 In the apparatus described in Example 1, 11a2 Parts of adipic acid, 600 parts of triethylene glycol, 435 parts of diethylene glycol, 67 parts 1,1,1-trimethylolpropane and 210 parts of solution A condensed under nitrogen at 190 ° C until the thermometer at the top of the column has dropped to 950 C, then increases if the temperature is raised to 2300 ° C. for 2.5 hours, the temperature is left at 1900 ° C. again decrease and the condensation ends in 15 hours at a pressure of 15 20 Torr.

The polyester amide has an OH number of 62.2 and an acid number of 3.5. Of the The content of S03Na groups is 122 mVal / kg, corresponding to 1.26 percent by weight.

Example 4 Following the procedure described in Example 1 are Adipic acid, hexanediol-1,6, 2, 2-dimethylpopanediol-1,3 and solution A gemiecht and condensed to polyester amide.

Table II (example 4) 4a 4b 4c Adipic acid (Tle) 1441 1423 1387 Bexanediol-1.6 (Tle) 767 767 828 2,2-dimethyl propanediol-1,3 (Tle) 550 550 445 Solution a (Tle) 105 210 420 Condensation time b. 190 ° C (12-20 Torr) (Hours) about 6 about 6 about 10 OH number 61 54 60 Acid number 2.8 3.7 1.1 SO3Na content (mVal / kg) 52.3 104.0 203.0 SO3Na content (Wt%) 0.54 1.07 2.09 EXAMPLE 5 Analogously to Example 1, 1423 parts of adipic acid, 605 parts of ethylene glycol, 152 parts of 1,2-propanediol and 210 parts of solution A are condensed under nitrogen at 180.degree. C. until the thermometer at the top of the column has dropped to 9500. The temperature is then increased to 20,000 for 2 hours. The temperature is then allowed to drop back to 185 ° C. and the condensation is terminated in 4-5 hours at a pressure of 15-20 Torr.

The polyester amide has an OH number of 74.4 and an acid number of 1.3. Of the Content of SO3Na groups is 130 meq / kg, corresponding to 1.34 percent by weight.

Example 6 Analogously to Example 1, 1095 parts of adipic acid and 822 parts are used Diethylene glycol, 67 parts of 1,11-trimethylolpropane and 364 parts of a 50% strength aqueous Solution of equimolar amounts of adipic acid and N- (2-aminoethyl) -4-aminobutanesulfonic acid Sodium (solution B) precondensed under nitrogen at 190 ° C until the thermometer the top of the column has dropped to 950c. You then raise the temperature for 2 hours at 2300C and ends the condensation in 15 hours at 190 ° C and one Pressure of 15 torr.

The polyester amide has an OH number of 68 and an acid number of 1.1. The salary of S03Na groups is 266 mVal / kg, corresponding to 2.74 percent by weight Manufacturing no of solution B 40 parts of caustic soda are dissolved in 346.4 parts of distilled water. 196.3 parts of N- (2-aminoethyl) -4-aminobutanesulfonic acid are then carried in succession with stirring and 146.1 parts of adipic acid in the sodium hydroxide solution, the temperature being increased to 60 - 65 ° C. The 50 k aqueous salt solution is then - possibly after Addition of a little activated carbon filtered and used for condensation of the polyester amides.

Claims (4)

Claims 1. Process for the production of hydrophilic undk thermally stable polyester amides with sulfonic acid groups by melt condensation from polycarboxylic acids, polyols and compounds containing sulfonic acid groups, characterized in that the compounds containing sulfonic acid groups are alkali salts of N - (# -aminoalkyl) aminoalkanesulfonic acids or of N, N'-alkylene- bis (# -aminoalkanesulfonic acids) be used. 2. The method according to Anepruch 1, characterized in that the sulfone groups containing compounds, compounds of the formula R1 - NH - (CH2) x - NH - (CH2) y - SO3Me in which R1 is a hydrogen atom or the remainder SO3Me, x the numbers 2 to 12, y denotes the number 4 or 5 and Me denotes an alkali metal ion, can be used. 3. Rydrophilic, thermally stable polyamides made from polycarboxylic acids, polyols, and N- (# -aminoalkyl) aminoalkanesulfonic acids. 4. Hydrophilic, thermally stable polyester amides from polycarboxylic acids Polyols, and -N, N'-alkylene- bis (# -aminoalkanesulfonic acids).