DE1123829B - Process for the production of spinnable mixed polyurea condensates from ªÏ-aminoalkylene ureas - Google Patents

Description

GERMAN

PATENT OFFICE

T17523IVd / 39c

REGISTRATION DATE: NOVEMBER 26, 1959

NOTICE THE REGISTRATION ANDOUTPUTE EDITORIAL: FEBRUARY 15, 1962

In the publication by Hopff et al. "Die Polyamide", Berlin (1954), pp. 53 and 56, become the different ones Properties of condensates and mixed condensates shown.

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 by ft) -Aniinohexamythylenharnstoff first heated for a time at 210 ⁰ C and then the polycondensation is carried out under heating to a temperature of 300 ⁰ C. This polycondensation should 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 secondary reactions, structures with bridging or branching arise in the polycondensates, which causes a deterioration in both the spinnability of the polycondensates and the properties of the fibers made from them.

On the other hand, it is known that polyureas produced by polycondensation of co-aminoalkyleneurea excellent physical and chemical properties as fibers and as plastic material exhibit. As fibers, they have high toughness, good elastic recovery and a favorable Young's modulus. 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. This unfavorable property is particularly pronounced when the used as the starting material β> -aminoalkyleneurea has a small number of methylene residues; but if the o-aminoalkylenurea has no more than 6 carbon atoms, shows the polyurea produced from it a melting point higher than its decomposition temperature. As a result, it prepares considerable Difficulties in making fibers from such polyureas by melt spinning without a Decomposition of the same takes place. Thus, from the standpoint of melt spinnability, such are polyureas to prefer those from cy-aminoalkylenureas have been made with a relatively large number of methylene residues. In this case occurs However, again another difficulty arises: in the same proportion as the number of methylene residues in the co-aminoalkylene ureas used Method of manufacture

of spinnable polyurea mixed

condensates from ω-aminoalkylenureas

Applicant: Toyo Koatsu Industries, Inc., Tokyo

Representative: E. Maemecke,

Berlin-Lichterfelde West, Ringstr. 10,

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

Claimed Priority: Japan December 1, 1958 (No. 34 399)

Yanosuke Inaba, Koji Kimoto, Fujisawa City, Hiromi Iyyama, Ödawara City, Ichiro Miwa,

and Kisaburo Ueno, Toyonuma, Sunagawa City

(Japan),
have been named as inventors

those from polyureas made from these monomers are increased by melt spinning achievable fibers inferior in terms of their ink absorption capacity. Because these polyureas also have strong crystalline properties, they are undesirable when molded as plastic Way pretty brittle.

In contrast, it has now been found that practically purely linear polyurea polycondensates from co-aminoalkylene ureas with excellent properties both as fibers and as plastic ίο material can be produced if one works according to the process according to the invention, which is characterized in that at least two different co- are Aminoalkylenharnstoffe having at least 6 carbon atoms in its alkylene or their carbonates initially at 115 to 12O ⁰ C reacted and the mass is finally condensed at about 250 ⁰ C. In carrying out the polycondensation of the invention the two above-mentioned various tw-Aminoalkylenharnstoffe or their carbonates at the specified temperature of 115 to 12O ⁰ C in an inert gas atmosphere, for example under nitrogen, heated to give a complete

209 509/354

3 4

Melting of the reaction product occurs, or the resin has a very uniform molecular weight ratio. B. water or phenol, dissolved and then shows shafts. In comparison to a customary temperature produced by reaction gradually up to the desired elevated temperature of a single alkylenediamine. The polycondensation begins as soon as the polyurea, the to-aminoalkyleneureas or their carbonate resin produced according to the invention, has a lower melting point and a lower melting point with the development of ammonia. The crystallinity on, whereby its spinnbarkeit to reaction progresses under a very violent fibers and pressing and deformation in casting molds ammonia development at temperatures between is facilitated. Continue to be carried to the invention about 170 and 180 ⁰ C. The fact that the condensed out superior Ansa animals of the coloring properties, strength, elongation, Young's modulus, the reaction mixture carried out io proper resins spun fibers at gradually elevated temperatures up to about 250 ⁰ C crimp stability and other chemical and physical and the reaction mixture then under vacuum lische properties.

is set, linear polyurea polycondens- In the following examples the parts are by weight

sate achieved. 15 parts.

The French example 1

see patent specification 907 479 achievable according to the invention Technical advantages result as follows: A mixture of 67 parts of ω-aminononamethylene-Im In general, co-aminoalkyleneureas dissociate urea, 125 parts of ω-aminooctamethyleneurea at elevated temperatures in the following way: ao and 2.6 parts of palmitic acid amide is

jj - ^ J ^ Njj QQ Njj _ ^ tight conversion vessel in which an inert

² HCNO + HN R. NH (1) atmosphere of practically pure nitrogen is present.

τι XT t> -NTXT r </ ~ i ² TS.TTT ² The mixture is stirred and brought to a temperature

H ₂ NR-NH-CO-NHa - * ■ brought from ₁₁₅ to 120 ⁰ C until it is slower

H _a NK JN-υυ + JN H ₃ (~) 25 evolution of ammonia is converted into a uniformly homo-liquid under the essentially mild reaction conditions. After handling in accordance with the present invention, the reaction (2) takes place mainly mixed at this temperature for about 1 hour, ie, it has been maintained, the temperature is slowly in addition to ammonia ω-aminoalkylene isocyanate, which leads to the presence of the inert atmosphere increased to 250 ⁰ C, an addition polycondensation to linear poly-30 until the liquid becomes viscous, which leads to a temperature condensates. According to the French Patent temperature of 170 to 180 ⁰ C, however, significant amounts of ammonia writing is mainly the reaction (1) to be developed. Has been After further 1 to 2 hours instead because there heats the polycondensation at above 200 ° C to 250 ⁰ C, the reaction temperatures lying begins. This is continued under reduced pressure. In the process, diamine is released from the reaction mixture, resulting in a light yellow, transparent molten mass both in a reduction in the yields of the polycondensate that is obtained, which can easily be spun into fibers, and in the formation of bridges in the polyurea which forms the molten mass and branched mixed condensate resin shows a melting point of gene in the final product. The viscosity number of 225 to 230 ⁰ C according to the invention and a basic molar in m-cresol is consequently that of the French patent 40 viscosity number from 0.7 to 0.9. The fibers spun from the resin from both the achievable yields and the melt show a tear with regard to the properties of the polycondensation length of 4.0 to 5.0 g / den, a Young's modulus of end products that is technically clearly superior. 350 to 450 kg / mm ² , an excellent crimp

The ω-aminoalkylene ureas, which have superior physical and chemical properties as starting compounds 45 in the case of the inven- tion stability, good staining speed and other processes according to the invention. Can be used in a suitable pure form. . ₁

produced from nitroureas in a known manner Example 2

or other known methods can be 111 parts of co-aminooctamethylene urea carbonate,

for the production of ω-aminoalkyleneureas and 108 parts of ω-aminohexamethyleneurea carbonate be turned. 50 1.6 parts of pelargonic acid amide are dissolved in 43 parts of water

Since the polyurea mixed condensate obtained by the process according to the invention at a temperature of 115 to 120 ^° C. under pressure is also set. After the reaction has been carried out under these conditions, the polyconditions produced by other processes for 2 or 3 hours, urea is drained at high temperatures, which has a tendency to the present water vapor and ammonia pressure, by dissociation of the isocyanate residue and the 55 and in the reaction vessel an inert amino residue due to a molecular rearrangement atmosphere, e.g. pure nitrogen, maintained, to depolymerize the urea, it is necessary, the temperature is slowly increased to 250 ° C, to prevent such depolymerization. During this time, water vapor and amdass the shape of the end group is different to that of the moniak emitted, and the mass becomes viscous in the case of urea. To this end, a small 60 state is made. The reaction is introduced under reduced pressure amount of a Alkylmonocarbonsäureamids or a melted at a temperature of 250 ⁰ C to form a N-Acylalkyldiamins as a stabilizer in the implementation polyurea mischkondensatharzesabsystem. The alkyl radical or acyl radical of the closed, which can easily be spun into fibers. Alkylmonocarbonsäureamids or N-Acylalkyldi- The resulting Polyharnstoffmischkondensat beamins should be at least three, and preferably six 65 sits a melting point 220-225 ⁰ C, in or more carbon atoms. m-cresol has an intrinsic viscosity of 0.7 to 0.9

It can be seen that by the inventive and excellent properties with respect to the Ver process produced polyurea poly-condensate spinnability from the melt. The other proprietary

Shafts are similar to those which the product described in Example 1 shows.

Example 3

82 parts of co-amino nonamethylene urea carbonate, 63 parts of ω-aminooctamethylene urea and 2.6 parts of N-caproyl nonamethylene diamine are dissolved in three times the weight of m-cresol and heated to 120 ° C. for 2 to 3 hours. The temperature is then slowly increased to 250 ° C. The reaction is effected in the presence of practically pure nitrogen, ammonia is given off and the solvent is distilled off. The condensation product is then converted into a viscous state. After the reaction has been carried out at a temperature of 250 ° C. for about 1 hour and the solvent has been completely distilled off under reduced pressure, the reaction is completed to form a molten mixed polyurea condensate which can easily be spun into fibers. The melting point of the resulting Polymischkondensats is 220 to 230 ⁰ C. The physical and chemical properties thereof, as well as those of the spun from the melt of this Polymischkondensats fibers are similar to those of the corresponding Polyharnstoffmischkondensats and fibers according to Example 2. FIG.

Within the scope of the invention, tw-aminoalkylene ureas can also be used may be used which have not been listed in the above examples, e.g. B. cu-aminoureas with decamethylene, dodecamethylene, Heptamethylene and other polymethylene radicals, which therefore have at least 6 carbon atoms.

Claims (2)

PATENT CLAIMS: 1. A process for the production of spinnable polyurea polymix condensates from co-aminoalkyleneureas, characterized in that at least two different ω-aminoalkyleneureas with at least 6 carbon atoms in their alkylene radicals or their carbonates are initially ^{reacted at 115 to 12O 0} C and the mass last at about 250 ⁰ C is condensed out. 2. The method according to claim 1, characterized in that the reaction in the presence of the Viscosity stabilizing amounts of an alkyl monocarboxamide or N-acylalkyldiamines. Considered publications:
French Patent No. 907,479;
Hopf et al., "Die Polyamide", Berlin 1954 pp. 53, 56. ® 209 509/354 2.