DE1123826B - Process for the production of linear polyureas with fiber-forming properties - Google Patents

Description

INTERNAT.KL. C 08 g

GERMAN

PATENT OFFICE

T 15843 IVd / 39 c

REGISTRATION DATE: NOVEMBER 6, 1958

NOTIFICATION THE REGISTRATION ANDOUTPUTE EDITORIAL: F E B RUARY 15, 1962

From the French patent specification 907 479 it is known to produce polycondensates by polycondensation of ω-aminoalkylene urea, which can be drawn into fibers. This extendable into fibers polycondensates are obtained according to one of the embodiments of this patent, by ω-Aminohexamethylenharnstoff first heated for a time at 21O ⁰ C and then the polycondensation is carried out under heating to a temperature of 300 ⁰ C. This polycondensation should also be carried out in the presence of a viscosity stabilizer and using increased or reduced pressure. According to the process of this French patent, however, only low yields of polycondensates are achieved as the end product; In addition, as a result of side reactions, structures with bridging or branching arise in the polycondensates, which leads to a deterioration in the properties of the fibers spun from them.

On the other hand, it is known that polyureas produced by polycondensation of cu-aminoalkylenurea excellent physical and chemical properties as fibers and plastics exhibit. As fibers, they have high toughness, good elastic recovery and a low cost Young module. However, such polyureas have a high melting point, so that it - compared with other synthetic fibers - it is quite difficult to process them into fibers by melt spinning.

In contrast, the invention proposes a method for producing purely linear polyureas with fiber-forming properties by two-stage reaction of cu-aminoalkyleneureas in the presence of a viscosity stabilizer at elevated temperature, which is characterized in that an ω-aminoalkyleneurea or ω-aminoalkyleneurea carbonate in the presence of an aliphatic Monocarboxamide with an alkyl radical containing at least 3 carbon atoms or an alkylenediamine substituted with an aliphatic acyl radical, the alkylene radical containing at least 6 carbon atoms, existing viscosity stabilizer is first heated to a temperature of 170 ° C to below 200 ° C and that the so formed Polycondensate is then condensed out in vacuo at a temperature of 250 to 265 ⁰ C, practically linear polyurea polycondensate end products with good spinning properties are achieved. To carry out the polycondensation according to the invention, the ω-aminoalkylene process is used for production

linear polyureas with fiber-forming

properties

Applicant:
Toyo Koatsu Industries, Inc., Tokyo

Representative: E. Maemecke,

Berlin-Lichterfelde West, Ringstr. 10,

and Dr. W. Kühl, Hamburg 36, patent attorneys

Yanosuke Inaba, Koji Kimoto, Fujisawa,

and Toshimi Nakagawa, Kamakura (Japan),

have been named as inventors

urea or carbonate first heated to about 115 to 12O ⁰ C in the presence of the viscosity stabilizing agent, wherein the starting material melts; or the starting material is first dissolved in a solvent, e.g. B. water, phenol or m-cresol, and the solution obtained is gradually heated. Here, the polycondensation proceeds with vigorous ammonia development at temperatures between about 170 and 200 ^° C. The polycondensates formed solidify. If the temperature is increased further, the polycondensates melt again. When a temperature is reached of about 250 to 26O ⁰ C, the condensation is carried out under vacuum, with virtually straight-chain, high molecular weight products are obtained of excellent quality and properties of high molecular weight polymers.

The polycondensation can advantageously be carried out in the presence of a small amount of alkylenediamine with the alkylenediamine having the same number of carbon atoms as that in that as the starting material used co-aminoalkylene urea or its Has carbonate containing alkylene group.

The ω-aminoalkylene urea used as starting material according to the process can be used in pure Form prepared in a known manner from nitrourea and alkylenediamine or by other methods will. In addition to co-aminoalkylene urea, derivatives of ω-aminoalkylene urea can also be used can be used as starting material.

209 509/351

The polyureas prepared by the process of the present invention (corresponding to a molar ratio of 100: 4: 2) and prepared according to the usual 40 parts of phenol are brought into a reaction vessel provided with a gas outlet process directly or as chips after the melt and added there under zen Fibers are spun. Furthermore, they can be heated with stirring, while other methods are used to process other methods to expel air, like other plastics, by molding or, after nitrogen, is introduced into the reaction vessel. At a temperature of about 100 ^° C., the

Unless otherwise stated, those in the mixture are a homogeneous liquid, with the following Examples given parts by weight. Gradual settling with the development of ammonia

expires. At a temperature of 170 to 180 ⁰ C Example 1 _{10 it} f _o igts with evolution of ammonia a stormy

100 parts of ω-ammononamethylene urea and 4 parts of implementation. The phenol is distilled off at 210 ° C. Palmitoylnonamethylenediamine (a molar ratio, the temperature is then increased to 250 ⁰ C, from 100: 2 accordingly) are brought into a reaction vessel provided with a gas outlet for the reaction at this temperature and reduced pressure of 1 to 2 mm Hg approximately there in the absence of Air under a nitrogen 15 is continued for 3 hours. A white atmosphere is heated while stirring. On reaching or slightly yellowish colored molten mass a temperature of about 5 ° C begins the co-aminotes, which in m-cresol has an intrinsic viscosity of 0.80 nonamethylene urea with formation of a homogeneous and properties that melt those of the products of the liquid, with development being the same as Examples 1 and 2 , of ammonia the reaction progresses gradually. 20 _ß . .

An example 4 takes place at a temperature of around 170 ° C

stormy implementation, while at about 180 ⁰ C a 95 parts ω-Aminooctamethylenurea and 4 parts

Solidification of the conversion mass occurs. If Palmitoylnonamethylendianiin (is further heated to a molar ratio, the reaction product melts of 100: 2 respectively) are placed in a with a further at a temperature of about 230 ⁰ C. After 25 gas outlet provided reaction vessel and heated to the homogeneous melting of the entire implementation there with stirring While to expel the mass it is passed under reduced pressure of air nitrogen into the reaction vessel. 1 to 2 mm Hg for about 3 more hours at 250 ° C at about 120 ⁰ C to melt the ω-Aminooctamethylen-

heated, whereby a white or slightly yellowish, through-urea, whereby a uniform, transparent, molten mass is obtained from the mixture, which easily becomes liquid and the reaction under ammonia can be spun into long fibers, which develop gradually. With further heating, a strength of 4.5 to 5 g / den, a specific weight of the reaction mass of about 170 ^° C. results in a strength of 1.06 and very good flexural strength. stormy implementation, which at a temperature

The molten mass may also by methods temperature solidified mass of about 180 ⁰ C.

as is known in the treatment of 35. The solidified melts on continued heating Plastics are used to be deformed. Mix the mixture at about 250 ° C to form a uniform mass.

The mass has a melting point of 235 to 240 ° C. The reaction is then reduced under a and an intrinsic viscosity of 0.75 in m-cresol. Pressure of 1 to 2 mm Hg at about 265 ° C approximately

. Continued for 3 hours, with a white or slightly

Example 2 ₄₀ yellowish colored, molten mass is obtained.

200 parts of ω-Aminononamethylenharnstoff, 6 parts of this mass, the mass has a higher melting point is obtained as the nonamethylenediamine and 5 parts of palmitic acid in the example 1, namely a (a molar ratio of 100: 4: 2 respectively) melting point of 255 to 26O ⁰ C Has Eigenbeisung together with 20 parts of water in a shaft similar to those of the reaction vessel provided by the process from a gas outlet, brought it and heated it there with stirring. At a . .

At a temperature of about 100 ° C., the mixture forms an example 5

homogeneous liquid, with 100 parts of ω-aminoheptamethylene carbonate and with distillation

of ammonia and water, the reaction gradually 2.16 parts Pelargonsäureamid (a molar ratio proceeds at a temperature of about 16O ⁰ C 50 100:. corresponding to 2.5), with the dead distillation of water, during subse- drive of Example 2 implemented, whereby the reaction with stormy ammonia evolution of ammonia and carbon dioxide continues at 170 evolution and the solidification of the up to 180 ⁰ C a stormy conversion and a Ver-conversion mass takes place at about 180 ° C. consolidation of the implementation mass takes place. With further

During the further heating to increase the temperature, the solidified blowing of air melts nitrogen into the reaction vessel mass at about 255 ⁰ C, whereupon the thereby obtained is initiated. When reaching a temperature of uniform mass under reduced pressure weüer about 230 ° C, the reaction mass melts again reacted and thereby a white, transparent, ge with formation of a uniform mass, which is obtained under melted mass. This product under reduced pressure according to that described in Example 1 can be converted into fibers with a strength of 4 to 5 g / the above process. to be spun. The product can also be deformed in other ways, as white or pale yellowish as plastics. Mass obtained whose properties are similar to those of the im.

Example 1 same product obtained. Example 6

". . ₁ , 65 100 parts »-aminodecamethylene urea and

.Example ό ₂₎ 6 parts of stearic acid amide (a molar ratio of

200 parts of ω-Aminononarnethylenurea, 6 parts 100: 2 corresponding) are in the presence of Nonamethylenediamine and 5 parts of palmitic acid amide 40 parts of m-cresol according to the described in Example 3

benen process implemented, with ^{a stormy implementation at about 180 0} C takes place. With further heating to 21O ⁰ C for distilling off the solvent and then at 215 ⁰ C the reaction is concentrated under reduced pressure, as described in Example 3, continued to give a white molten mass is obtained. The product can be spun into fibers which have a strength of 5 g / denier, a Young's modulus of 500 kg / mm ² and good flexibility.

Unless otherwise stated, the parts mentioned here are parts by weight.

In the term “co-aminoalkyleneurea” used here, the term “alkylene” is intended to mean alkylene groups denote with 6 to 12 carbon atoms. Corresponding urea derivatives, the such Containing alkylene derivatives of urea can also be used in the processes discussed here will.

Instead of phenol, other phenol-like solvents, such as m-cresol, can be used.

The term used here "high molecular weight alkylamides and high molecular weight alkyloyldiamines" is intended to denote compounds whose carbon chains contain 3 to 18 carbon atoms.

Claims (2)

PATENT CLAIMS: 1. A process for the production of linear polyureas with fiber-forming properties by two-stage reaction of ω-aminoalkyleneureas in the presence of a viscosity stabilizer at elevated temperature, characterized in that a co-aminoalkyleneurea or cu-aminoalkyleneurea carbonate in the presence of an aliphatic monocarboxamide with at least 3 Carbon atoms containing alkyl radical or an alkylenediamine substituted with an aliphatic acyl radical, the alkylene radical containing at least 6 carbon atoms, existing viscosity stabilizer is ^{heated to a temperature of 170 0} C to below 200 ° C and that the polycondensate thus formed is then in a vacuum at a Temperature of 250 to 265 ⁰ C is condensed out. 2. The method according to claim 1, characterized in that the polycondensation of the cü-aminoalkylene urea or co-aminoalkylene urea carbonate in two stages and in the presence of one small amount of alkylenediamine is carried out, the alkylenediamine having the same number of carbon atoms such as the alkylene group contained in the co-aminoalkyleneurea. Considered publications:
U.S. Patent No. 2,145,242;
French Patent No. 907,479;
"Excerpts from German patent applications", Vol. 8 (1948), p. 511, "P 84386 IV c / 39 c". When the registration was announced, nine pages of the test report were laid out. © 209 509/351 2.62