DK150981B - PROCEDURE FOR THE PREPARATION OF DIESTER DIAMIDS - Google Patents

Description

150981

The present invention relates to a process for the production of diester diamides which can be used for the synthesis of regular structure polyester amides.

Polyesteramides are known in which the macromolecule has characteristic units of both the type - COO - R - (1) and of the type - CO - NH - R (2). Such compounds can be obtained in many ways, e.g. by polymerizing mixtures of diacids, diols and amines or from oxy acids and amino acids or by similar reactions. Using these processes, polyester amides with a 2,150,981 are obtained

Such an irregular structure adversely affects the mechanical properties of the products obtained, and furthermore, the properties of these products are difficult to reproduce.

In addition, methods for producing regular structure polyester amides have been proposed, in which processes the units 1) and 2) exist in a uniform and predetermined pattern. The proposed methods are based on the prior synthesis of comolexic monomeric compounds such as

ROOC - R '- CO - NH - R "- NHCO - R' - COOR

wherein R is usually a hydrogen atom or an alkyl group having a small number of carbon atoms, e.g. a methyl group, R 'is a divalent group, preferably a p-phenylene group, R "is a divalent group of the type - (CH 2 -) where n is a number in the range from 2 to 10.

To prepare such a complex monomeric compound, two methods have so far been proposed which can be illustrated by the following reaction schemes: a) 2 ROOC - R'COCl + H2N - R "- NH 2> ROOC - R'CONH - R" - NHCOR ' - COOR + 2HC1 b) 2 H00C - R '- C00H + H2N - R "- NH2—> H00C - R' - CQNH - R '<- NHCOR'COOH + 2H20

These methods have significant practical drawbacks.

In particular, carrying out process a) requires the preparation of expensive intermediates and a very complicated synthesis. Execution of process b), although very simple from a theoretical point of view, also requires critical conditions as it is performed by forming an intermediate salt having two quaternary ammonium atoms and such a reaction is limited to a few kinds. diamines and especially diamines which have an aromatic core in the molecule.

A process for the preparation of diester diamides from diethyl malonate and benzidine, tolidine or p-phenylenediamine is obtained, but mixtures of the diester diamides are obtained (cf. Journal of The Indian Chemical Society, vol. 15, pages 629-632, 1938). one or more other compounds, and a process of this type could therefore not be considered suitable for industrial production on payroll meeting a diester diamide of a purity which would make it suitable for the production of regular structure polyester amides.

However, it has now surprisingly been found that the reaction of reacting esters of higher dicarboxylic acids than malonic acid and diamines proceeds differently from the known reactions, and that in this simple and inexpensive process, only one product, namely the diester diamides, is formed. in high yield and with high purity.

The present invention, based on this finding, relates to a process for the preparation of diester diamides of general formula I according to claim 11. wherein R, M is a hydrocarbon group selected from alkyl groups 3 to 10 8 carbon atoms, aryl groups having 6 to 10 carbon atoms and cycloalkyl groups having 4 to 10 carbon atoms, A represents 1 - 3 - (CH 2) n - (CH 2) m - CH -m 2) m - C - (CH

Cli3 ™ 2

CH3 CH- CH. CH - CH- I 3 i 3 I 2 3

- (CHJ - CH - CH - (CH.) - CH - (CH_) - C

2 m 2 mj 2 mj ch 3 ch 3 where n is an integer from 4-20 and where m is an integer from 2-20, or a p-phenylene, toluylene, p-xylylene, m-phenylene, m-toluylene or m-xylylene group, or a 1,4-cyclohexylene, 1,3-cyclohexylene, 1,3-cycloamylene, 2-methyl-1,3-cycloamylene, 2-methyl-1, 4-cyclohexylene, 2-methyl-1,3-cyclohexylene, 1,3-cycloheptylene, 1,4-cycloheptylene or dicyclohexylmethane group, and B has the same meaning as A and may further denote ~ (CH2) < and and the process is characterized in that an excess of a dicarboxylic acid diester of the formula R "- O-CAC - OR" "wherein R" and A have the indicated meaning is reacted with a diamine of the formula H 2 N - B - NH 2 wherein B has the stated meaning, the reaction being carried out by heating the constituents as such or in the presence of an organic solvent in an inert gas atmosphere, preferably at atmospheric pressure.

When the reaction is carried out with a solvent, an aliphatic or aromatic hydrocarbon may advantageously be used.

The temperature of the reaction is not critical. It is advantageously selected in the range up to 250 ° C, taking into account the working conditions used. Preferably but not necessarily a distillation is carried out during the reaction to remove the alcohol.

As mentioned above, an excess of the diester must be used; this excess may advantageously be 1.5 to 5 parts over a stoichiometric part.

As mentioned, the reaction is preferably carried out at atmospheric pressure; however, it can also be performed at reduced pressure.

The reaction can be carried out without the use of catalyst, but the usual compounds which promote transesterification reactions can also be used.

The process according to the invention is further explained by the following examples.

Example 1 N, N1-p-carbobutoxybenzoyl dodecanediamine.

2780 g (10 moles) of di-n-butyl terephthalate (obtained as a quantitative yield by transesterification between dimethyl terephthalate and butanol) and 200.3 g (1 mole) of 1,12-dodecanediamine were placed in a 5 liter four-neck flask. with a stirrer, a nitrogen supply, a small stripping column and a submerged thermometer. The mixture was bubbled under nitrogen and the temperature was increased to 200 to 210 ° C over 1 hour and raised to 220 to 225 ° C after 3 hours and held there. for 1 hour. They got approx. 100 ml of butyl alcohol (theoretical yield = 165 ml). The reaction vessel was cooled to 130 to 140 ° C. The small stripping column was replaced by a reflux condenser.

Then 2000 cc of butyl alcohol was added and the suspension cooled to 100 ° C.

Filter was carried out by means of a thermostatically controlled funnel, where the temperature was maintained at 100 ° G.

The product is separated from the filtered solution by cooling. It was recovered by filtration, washed twice with 1500 cm 2 of acetone and dried at 70 - 80 ° C.

The yield of the crude product was 598 g. It was purified by dissolving in 7500 cm of boiling n-butyl alcohol and filtered by a funnel which was heated to 100 ° C from the outside.

The oligomers remained on the filter while the monomer crystallized with butyl alcohol.

The yield was 432 g (717. with respect to the diam. Mp = 167-168 ° C. Free groups = 8.6 eq / 10 g. Elemental analysis: C = 71.57 (theoretical 71.0); H 8.7% (theoretical = 8.6); N = 4.6% (theoretical 4.6).

Example 2 N, N 'tu-carboethoxyvalerylethylenediamine.

202 g (1 mole) of diethyl adipate and 6.6 ml (0.1 mole) of ethylenediamine were applied.

in an apparatus such as that described in Example 1. The mixture was heated to 150 ° C

over 1 hour and then for 2 hours to a temperature between 150 and 180 ° C, the ethyl alcohol formed being distilled off. The mixture was cooled and product 3 was dispersed in 500 cm of ethyl ether. The solid was filtered off, washed with an additional 500 cm 2 of ethyl ether and dried at 40 ° C. 32 g of crude product were obtained.

3

The product was purified by hot extraction with 300 cm benzene. Cooling 3 of the benzene solution, filtration, washing the solid with 500 cm of benzene and drying afforded 16.2 g of the monomer (yield = 43% with respect to starting diam.

Example 3 N, N'-p-carbobutoxybenzoylhexamethylenediamine.

2780 g (10 mole) of di-butyl terephthalate and 116 g (1 mole) of hexamethylenediamine were placed in a 5 liter flask equipped with a mechanical stirrer, a immersed thermometer, a Vigreux column and a distillation assembly. The air was replaced with hydrogen and heated so that the temperature was raised to 200 ° C over 1 hour. The temperature of the reaction mixture was maintained between 200 and 220 ° C for 4 hours with distillation of liberated butyl alcohol. It was then cooled, also in an inert atmosphere. As the temperature was lowered to approx. At 150 ° C, 2000 cm 3 of butyl alcohol was added continuously while cooling the suspension to 100 ° C. Filtration was carried out through a thermostatically controlled funnel where the temperature of KLev was maintained at 100 ° C. The product precipitated from the filtered solution upon cooling. It was collected by filtration, washed four times with 2 liters of acetone and dried under vacuum at 60 ° C. 460 g of crude product were obtained. It was purified by boiling with n-butyl alcohol and hot filtration. 328 g of the monomer was obtained from the cooled butyl solution (yield = · 62.5% with respect to the starting diamine). Mp. = 187 ° C.

β

Free amine groups = 10.6 eq / 10 g. C = 68.9% (theoretical = 68.8); H 7.6 (7.6), N = 5.1 (5.34).

Example 4 Ν, Ν'-β-carbopropoxybenzoylhexamethylenediamine.

500 g (2 moles) of dipropyl terephthalate and 23.2 g (0.2 moles) of hexamethylenediamine were placed in an apparatus as described in Example 3. The mixture was heated to 200 ° C for 45 minutes and the mixture maintained at 220 °. C for 4 hours under distillation of released propyl alcohol. It was cooled and the mass recovered by distribution in 1 liter of acetone. Filtered. The solid was washed with 600 3 cm of acetone and dried in an oven.

The product was purified by extraction with hot n-propyl alcohol in a Kumagawa extractor.

Mp. = L93-L94 ° C. Yield = 50% with respect to the starting amine.

β

Free amine groups = 28 eq / 10 g.

Example 5 Ν, Ν'-β-carbobutoxybenzoylethylenediamine.

278 g of n-butyl terephthalate and 6.6 ml of ethylenediamine were refluxed for 2 hours at 200 ° C and under pressure. Then the volatiles were partially distilled for 2 hours again at 200 ° C. The mass was cooled to ca. 150 ° C and 500 cc of n-butyl alcohol were added continuously. The mixture was left overnight. It was filtered and the 3 solid collected. This HLev washed with 150 cm of butanol and dried. 346 was obtained, while the oligomeric compounds remained undissolved.

Cooling of the butyl solution gave 22 g of product. Mp. = 210 ~ 212 ° C. Elemental Analysis: C = 66.8 (theory - 66.6); H = 7.1 (6.83); N = 5.6 (5.97).

Example 6

N₂N₂ &-carboethoxyvaleryldodecamethylenediamine, 20 g of 1,12-dodecamethylenediamine and 202 g of diethyl adipate were placed in a 3-neck, 500 cm flask equipped with a mechanical stirrer, a submerged thermometer and a small stripping column. An inert atmosphere was obtained and temperature was raised to L152 ° C and heating continued for 3 hours. Then the temperature was increased to 170 ° C and a new heating was carried out for 3 hours. The ethyl alcohol formed by the reaction was distilled off. After the reaction was complete, the mass was cooled and left overnight. The semi-solid mass formed was collected in 250 cm 3 of ethyl ether. It was filtered and washed three times with 100 cm of ethyl ether.

The solid thus obtained (57 g) was purified by hot extraction with benzene for 3 hours. The monomer crystallized from the benzene solution upon cooling. The 3 was filtered off, washed with 100 cm of ethyl ether and dried. 34 g of a product were obtained with m.p. 116-ll9 ° C.

Elemental analysis: C = 65.7 (theoretical = 65.6); H = 10.2 (10.1); N = 5.7 (5.4).

Example 7 Ν, Ν'-v-carboethoxyvaleryldiamindicyclohexylmethane.

202 g of diethyl adipate and 21 g of 4,4-diaminodicyclohexylmethane were reacted in an inert atmosphere and at 160 ° C for 4 hours and at 170 ° C for 1 hour.

The ethyl alcohol formed was distilled off. It was cooled and the semi-solid mass was collected in 200 cm of ethyl ether, filtered off and washed 3 times with 3 to 3 100 cm of ethyl ether. The crude product was purified by hot extraction with 900 cm benzene. The monomer crystallized on cooling the benzene solution. After 3 filtration, washing with 100 cm of benzene and then with 200 cm 3 of ethyl ether, V, 3 g of product with m.p. = 200-205 ° C.

Elemental analysis: C = 67.1 (theoretical = 66.7); H = 9.8 (9.57); N = 5.6 (5.36)

Example 8 Ν, Ν'-β-carbobutoxybenzoyl-metha-xylylene diamine.

278 g of n-butyl terephthalate and 13.6 g of m-xylylenediamine were placed in the 3-neck 500 cm flask equipped with a mechanical stirrer, a submerged thermometer and a small stripping column. It was heated to 200 ° C for 6 hours in an inert atmosphere. It was then slowly cooled to 80 ° C, then 200 cc of benzene was added and the mixture was allowed to stand. The white precipitate formed was collected 3 by filtration and washed three times with cold benzene (50 cm no. Sane) and then benzene (200 ml) for 3 hours. The monomer crystallized from the hot 3 benzene solution upon cooling, filtered, washed with 30 cm cold benzene to give 5.2 g. = 142-144 ° C.

Elemental analysis; C = 70.1 (70-6); H = 6.8 (6.6); N = 4.9 (5.15).

Example 9 N, N'-p-carbomethoxybenzoylhexamethylenediamine.

305 g (1.57 mol) of dimethyl terephthalate, 18.2 g (0.157 mol) of 1,6-hexamethylene diamine, 1084 cm of anhydrous toluene, 361 cm of absolute methyl alcohol, and 40 cm of a 1.23 M methyl solution of CH - Li + was placed in a 3 liter flask equipped with a reflux condenser, a mechanical stirrer and a nitrogen supply.

The mass was stirred during heating and refluxing. From the initially clear solution, the reaction product, after 1.5 hours of boiling, began to be separated again. The heating was continued for an additional 6.5 hours and then the mixture was filtered at a temperature of 65 ° C. The solid obtained was again partitioned into 200 cm 2 of toluene at 65 ° C and then filtered and repeated twice. The mass 3 was then washed twice with 200 cm of boiling methyl alcohol. The product, which was dried in an oven, weighed 64.2 g (93.870 yield of the diamine time) and can be polymerized in sera without further purification. Mp. --233-236 ° C.

C = 65.7 (65.5); H = 6.6 (6.36); N = 6.6 (6.36).

Example 10 Ν, Ν'-β-carbomethoxybenzoyl dodecamethylenediamine.

3 40.04 g (0.2 mole) of 1,12-dodecamethylenediamine in 1456 cm of anhydrous toluene and 3 484 cm of absolute methyl alcohol containing 0.063 mole of CH 2 OLi were reacted with 388 g (2 moles) of dimethyl terephthalate in an apparatus similar to that of Example 9 described.

The mixture was heated at reflux and from the initially clear solution, after 1.5 hours of boiling, the product Ν, Ν'-β-carbomethoxy-benzododeca-methylenediamine began to be separated.

Heating was continued for 8.5 hours, then the mixture was filtered at 65 ° C. The solid was washed 2 times with 200 cnf * toluene at 65 ° C and then 3 times with boiling methyl alcohol (200 cm each time). Then the solid was dried in an oven. The product thus obtained could be directly used for polymerization without further purification and had the following characteristics: m.p. = 203-205 ° C. C = 68.8 (68.7), H = 7.82 (7.64), N - 5.45 (5.34).

Example 11

N, N'-p-carbomethoxybenzoyldecamettslendiamin.

1940 g (10 moles) of dimethyl terephthalate and 400.4 g (2 moles) of 1,12-dodecanediamine were dissolved in 6.4 liters of anhydrous toluene and 1.6 liters of absolute methyl alcohol in a CH 2 O 1 was added. The mixture was heated at reflux. Β, β-carbo-methoxybenzoyl dodecamethylenediamine is separated from the initially clear solution after 0.5 h of boiling. The heating was continued for 6.5 hours, then the mixture was filtered hot (65 ° C) and the solid was washed twice with 3 liters of hot toluene (65 ° C) and 2 times with 5 liters of boiling methyl alcohol. After drying in an oven, it weighed 981 g (93.5% with respect to the diamine) m.p. 203-205 ° C.

Example 12 Ν, Ν'-β-carbomethoxybenzoyl dodecamethylenediamine.

In an apparatus such as that described in Example 9 and under an indifferent atmosphere, 116.4 g (0.6 mole) of dimethyl terephthalate with stirring and refluxing were reacted with 40.04 g (0.2 mole) of 1.12 dodecamethylene-3 diamine dissolved in 645 cm of anhydrous toluene and 162 cm of methyl alcohol to which 3

was added 185 cm of a 1.41 M solution of CH 2 OLi. NjN'-p-carbomethoxybenzoyldodeca-methylenediamine is separated from the initially clear solution after ca. 0.5 hours of cooking. The heating was continued for 6.5 hours, after which the mixture was filtered hot at 65 ° C. The solid was washed twice with 200 cm 3 of toluene at 65 ° C

3 and 2 times with 200 cm of boiling methyl alcohol. After drying in an oven, the product weighed 84 g (80% with respect to the diamine) and had a m.p. at 202-204 ° C.

Example 13

The example illustrates the use of the diester diamides prepared by the process of the invention.

Polyesteramide from Ν, Ν'-β-carbobutoxybenzoyl dodecamethylenediamine and 1,12-dodecanediol [12 N T 12J.

262 g (0.43 mole) of Ν, Ν'-β-carbobutoxybenzoyl dodecamethylenediamine obtained 3 according to Example 1 were placed in a 1000 cm flask equipped with a vacuum stirrer, an inert gas supply tube and a Vigreux column with a distillation assembly. The product was freed from gas under vacuum for 1 hour and then an indifferent atmosphere was added to 217 g (1.075 mol) of 1,12-dodecanediol and 0.43 cm of a butyl solution of 0.2 M tetrabutyl titanium. The flask was dipped in a bath of 200 ° C and stirred in an inert atmosphere at this temperature for 180 minutes and then for 205 minutes at 220 ° C. 77 cc of butyl alcohol was recovered. The Vigreux column was replaced by a short distillation assembly. It was connected to a vacuum tube and within 100 minutes the pressure increased from 760 to 0.5 mm Hg, while the temperature of the heating medium increased from 220 to 260 ° C. Then, at constant residual pressure, the temperature was raised to 270 ° C and after 55 minutes the polycondensation was stopped and a polymer compound which was essentially unstained and had a relative viscosity of 2.52 measured at 25 ° C in a phenol tetrachloroethane solution was obtained ( 50:50) and a concentration of 1 g / dl.

No. 9 150981 to a single thread by means of a melt spinning apparatus at a temperature of 280 ° C and then drawn, the needle and plate having temperatures of 30 g 150 ° G.

The extracted wire was stained at 100 ° C using Cl Cl Dispersed Orange 13 in large excess (greater than 100%) and with a pH 5.5 buffer [(NH 4) 2 SO 4 + H C00H] and a bathing ratio of 1: 100.

From the saturation isotherm, the staining rate constant and the value of the saturated concentration were obtained.

Table 1 gives the values of the mechanical properties and color characteristics obtained:

Table L

Thickness (den) 10.7

Toughness (g / den) 5.1

Filament extension% 15

Modulus (g / den) 60 Wet modulus%.

Dry modulus 2 2

Dye color K100g ^ kg sec * 15.3 C®®% 40.5

Toughness 4.5

Filament after extension ° Boiling in water for 20 min. modulus (g / den) 40 Wet modulus% Dry modulus

Toughness 4.6

Filament treated extension% 20 in air for 10 min at 160 ° C and then boiled modulus (g / den) 42 for 30 min in water Wet modulus% Dry modulus 0

Example 14 N-N '- (p-carbomethoxybenzoyl) -m-xylylenediamine.

3,960 cm 2 of anhydrous toluene, 210 cm 2 of pure methyl alcohol, 40.8 g (0.3 mole) of m-xylylenediamine and 407.8 g (2.1 mole) of dimethyl terephthalate placed in a 3 liter three-neck flask fitted with a stirrer , a reflux condenser and supply for inert o 3 gas. The mixture was then heated to 67-70 ° C and then 65.2 µm of a 0.83 M • methyl alcohol solution of CH 2 OLi was added.

After 70 minutes, a precipitate formed and the reaction was considered complete after 7 hours. The product was separated by hot filtration, washed with toluene to remove m.p. at 213 C. It had a content of basic groups corresponding to 28.2 raeq and the following elemental analysis:

C Η N

calculated 67.80 5j20 6.10 found 68.00 5.30 6.20

Example 15 N, N '- (p-carbomethoxybenzoyl) -1,4-diamine dimethylcyclohexane.

In an apparatus such as that described in the previous example, 407.4 g of 3 dimethyl terephthalate and 42.6 g of 1,4-diaminodimethyl ylcyclohexane were dissolved in 960 cm 2 of anhydrous toluene and 235 ml of pure methyl alcohol. The mixture was stirred to 67-70 ° C and then 3 added 49.4 cm of a 1.21 M methyl alcohol solution of CH 2 OLi. The reaction was complete after 9 hours.

The precipitated product was filtered hot on a biichner funnel, washed with 1 liter of hot toluene and then with hot water to remove the catalyst. The solid content obtained in 79% yield with respect to the starting diamine had a m.p. at 278 ° C, a content of amine groups corresponding to 41.3 meq / kg and the following elemental analysis:

C Η N

calculated 66.90 6.44 6.01 found 66.80 6.70 6.30

Example 16 N, N1- (p-carbomethoxybenzyl) -1,2-diamino-ethane.

Using the same apparatus as described in Example 1, 12 g of 1,2-diaminoethane was reacted with 233 g of dimethyl terephthalate dissolved in 650 3 3 3 boiling toluene and 170 cm boiling methyl alcohol. 14.4 cm of a 1.91 M methanol solution of CH 2 OLi was added.

The reaction was stopped after 5 hours. The product was filtered hot 3 o 3 off on a biichner funnel, washed with 500 cm hot toluene (70 C) and then with 500 cc of cold water to remove the catalyst.

The white solid (25 g) was crystallized with dimethylformamide at 80 ° C.

It had a m.p. of 315 ° C and a content of basic groups corresponding to 28.6 meq / kg.

Elemental analysis performed on ^ 20 ^ 20 ”2 ^ 6 of:

C Η N

calculated 62.6 5.4 7.3 found 65.7 5.4 7.5

Example 17 N, N- (carbomethoxycapryloyl) -1,2-dodecanediamine.

Using an apparatus such as that described in Example 14, 40 g of 11 g

After adding 260 g of dimethyl azalate, the mixture was heated to complete solution (70 ° C). Then 14.4 g of a 1.91 M methyl alcohol solution of CILOLi was added. The reaction was continued for 9 hours. The product was cooled and filtered by J 3 using a buchner funnel. The precipitate was washed cold with 500 cm of ethyl ether. The product (81 g) was crystallized with boiling methyl alcohol in a volume ratio of 1/50. The white solid, which was obtained in a 71% yield with respect to the amine used, had a m.p. at 129 ° C, calculated by differential thermal analysis and a content of free amine groups corresponding to 44.6 meq / kg. The Elemental Analysis for ^ 32 ^ 60 ^ 2 ^ 6 Var

C Η N

calculated 67.6 10.57 4.93 found 67.8 10.7 5.3

Example 18 N, N '- (p-carbornethoxybenzene and yl) -1,7-hep ta nd iami n.

Using an apparatus such as that described in Example 14, 26 g 3 o 1.7 heptanediamine was dissolved in 780 cm 3 of anhydrous toluene and 220 cm 3 methyl alcohol. 233 g of dimethyl terephthalate were added and the mixture was heated to complete solution. Then 17.3 g of a 1.91 M methyl alcohol solution of CH2 OLi was added. After 60 minutes, the diamide ester began to secrete. The reaction was continued with stirring for 270 minutes. It was cooled to room temperature and 2 liters of chloroform was added to dissolve unreacted dimethyl terephthalate. The remaining product was filtered off and dried under high vacuum. The white solid (93 g) was further washed by boiling with chloroform and then with cold methyl alcohol to remove all sports of the catalyst. The obtained diamide ester (yield of 51% with respect to the diamine) had a m.p. of 220 ° C calculated by differential thermal analysis and a content of free amino groups corresponding to 39.2 meq / kg and the following elemental analysis:

C Η N

calculated 66.0 6.61 6.17 found 66.50 7.0 6.53

Example 19 N, N '- (p-carbomethoxybenzoyl) -1,5-diaminopentane.

In the same way as described in the previous example, 24.5 g of 1,5-pentomethylenediamine and 233 g of dimethyl terephthalate were dissolved hot in a mixture of 3,780 cm 2 of anhydrous toluene and 22 cm 2 of methyl alcohol. When the solution had become clear 3, 17.3 cm of a 1.91 M methyl alcohol solution of CH 2 OLi was added. After 65 minutes, a precipitate formed. The reaction was continued with stirring for 270 minutes. The diamide ester compound was filtered from hot to reach a buchner-stained oe washed with 1 liter of inorganic salt. The white solid obtained weighed 61 g (yield of 59.6% for diamine used). It was crystallized with dimethylformamide at 90 to 100 ° C. In differential thermal analysis it showed a m.p. at 229 ° C. The content of free amino groups was 29.3 meq / kg and the elemental analysis for ^ 23 ^ 26 ^ 2 ^ 6 was consistent with the theoretical composition.

Example 20 N, N * - (carbomethoxycapryloyl) m-xylylendiamine.

Using the apparatus described in Example 14, 28 g of m-xylylene 3 diamine and 250 g of dimethyl azalate were dissolved hot in a mixture of 390 cm 3. 3 anhydrous toluene and 110 cm of methyl alcohol. Then, 17.3 cm of a 1.91 M methyl alcohol solution of CKLOLi was added. The reaction was continued at 67-70 ° C for 300 minutes and then 1500 cm of a mixture of heptane and ethyl ether (1: 1) was precipitated to precipitate the diamide diester.

The separated product was filtered off by means of a biichner funnel, washed with the same mixture of solvents and then with water to remove the catalyst. The dried product weighed 40 g. Differential thermal analysis showed a m.p. at 113 ° C and the elemental analysis for ^ 28Η44Ν2 ^ 6 was

C Η N

calculated 66.7 8.73 5.56 found 66.8 8.70 5.60

Example 21 N, N '- (p-carbobutoxybenzoyl) -1,12-dodecanediamine.

In the same way as described in the previous example, 40 g of 1,12-3 dodecanediamine and 334 g of dibutyl terephthalate were mixed down 650 cm of anhydrous n-heptane and 170 cm of n-butyl alcohol. The mixture was heated to 95 ° G and when the mixture 3 was clear 14.5 cm of a 1.17 M methyl solution of n-C CHgOLi was added. The amide ester is excreted almost immediately. The reaction was considered complete after 70 minutes. The product was filtered at 70 ° C, washed with acetone and crystallized with boiling n-butyl alcohol. The white solid had a m.p. of 166-168 ° C and a content of free amine groups of 29.4 meq / kg. The elemental analysis corresponded to the theoretical composition:

C Η N

calculated 71.0 8.6 4.6 found 71.3 8.7 4.6 13 150981

Example 22

A reaction was performed between dibutyl terephthalate (DBT) and dodecamethylene diamine (DMDA) in a xylene-butyl alcohol mixture.

DBT 166.8 g (0.6 mole) DMDA 20 g (0.1 mole)

MeONa 0.54 g (0.01 mole)

Xyl / butyl alcohol 75/25 400 ml

A 1 liter three neck flask equipped with a reflux condenser, a stirrer and a nitrogen supply was used.

The flask was put under nitrogen, then the DBT was dissolved in the solvent and heated. The catalyst and diamine were added and the reaction was boiled for 7 hours. The reaction mixture was added with 1 liter of acetone to facilitate filtration. Finally, the product was washed with acetone and then with ethyl ether.

It was then dried in an oven under vacuum at 70 ° C. DTA had a m.p. at 171 ° C and the elemental analysis was:

C Η N

calculated 71.05 8.55 4.60 found 70.8 8.55 4.65

20 g of product were obtained corresponding to a yield of 337 of the theoretical.

Example 23 N, N '- (p-carbome thoxybenzyl) -1,12-dodecaridiamine.

3,388 g (2 moles) of dimethyl terephthalate, 80 g of 1,12-dodecanediamine, 1280 cm of anhydrous toluene, 320 cm of absolute methyl alcohol, and 37.6 cm of a 1.41 M methyl alcohol solution of CH 3 liters of autoclave provided with an effective stirrer and the process was carried out under an inert atmosphere. After closing the autoclave, the reaction vessel was put under a stream of nitrogen (by replacing a vacuum with a nitrogen atmosphere). It was then heated to a temperature of Λ 130 ° C. The pressure was increased to approx. 9 kg / cm.

The reaction was complete after two hours. The mixture was removed from the autoclave, filtered hot (650 ° C), and the solid washed twice with 600 cm 2 of hot toluene and twice with 1 liter of boiling methyl alcohol. The product weighed after drying in an oven 190 g (the yield was 90.9% with respect to the starting diamine). Mp. = 203-205 ° C * Content of free amine groups = 55 meq / kg. The elemental analysis was consistent with the theoretical composition.

Claims (3)

Example 24 N, N '- (p-ca rb ome thoxybenz oy1) -4,4'-diaminediphenyl ether · At a temperature of 67-70 ° C and using an apparatus such as 3 described in Example 14, 116.4 g of dimethyl terephthalate dissolved in 400 cm of a mixture of toluene and methyl alcohol (72:25 by volume). 10.8 g of sodium methylate and 20 g of 4,4-diaminodiphenyl ether were then added. A gray and barely recognizable dispersion was formed. The mixture was heated under a nitrogen atmosphere for boiling for 10 hours. Then it was cold treated with HCl in a stoichiometric amount with respect to the catalyst and stirred for 1 hour. The solid was then filtered off again and washed with chloroform to remove dimethyl terephthalate and then with methyl alcohol. The white solid obtained in a yield (with respect to the starting diameter) of 38% had a m.p. at 341 ° C and the following elemental analysis: C Η N calculated 68.2 4.6 5.2 found 68.7 4.5 5.3 A process for the preparation of diester diamides of the general formula IR "-O-CAC-NH-B-NH-CAC-0- R, M II II II II T 0 0 0 0 1 wherein R" represents a hydrocarbon group selected from alkyl groups of 1 to 8 carbon atoms, aryl groups of 6 to 10 carbon atoms and cycloalkyl groups of 4 to 10 carbon atoms, A represents -3 - (CH) -, - (CH) - CH - (CH) - C - (CH) -, / Z tu i Z mi · m CH CH 3. L ch3 CH0 CH2 CH9-CH I 3 I 3 I 3 - (CH0) - CH - CH - (CHJ -, - CH - (CH) - C 2. lmizmi £ h3 CH3 150981 where n is an integer from 4-20, and where m is an integer in the range of 2-20, or a p-phenylene, toluylene, p-xylylene, m-phenylene, m-toluylene or m-xylyl group, or and 1,4-cyclohexylene, 1,3-cyclohexylene, 1,3-cycloamylene, 2-methyl-1,3 'cycloamylene, 2-methyl-1,4-cyclohexylene, 2-methyl-1, 3-cislohexylene, 1,3-cycloheptylene, 1,4-cycloheptylene or dicyclohexylmethane group, and B has the same meaning as A and can further denote and - (CH 2) ^ - know the sign that an excess of a dicarboxylic acid diester of the formula R "-O-CAC-OR" II II 0 0 wherein R "and A have the indicated meaning are reacted with a diamine of the formula H2N - B - NH2 wherein B has the indicated meaning the reaction being carried out by heating the constituents as such or in the presence of an organic solvent in an inert gas atmosphere, preferably at atmospheric yk. Process according to claim 1 using a solvent, characterized in that the solvent is an aliphatic or aromatic hydrocarbon. Process according to claim 1 or 2, characterized in that the reaction is carried out at a temperature of up to 250 ° C.