DE1187014B - Process for the production of polyureas - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

C08g

German class: 39 c - 6

Number: 1187014

File number: T18554IV d / 39 c

Filing date: June 22, 1960

Opening day: February 11, 1965

Resins or fibers obtained from polyureas having linear alkylene groups have excellent properties physical and chemical properties. They have a high level of toughness, a good one Young's modulus, good resilience, water resistance and resistance to chemicals. However, because of its high melting points and low decomposition temperatures, it is with Disadvantages associated with spinning them from the melt, and the dyeability of the resulting Fiber is bad. Furthermore, difficulties arise in the deformation of such polyurea resins because of their high melting points and low decomposition temperatures and their tendency to Lather up. The molded products obtained are quite brittle and not transparent. The mentioned Disadvantages occur in particular with those polyureas that are not less than Contains 6 carbon atoms.

Usually, polyureas tends to be produced by polycondensation with heating from a urea compound and an alkylenediamine, the reaction product to be in Solidify the course of condensation. This leads to local overheating. The reaction proceeds then not uniformly and homogeneously, and the product contains branching and crosslinking points.

On the other hand, fibers made from polyureas with heteroatoms have alkylene radicals spun with at least one ether group (—O—) or one thioether group (—S—) excellent dyeability and heat resistance. However, these fibers have a relatively low Young's modulus and thus a little wool-like handle when they are too Fabrics are processed. Such polymers also have the disadvantage of high density and become opaque when cooled in a molten state. However, their disadvantages are compared to those of the polyureas with straight-chain polymethylene residues, much smaller.

From British patent specification 530 267 and from United States patent specification 2,145,242 is also the Production of certain polycondensates from urea and diamines is known. In contrast to present invention, which leads to pure linear polyureas, are carried out in these processes the high initial temperature branched or crosslinked polycondensates are produced.

Furthermore, since the reaction conditions in the processes mentioned, in particular the molar ratio Process for the production of polyureas

Applicant:

Toyo Koatsu Industries, Incorporated, Tokyo
Representative:

Dr.-Ing. H. Ruschke, patent attorney,
Berlin 33, Auguste-Viktoria-Str. 65

Named as inventor:
Yanosuke Inaba, Fujisawa-shi;
Kunihiko Miyake, Kamakura-shi;
Goro Kimura, Fujisawa-shi (Japan)

Claimed priority:

Japan June 24, 1959 (20 177)

from urea to diamine, which differ significantly from those of the present process, the preparation of the polycondensates according to the invention, which are distinguished by unusually favorable properties, is not possible with their aid.
The method according to the invention eliminates the disadvantages associated with the known polyureas described above. Specifically, the invention proposes a process for the preparation of polyureas by reacting branched-chain ω, ω'-diaminoalkylalkanes or their carbonates with ureas, which is characterized in that branched-chain cj, a / -diaminoalkylalkanes having 4 to 11 carbon atoms and at least a branched alkyl chain with not more than 3 carbon atoms or their carbonates with urea, thiourea, methylenediurea, ethylenediurea, methylenedithiourea or ethylenedithiourea using a molar ratio of diamines to urea compounds of 1.01 to 1.02: 1 in a manner known per se.

The applicable molar ratio of diamine to urea, thiourea, alkylenediurea or Alkylenedithiourea is of critical importance to achieving the goals of the invention.

The reaction is carried out by preferring the starting materials, but not necessarily in Solvents such as B. water, phenol, m-cresol,

509 508/386

dissolves and then as a final process step the resulting mixture in an inert gas atmosphere, such as nitrogen or hydrogen, at a temperature of 200 to 280 ° C.

The diamines used in the process have the following chemical composition:

R ₁ Rj Ran-3 Ran-i NH ₈ -C ₁ -C ₈ ... C _n -, C _n -NH ₂

R ₂ »-2

2 η

where η is in the range from 2 to 10 and R ₁ , R ₂ ... R _{2n are} radicals of the composition C _m H, _{m + 1} , where m is in the range from 0 to 3. The diamines used according to the invention have a total of 4 to 11 carbon atoms, in which the alkyl side chains should not contain more than 3 carbon atoms and can have normal or branched chains. Polyureas made from diamines having a total carbon number of not more than 3 have higher melting points and are unstable in heat, while the polyureas made from diamines having more than 12 carbon atoms have lower melting points. Furthermore, when using the diamines described above, there is no solidification of the reaction mass in the course of the polycondensation. This means that the reaction can easily be kept under control and that the polyureas formed do not contain any crosslinking or branching points.

In order to obtain the linear polyureas, it is useful if the polycondensation after a Process is carried out in three stages: (a) First stage: At least one of the diamines described above or its carbonate and one of the urea compounds described above are in the molar amount indicated according to the invention, preferably dissolved in one of the solvents indicated above. The resulting mixture is under Heating to 80 to 130 ° C until the ammonia development from the reaction mass ceases, implemented, being almost completely a bimolecular condensate or a mixture of bimolecular condensates (b) Second stage: The intermediate compound obtained in the previous stage is gradually heated to continue condensation. Violent ammonia development occurs between 140 and 190 ° C, which temperature is maintained for a certain time around the Inhibit the course of the reaction. Any solvent present is distilled off, whereupon is further heated to free the mass of ammonia, and a prepolymer is formed, (c) Third stage: The prepolymer obtained in the previous stage is further between 200 and 280 ° C and preferably reacted at reduced pressure of 1 to 2 mm Hg until the polycondensation reaction is completed.

Since polyureas show a tendency to so-called »urea degradation« at elevated temperatures, d. H. for decomposition or depolymerization, a viscosity stabilizer is preferably used which an aliphatic monocarboxylic acid, an alkyl monoamide, an alkyl monoamine or an N-acylalkylenediamine can be, and which reacts with the terminal urea residues of the polyurea and him gives thermal resistance. It is desirable that any alkyl, acyl or alkylene group in these Stabilizers 6 to 18 carbon atoms and that the stabilizer in an amount of 0.001 to 0.07 mole per mole of urea compound is used. He can be in any reaction stage before the above described third stage are added.

The polyureas prepared according to the invention can be spun from the melt extremely well. The fibers made therefrom can be stretched at room temperature and have excellent properties Toughness, excellent flexural properties and dyeability. The melted one Polyurea can be gradually cooled to a colorless clear resin. The educated Resin is easy to mold, has excellent impact strength and electrical properties Properties, is very waterproof and also has a low density. The following table shows Comparisons between inventive 2-ethyl

Type of threads

density

Melting point

Softening point tensile strength
g / d

when dry in wet
State

Loop tensile strength

g / d

strain
Vo

dry

wet

6,6 nylon

Polycaproamide

Nonamethylene

polyurea
Ditetramethylene ether

polyhane fabric
2-ethyloctane

polyurea
2,5-diethylhexane

polyurea

1.09 to 1.14

1.10 to 1.14 1.05 to 1.08 1.14 to 1.16 1.01 to 1.02 0.95 to 1.02

250

215 236 216 200 185

235

180 225 200 182 183

4.6 to 5.9

5.0 to 6.4 4.5 to 5.5 4.4 to 5.5 4.0 to 5.0 3.8 to 4.5 4.0 to 5.2

4.2 to 5.9
4.5 to 5.5
4.2 to 5.3
4.0 to 5.0
3.8 to 4.5

3.9 to 5.1

4.5 to 5.4
3.3 to 4.0

3.6 to 4.0
4.0 to 4.8
3.8 to 4.5

26 to 32

28 to 36
20 to 22
28 to 30
24 to 26
22 to 26

30 to 37

38 to 48

22 to 24 30 to 33 24 to 27

23 to 28

octane polyurea, 2,5-diethylhexane polyurea and some other polyureas and polyamides.

example 1

A mixture of 176 parts of 1,8-diamino-2-ethyloctane, 60 parts of urea, 2.5 parts of palmitic acid (corresponding to a molar ratio of 102: 100: 1) is placed in a reaction vessel with a gas outlet. Nitrogen is introduced to prevent the mixture from coming into contact with air. The mixture is ^{heated to 110 ° C for Ι 1} / hours and heated further after melting. The reaction mass reacts violently at 70 to 180 ° C with evolution of ammonia. During the evolution of ammonia, the temperature is temporarily not increased any further. When the evolution of gas subsides, heating is continued up to 245 ° C. The reaction is then continued at 1 mm Hg for about 4 hours to give a colorless, transparent, molten product. The reaction mass does not solidify during the heating process, but rather forms a viscous liquid during the evolution of ammonia, and the polycondensation reaction proceeds uniformly and homogeneously. The melted product remains completely transparent and colorless after it is gradually or rapidly cooled to room temperature. It has a melting point of 195 to 200 ° C and a density of 1.0164.

It is deformed in a deforming device; the deformed product is colorless, transparent and very temperature-resistant as well as excellent flowability.

The melted product is excellent for spinning and can be processed into long fibers. the Fibers can be dyed evenly and deeply with various dyes; they are extraordinary resistant to washing and sunlight.

Example 2

40

A mixture of 174 parts of l, 6-diamino-2,5-diethylhexane, 132 parts of methylenediurea and 2.6 parts of octylamine, corresponding to a molar ratio of 101: 100: 2, becomes phenol in 200 parts solved. The resulting solution is placed in a reaction vessel with a gas outlet, in which it is 2 hours is heated up to 120 ° C. After it has completely dissolved, the reaction mixture is heated further, wherein nitrogen is bubbled through the reaction vessel. At 160 to 175 ° C the reaction will violent with evolution of ammonia. During the evolution of ammonia, the temperature does not rise further increased. After the development has subsided, heating to 200 ° C. is continued. Then it will be the solvent is distilled off, and it is further up to 260 ° C and then a further 5 hours below 1.5 mm Hg heated to 260 ° C. A colorless, transparent, molten product results which turns into a shiny, translucent, colorless substance when it is gradually cooled. It can be easily deformed and also easily into fibers in the molten state or in chips spin. It has a density of 0.956 to 1.012 and a melting point of 185 to 193 ° C.

Example 3

A mixture of 119 parts of 1,5-diamino-3-methylheptane, 76 parts of thiourea, 2.6 parts of palmitic acid amide, corresponding to a molar ratio of 102: 100: 1, is dissolved in 100 parts of water and the resulting mixture is placed in a reaction vessel with a gas outlet. Hydrogen is passed through, to prevent the mixture from coming into contact with the air. The mixture will be about Heated for 3 hours to 110 ° C., the greater part of the water contained therein being distilled off and a lower condensate is obtained. It is heated further and the reaction mass develops between 160 and 170 ° C lively ammonia. During the evolution of ammonia, the temperature not increased. After the evolution of ammonia has subsided, heating is continued up to 250 ° C. During the evolution of ammonia, the viscosity of the reaction mass increases. Solidified when heated the reaction mixture does not and the reaction proceeds homogeneously and uniformly. The reaction continued for about 6 hours at 2 mm Hg, leaving a colorless, translucent, molten Product is obtained.

Young resistance 1* (·/")
in4O «/ o Dyeability ** Disper
sion tuastiscne module against chemical H ₂ SO ₄ k (mg / g ■ h) dye ΓΟΠΠ-
resistance kg / mm ² Kaliei
in 20Vo immediately acidic 26th % 150 to 250 NaOH solved dye 100 96 36 (2 to 8 »/ 0 immediately 28 Strain) 250 to 400 solved 98 to 100 97 91 32 31 (3% elongation) 450 to 600 100 92 50 20th 35 (3% elongation) 270 to 350 99 to 100 93 92 2040 70 (3% elongation) 350 to 450 100 93 91 550 80 (3% elongation) 300 to 400 99 to 100 93 1240 (3% elongation)

* Decrease in toughness after 10 hours

Immersion.

** k means the equilibrium rate constant (mg / g · h). The acidic dye is Acid-Milling-Red B and corresponds to the following formula:

CH ₉

OH NH-SO ₂

/ -CH ₃

SO ₈ Na SO ₈ Na

The bath concentration is 3%, the bath temperature 100 ° C., the pH value 2, the bath ratio 100. The disperse dye is Celliton Fast Brown 3R (C. J. Disperse Orange 5), the conditions are otherwise the same.

The product is extremely easy to spin from the melt into long fibers. The one with it obtained fibers can be dyed deeply and evenly with various dyes, and their durability against washing and sunlight is very good. The product has a melting point of 245 bis 250 ° C and the density 1.004 to 1.015. Compacts made from this product (diameter 3 to 5 mm, height 4 to 7 mm) can be shaped excellently; the molded objects are colorless and transparent.

Example 4

A mixture of 178 parts of the carbonate of 1,6-diamino-3-methylhexane, 60 parts of urea and 1.6 parts of pelargonic acid are dissolved in 100 parts of water and placed in a reaction vessel with a gas outlet. Nitrogen is then passed through to prevent contact of the mixture with air. The mixture is heated to 120 ° C. for 4 hours, most of which is contained Water is distilled off and the ammonium carbonate formed as a by-product is decomposed and in vapor form is distributed. With further heating, the reaction mass violently develops ammonia. While the ammonia development does not increase the temperature any further. After the ammonia development has subsided is further heated up to 250 ° C. In the course of the ammonia evolution mentioned above the viscosity of the reaction mass increases. The implementation will take another 4 hours continued below 1 mm Hg to give a colorless, transparent, molten product will. It has a melting point of 235 to 240 ° C and a density of 1.002 to 1.030. On cooling down A colorless, transparent resin is obtained at room temperature.

The melted product can be easily spun from the melt, and those obtained therefrom Fibers can be dyed evenly and deeply with various dyes. You have excellent Resistance to light and alkalis. Furthermore, those produced from the polymer are Resins resistant to heat and can be shaped excellently.

Example 5

A mixture of 133 parts of 1,5-diamino-2,4-dimethylpentane, 60 parts of urea and 2.6 parts Palmitic acid amide, corresponding to a molar ratio of 102: 100: 1, is added to a reaction vessel Given gas outlet. Nitrogen is introduced to prevent the mixture from coming into contact with the air. The mixture is heated to 70 to 100 ° C for 7 hours, the urea contained melts with evolution of ammonia. The amount of ammonia developed corresponds to 50% of the theoretical Lot. The lower condensate present at this stage contains over 98% ω-amino-2,4-dimethylpentylurea. With further heating, the viscosity of the lower condensate gradually increases with evolution of ammonia. Between 170 and 180 ° C the reaction mass violently develops ammonia and forms a viscous liquid without ever to solidify, and the reaction is homogeneous and even. After the temperature has risen to 240 ° C, the reaction is continued for about 5 hours under 1 mm Hg, with a colorless, clear, molten product is obtained. The melted product can be extremely easy to spin into long fibers. The threads obtained have a tenacity of 5 to 6.5 g / d and can be colored deeply and evenly with various dyes. aside from that they have excellent resistance to alkaline substances and light.

The melted product remains colorless, transparent and temperature resistant after it is on Room temperature has been cooled. The resin produced therefrom is in a deforming device deformed. The deformed product is very notch-resistant, colorless and transparent. The melted one Product has a density of 0.98 to 1.015 and a melting point of 220 to 225 ° C.

Example 6

A mixture of 73 parts of 1,6-diamino-2,4-dimethylhexane, 66 parts of 1,6-diamino-2-methylhexane, 60 parts of urea and 1.2 parts of caproamide, corresponding to a molar ratio of 51: 51: 100: 1, is dissolved in 100 parts of water and placed in a reaction vessel with a gas outlet. Then it will be Introduced hydrogen, and it is heated to 98 to 100 ° C for 3 hours. Then it is gradually warmed up, the water obtained being distilled off from the reaction mixture. Here the Reaction mass violently ammonia. The temperature is not changed during the evolution of ammonia. After the evolution of ammonia has subsided, heating is continued up to 240 ° C. then the reaction is continued under 1.5 mm Hg for about 3 hours to obtain a molten mass will. The mass is difficult to crystallize and can easily be turned into films and other objects process and deform. The products obtained are transparent and colorless. The substance has a melting point of 220 to 225 ° C and a density of 0.94 to 1.012.

Example 7

A mixture of 160 parts of 1,6-diamino-3-isopropylhexane, 60 parts of urea and 2.6 parts of palmitic acid amide, corresponding to the molar ratio 101: 100: 1, is placed in a reaction vessel with a gas outlet. Then nitrogen is introduced to prevent contact of the mixture with air. Nitrogen continues to be passed in until the pressure reaches 2 kg / cm ² . It is heated to 120 ° C. for 4 hours and then gradually heated further. During this time the reaction mixture reacts violently with evolution of ammonia. The ammonia that has evolved is removed in order to avoid an increase in pressure. After the evolution of ammonia has subsided, heating is continued up to 250 ° C., the mass being reacted for a further 3 hours under 1.5 mm Hg. The polycondensation reaction proceeds homogeneously and evenly to the end, and a transparent, colorless, molten product is obtained. This can easily be spun from the melt into long fibers. It is also easy to process into films and other objects. The product has one

Melting point from 180 to 185 ° C and the density 1.008 to 1.025.

Example 8

A mixture of 221 parts of the carbonate of 1,6-diamino-2,5-methylisopropylhexane, 76 parts Thiourea and 2.5 parts of palmitic acid, corresponding to the molar ratio 102: 100: 1, is used in given a reaction vessel with a gas outlet. Nitrogen is introduced to keep the mixture in contact with air to prevent. It is heated to 120 ° C for 3 hours and then gradually further. Between At 160 ° and 170 ° C., the reaction mixture reacts violently with evolution of ammonia. During this Time, the temperature is not changed in order to inhibit the reaction. After the Ammonia development is further heated. The viscosity increases during the development of ammonia the reaction mass without it becoming solid. The reaction is still 4 hours at 250 ° C ao continued below 1 mm Hg to give a clear, colorless, molten product. the end Compacts produced with this product (diameter 3 to 5 mm, height 4 to 7 mm) can be removed easily spin the melt. In addition, the polymer product is temperature-resistant and can easily deform into films and other items; it has a melting point of 170 to 176 ° C and the density 0.97 to 1.020.

Claims (1)

Claim: Process for the production of polyureas by reaction of branched ω, ω'-diaminoalkylalkanes or their carbonates with ureas, characterized in that branched ω, ω'-diaminoalkylalkanes are used with 4 to 11 carbon atoms and with at least one branched alkyl chain with not more than 3 carbon atoms or their carbonates with urea, thiourea, methylenediurea, Using ethylene diurea, methylenedithiourea, or ethylene dithiourea a molar ratio of diamines to urea compounds of 1.01 to 1.02: 1 in an is implemented in a known manner. Considered publications:
U.S. Patent No. 2,145,242;
British Patent No. 530 267. 509 S08 / 386 2.65 © Bundesdruckerei Berlin