DE2066093C2 - Polymeric triketoimidazolidines - Google Patents

Description

where R is a hexamethylene radical, a D> cyclohexylmethane radical or denotes mixtures thereof, optionally in a mixture with a structural unit

/ \
-R ₁ -NN -

wherein Ri denotes a diphenylmethane radical or a diphenylether radical, the content of R residues are 99 to 20 mol% and the content of Ri residues is 1 to 80 mol%.

2. Polymeric triketoimidazolidines according to claim 1, characterized in that R and Ri in one Molar ratio of about 1: 1 are included.

The invention relates to polymeric triketoimidazolidines, which by the structural unit

Il c

-R ₁ -N
CO

Ν -
-C

in which R has the above meaning and Ri is a diphenylmethane or diphenylether radical, where the content of R radicals is 99 to 20 mol% and the content of Ri radicals is 1 to 80 mol%, Marked are.

The heterocyclic polymers according to the invention can be prepared by hydrolysis of polymeric precursors be prepared, which by reacting hydrogen cyanide with a diisocyanate or a Mixture of diisocyanates by reacting a dicyanoformamide or a mixture of dicyanoformamides with a diisocyanate or a mixture of diisocyanates or by polymerizing a cyanoformamidyl isocyanate be won. The heterocyclic polymeric precursors can by formula

- N

N -

in which X stands for NH or Ν ^θ and occupies the 4- or the 5-position.

The heterocyclic polymers of the present invention contain all regardless of the particular Method of obtaining the polymeric precursors, the following imidazolidine trione or triketoimidazoline ring:

- R —N

N -

in which R is a hexamethylene radical, a dicyclohexylmethane radical or mixtures thereof, or by a mixture of structural units

- R —N

N-

- N

Ν -
C.

55 The polymeric precursors prepared by any of the above processes can be hydrolyzed directly without being isolated, or they can be isolated and redissolved in a suitable solvent and then hydrolyzed to the poly (1,3-imidazolidinetrione) polymers of the present invention will.

A specific poly (1,3-imidazolidintrione) polymer, that by a specific process and / or from a specific diisocyanate or mixture of Diisocyanates made can be different from another polymer made by different processes and / or from another diisocyanate or mixture

derived from diisocyanates, within a wide range of chemical and physical Distinguish properties. These differences in chemical properties stem in part from the specific polymerization reaction, which leads to the recovery of the subsequently hydrolyzed polymers was used, as well as in part by the large number of diisocyanates, dicyanoformamides and cyanformamidyl isocyanates which can be used as starting materials. ι ο

The production of the polymeric precursors (the products that can be used without subsequent modification are) using cyanide ions as a catalyst is in patent application P 20 03 938.7 (DE-OS 20 03 938) described and claimed the method described there canoe for the production of Pre-products are used which are suitable for the production of the polymers according to the invention. The reaction to obtain the heterocyclic polymeric precursors, which lead to the invention Products that should be hydrolyzed can also be done with a base or an organometallic Compound instead of cyanide ion are catalyzed (Die Makromolekulare Chemie 78, 186, 1964). However can use a base or an organometallic compound as a catalyst for crosslinking and Gel formation if the reaction conditions are not controlled. The interlinked Reactions that can occur when using such a catalyst are explained below:

H

Cat.

- R-NCO + HCN-i ^^ - »_R_N - C - CN

R-N-C-CN + -R-NCO —R — N N — R—

- R —N N —R -

where R is an aliphatic or aromatic radical, a mixture of such radicals or a functionally substituted one Is a derivative of such radicals, provided that the functional group is not an isocyanate group reacted.

In the presence of a basic or organometallic catalyst, side reactions can easily occur enter. Such a side reaction, which occurs via the imino groups, leads to polymeric precursors with the following ring structure:

- Ν C.

Ν -
C.

60

65

in which X stands for = NH or = Ν ^Θ and is in the 4- or 5-position.

Bases which are sufficiently effective to accelerate all three reactions 4, 5 and 6 are tertiary nitrogen compounds that do not have an active hydrogen atom. A variety of connections catalyzes these reactions. These compounds include the tertiary nitrogen compounds, the none have active hydrogen atoms, including the tertiary amines, such as. B. triethylamine, triethylenediamine, 1 - aza-3,3,7,7-tetramethylbicyclo- (3.3.0) -octane, 1-methylpiperidine, N, N-dimethylaniline, N-methyldicyclohexylamine, Ν, Ν-dimethylcyclohexylamine, N-cyclohexylpiperidine and N-cyclohexylmorpholine; heterocyclic Bases such as pyridine, 2-picoline, 4-picoline, 3-picoline, 2,6-lutidine, 2,4-lutidine, and quinoline; Phosphorus compounds, such as triphenylphosphine and tributylphosphine; Tin compounds, such as dibutyltin dilaurate, dibutyltin diacetate, Bis (tributyltin) oxide, dibutyltin bis (2-ethylhexoate), dibutyltin bis (isooctyl maleate) and tetrabutyltin, and lead compounds such as trimethylplumbyl acetate and 1- (tri-n-butylplumbyl) imidazole.

Those formed under the catalysis of cyanide ions or a base q of the organometallic compound polymeric "precursors can be isolated by precipitation. Before the precipitation of the polymer

This precursor can be with a reactive compound such as an alcohol, a secondary amine or primary amine are treated, which react with the isocyanate end groups. This will make the Isocyanate groups effectively eliminated, so that no crosslinking as a result of reaction with the imino groups heterocyclic rings occurs.

The product can then be precipitated by placing the reaction solution in a reactive solvent such as Methanol, ethanol, propanol, dilute ammonium hydroxide, primary and secondary amines or water, or poured into a non-reactive solvent such as benzene, toluene or acetone. The reactive one Solvent reacts with the terminal isocyanal groups to form carbamates and ureas or amines, as a result of which further conversion and undesired side reactions are prevented. If precipitation occurs in a reactive solvent, a more stable polymeric precursor is obtained.

The heterocyclic polymers according to the invention contain the l.S-imidazolidine ^^. S-trione-l.S-diyl ring. The hydrolysis can be carried out in situ immediately after the formation of the precursors, but it can also be carried out, also in situ, after a reactive solvent has been added which reacts with the isocyanate end groups. In addition, any of the above can be used Methods formed polymeric precursors are precipitated in a reactive or non-reactive solvent and then either as a solid suspension or after redissolution in a suitable solvent be hydrolyzed.

The hydrolysis can be carried out by bringing the heterocyclic, polymeric precursor, characterized by the imino-1,3-imidazoiidindione rings, into contact with aqueous solutions of Brönsted acids, such as hydrochloric, hydrobromic, sulfuric, formic acid and the like or by adding anhydrous hydrogen chloride or hydrogen bromide or a salt of a very weak base to this polymer so that when the polymer is contacted or precipitated in water, hydrolysis of the imino groups to form the 13-imidazolidine-2,4 Desired polymer marked, 5-triton-1,3-diyl rings. When an aqueous solution of an acid is added to a solution of the heterocyclic polymer marked by 1,3-imidazolidinedione rings, the degree of hydrolysis used may Amount of acid can be controlled. Complete hydrolysis requires a molar amount of acid that is equal to the molar amount of ending up to nyiiroiyMci

inunogrüpperi is equivalent. the

Concentration of the acid solution is not important to the hydrolysis reaction. The heterocyclic polymers before and after hydrolysis are insoluble in water, and the heterocyclic polymeric precursors can be hydrolyzed in suspension or solution.

To overcome the heat of solution that occurs when the aqueous acid of the reaction solution or a solution of the redissolved in a solvent Imino-13-imidazolidin-dione polymer is added, can the aqueous acid first with the reaction solvent or the solvent in which the Polymers is redissolved, mixed and this mixture then added to the polymer solution. This premixing of acid and solvent allows the hydrolysis reaction to take place in a shorter time perform.

To avoid the precipitation caused by the addition of aqueous acids, the hydrolysis reaction can be used Perform in another way by taking anhydrous hydrogen chloride or hydrogen bromide blows through the solution to first form the acid salt of the polymer, and then precipitate in water to form the Complete hydrolysis. The acid salt of the one characterized by the imino-1,3-imidazolidinedione rings Polymer is soluble in dipolar aprotic solvents. Considerable heat build-up occurs when added anhydrous hydrogen chloride or hydrogen bromide to a dipolar aprotic solvent will. Therefore, in order not to have to cool the polymer solution during the hydrolysis, a solution can be used of anhydrous hydrogen chloride or hydrogen bromide in the solvent in the same manner as it has been described for the premixing of the aqueous acid, prepare it, cool it and then the stirred Add solution of polymer. Thereafter, the polymer undergoes hydrolysis during its precipitation Water completed. It has been found that when the hydrolysis is carried out using anhydrous hydrogen chloride or hydrogen bromide apparently a polymer with a higher bulk density and A more uniform particle size is produced than when aqueous acid solutions are used for the hydrolysis will.

The hydrolysis is rapid and can be completed within a few minutes at room temperature. The temperature for the hydrolysis is generally between 10 and 120 ^° C., preferably between 20 and 40 ^° C. The hydrolysis conditions can be maintained for a period of a few minutes up to several hours.

Crosslinked heterocyclic, polymeric precursors can by reacting with hydrogen cyanide Diisocyanates or by reacting dicyanoformamides with diisocyanates, in particular then when high temperatures (above 80 ° C) and basic catalysts in the introduction and Continuation of the polymerization reaction can be used. When networking while emerging the heterocyclic, polymeric precursors takes place with gel formation, a soluble polymer according to the invention obtained by acid hydrolysis of this crosslinked precursor with an excess of acid will.

The following examples serve to further illustrate the invention. In all examples, the basic molar viscosity (intrinsic) in dimethylformamide at 25 "C and the Eiger.viskcsität (inherent) at a Concentration of 0.5 g polymer per 100 ml dimethylformamide at 25 ° C determined unless otherwise is specified

example 1

A solution of 28 g of hydrogen cyanide in 168 g of N-methylpyrrolidone and 175 g of pure hexamethylene diisocyanate were simultaneously to 500 ml of N-methylpyrrolidone and 15 ml of the same solvent, saturated with sodium cyanide. The temperature rose 87 ° C After the reaction solution was cooled to 30 ° C, 24 g of triethylamine were added, and the Reaction solution was heated to 67 ° C. About 1 hour later, the reaction solution had reached 45 ° C cooled, and there were 100 ml of 37% aqueous Hydrochloric acid added dropwise. The temperature

never exceeded 53 ° C during hydrolysis.

The polymer was precipitated in water. It had an intrinsic viscosity of 0.24 and melted on 55 ° C; it can be characterized by the following structure:

O C.

- (CH ₂ ) ₆ -

The reaction was carried out in a dry flask under nitrogen. The temperature was maintained between 28-30 ° C during the addition, which took one hour. The reaction solution was then ^{heated to 35 °} C. and held there for 3 hours.

The reaction solution was slowly diluted with concentrated (43%) aqueous hydrochloric acid until a solid began to separate out of the solution. The reaction was exothermic. The solution was in ice and water cast to precipitate the hydrolyzed polymer, which had the following structural repeating units:

Example 2

A solution of 5 g of hydrogen cyanide in 150 ml of toluene became a solution of 50.4 g of hexamethylene diisocyanate in 150 ml of toluene containing 3 ml of dry pyridine at 7 ° C.

Then 1.5 g of triethylamine were added to the reaction solution, and further hydrogen cyanide, from 0.3 mol Sodium cyanide formed was passed through. The temperature rose spontaneously to 48 ° C, and so did the solution became viscous. Then 50 ml of methyl alcohol was added to the reaction solution, the one with the isocyanate end groups reacted to their further implementation with the imino groups on the imidazolidine rings block that would have resulted in a crosslinked polymer. It became an off-white product weighing 16 g Weight received. The polymer was soluble in chloroform, tetrahydrofuran, formic acid, pyridine, Dimethylformamide and dimethyl sulfoxide; it had an inherent viscosity of 0.11.

A portion of the polymer formed was mixed with 100 ml of concentrated (43%) aqueous hydrochloric acid to hydrolyze the imino groups on the product. The reaction was extremely exothermic and produced a white Product collected on a filter, suspended in acetone diluted with petroleum ether, filtered and dried. The product showed an infrared absorption maximum at 5.8 µ (broad). That Polymers was soluble in cold formic acid, dimethylformamide, hexamethylphosphoramide, and dimethyl sulfoxide; it was insoluble in cold and hot chloroform, acetone, methyl ethyl ketone, tetrahydrofuran, ethyl acetate and pyridine. It had an inherent viscosity of 0.08.

Example 3

A solution of 8.4 g (0.05 mol) of hexamethylene diisocyanate in 25 ml of dry N-methylpyrrolidone was dropwise to a solution of 11.1 g (0.05 mol) of hexamethylenedicyanformamide and 1 ml of triethylamine in Given 25 ml of dry N-methylpyrrolidone. the

- (CH ₂ ) ₆ -

2 ^r > After cleaning twice by dissolving it in dimethylformamide and precipitating it in water, the colorless polymer had an inherent viscosity of 0.14. The polymer was soluble in acetone, tetrahydrofuran, pyridine, dimethylformamide, dimethyl sulfoxide and He-

jo xamethylphosphoramide. The thermogravimetric analysis showed that it was stable ^{in nitrogen up to about 380 ° C.}

The hydrolyzed polymer of Examples 6 and 7 is characterized by the same formula above;

j5 is the chain length of the implementation of the Diisocyanate with hydrogen cyanide formed the same as that of the polymer formed by reaction of the Diisocyanate with its dicyanoformamide formed polymer, then the hydrolysis gives identical Polymers.

Example 4

3 ml of triethylamine were added to a solution of 15.2 g (0.05 mol) of diphenylmethanedicyanformamide and 8.4 g (0.05 mol) of hexamethylene diisocyanate in 60 ml of dimethylformamide. The temperature rose within 5 minutes from 27 ° C. to 56 ° C., and 30 minutes after the addition of the catalyst solution, the temperature had increased cooled to 37 ° C. The reaction solution became

-, ti then poured into toluene to precipitate the polymer. After washing with petroleum ether and drying, the polymer had an inherent viscosity of 0.18. The infrared spectrum showed absorption maxima at 3.06, 4.41, 5.56, 5.75 and 5.98 μ, which are for the putative structure are characteristic. The polymer is characterized by the following repeating structural units:

HN

Analysis:

Calculated for (C ₂₅ H ₂₄ N ₆ Oi) _n :

C 63.55; H 5.12; N 17.78;

Found:

C 63.25; H 5.27; N 17.64.

10 ml of 37% strength aqueous solution were slowly added to a solution of 4 g of the polymer in 40 ml of dimethyl sulfoxide Given hydrochloric acid. The product precipitated out of solution, slowly solidified and became crumbly. After this the reaction mixture was poured into ice water, it was filtered and washed with water until it was was neutral to pH paper. After drying, it weighed 3.5 g and had an inherent viscosity of 0.18.

Example 5

A solution of 55 g (0.22 mol) of diphenylmethane diisocyanate in 125 ml of N-methylpyrrolidone was added to a solution of 44.4 g (0.20 mol) of hexamethylenedicyanformamide and 2 ml of triethylamine in 150 ml of N-methylpyrrolidone in a dry nitrogen atmosphere. The addition required 1 hour and the temperature was maintained by a water bath at 25 -30 ⁰ C. After stirring for four hours, one half of the reaction solution was poured into toluene to precipitate 47 g of polymer which had an inherent viscosity of 0.70 in N-methylpyrrolidone (0.3 g / 100 ml) at 25 ° C. A film formed from this polymer had a tear strength to break of 851 kg / cm ² and a 1% Sekans modulus of 22,700 kg / cm ² .

One half of the solution of the polymer in N-methylpyrrolidone was diluted by slowly adding 60 ml of 37% strength aqueous hydrochloric acid. The product was poured into water, whereby 46 g of hydrolyzed polymer precipitated. The polymer had an inherent viscosity of 0.51 in N-methylpyrrolidone (0.5 g / 100 ml) at 25 ° C. The hydrolyzed polymer was pressed at 35O ⁰ C under a pressure of 20 tons to a clear film. The polymer had a tensile strength to break of 910 kg / cm ² and a 1% Sekans modulus of elasticity of 23,750 kg / cm ² . The clear film showed no weight loss in air or nitrogen at 350 ^° C. in the differential thermal analysis.

Example 6

1 ml of triethylamine was added to a solution of 22 g (0.01 mol) of hexamethylene dicyanoformamide and 2.5 g (0.01 mol) of diphenylmethane diisocyanate in 20 ml of dimethyl sulfoxide. After 2 hours the solution was poured into water, whereupon a white polymer was precipitated. It had a Eigenviskositat of 0.17 in dimethylformamide (0.5 g / 100 ml) at 25 ° C. The molecular weight determined by vapor phase osmometry in dimethylformamide at 100 ⁰ C was 1150. The nuclear magnetic resonance spectrum showed that only about half the expected

ίο imino groups were present. Half of the imino groups so had been hydrolyzed in water during the precipitation. The polymer formed at 205 ° C a clear, pliable film under a pressure of 10 tons.

The following examples illustrate the preparation of a number of different interpolymers. The copolymers can contain two or more different organic radicals in changing molar ratios contain. The organic groups can be used in the copolymers in concentrations of 1 to 80 Mol% are present.

Example 7

A solution of 64 g of hydrogen cyanide and 70 g of hexamethylene diisocyanate in 145 ml of N-methylpyrrolidone and a solution of 470 g of 4,4'-diphenylmethanedi-

jo isocyanate in 1000 ml of N-methylpyrrolidone were at the same time to 4000 ml of N-methylpyrrolidone, the 25 ml of the same solvent saturated with sodium cyanide were added. The temperature reached 53 ° C during the 8 minute addition.

J5 During the next 2 hours the reaction solution slowly cooled to 38 ° C. Then 24 g Triethylamine added. The temperature was raised to 58 ° C. and held there for 1 hour. These additional heat was applied to the formation

w to ensure the heterocyclic rings. It was then cooled to 32 ° C. and 240 ml of 37% hydrochloric acid was added dropwise to hydrolyze the imino groups on the heterocyclic rings.

The product was precipitated in water. The almost λ white product weighed 590 g and had an intrinsic viscosity of 0.35. The polymer melted at 247 ⁰ C and is characterized by the following recurring structural units, which are represented in the polymer chain in the specified proportions:

0.8 η

Analysis: Calculated C 6636; H 4.00; Found: C 67.05; H 4.07;

N 10.71; N 10.64.

Example 8

A solution of 613 g of hydrogen cyanide in 160 ml of N-methylpyrrolidone and a solution of 454 g of 4,4'-Diphenylmethyküisocyanat and 76ß g of hexamethyl

Lene diisocyanate in 1000 ml of N-methylpyrrolidone were at the same time to 2000 ml of N-methylpyrrolidone, the 25 ml of a solution saturated with sodium cyanide in the same Solvent contained, given. After 2 hours, 23 g of triethylamine were added, and the solution was stirred for a further 2 hours. Then 230 ml of 37% aqueous hydrochloric acid were added dropwise added at a temperature of 44-50 ° C. The product was precipitated in water. It weighed 576 g and had an intrinsic viscosity of 0.57. The polymer melted at 247 ° C and can by a structural formula similar to that of the product of Example 11, with the difference that the repeating structural units, as shown by calorimetric differential measurements, are more irregular were distributed.

Analysis:

Calculated for (

C 66.96; H 4.00;

Found:

C 66.71; H 3.82;

N 10.71;
N 10.68.

Example 9

A solution of 56 g of hydrogen cyanide in 158 ml of N-methylpyrrolidone and a solution of 261 g 4,4'-Diphenylether diisocyanate and 174 g of hexamethylene diisocyanate in 900 ml of N-methylpyrrolidone were at the same time to 4000 ml of N-methylpyrrolidone, the 25 ml of a solution saturated with sodium cyanide in the same Solvent contained, given. The temperature rose to 52 ° C. Then 21 g of triethylamine were Reaction solution added. The temperature was maintained at 43-48 ° C. The irregular polymer was precipitated in water. The dry product weighed 475 g, had an intrinsic viscosity of 0.36 and melted at 178 ° C.

Example 10

A solution of 58 g of hydrogen cyanide in 150 g of N-methylpyrrolidone and a solution of 271 g of diphenyl ether diisocyanate and 181 g of hexamethylene diisocyanate in 900 ml of N-methylpyrrolidone were added simultaneously to 500 ml of N-methylpyrrolidone, which contained 25 ml of a solution saturated with sodium cyanide in the same solvent . 22 g of triethylamine were then added. The reaction mixture was heated and stirred at 65 ° C. for 2 hours. Thereafter, 200 ml of 37% aqueous hydrochloric acid was added dropwise. The temperature was maintained at 44-55 ° C during the addition. Then 1000 ml of solvent was added to dilute the solution. The product was precipitated in water. The dry, irregular mixed polymer weighed 486 g, had an intrinsic viscosity of 047 and melted at 178 ° C

methylene diisocyanate ir 900 ml of N-methylpyrrolidone and 25 ml of N-methylpyrrolidone saturated with sodium cyanide. The temperature rose from 24 to 113 ° C. The very viscous reaction solution was diluted with 2200 ml of N-methylpyrrolidone. Then 27 g of triethylamine were added. After the reaction solution had cooled to 42 ° C., 270 ml of 37% hydrochloric acid were added added slowly, maintaining the temperature at 42-47 ° C. The polymer was in water failed. After drying, it weighed 585 g, had an inherent viscosity of 0.70 and melted at 180 ° C.

Example 12

A solution of 66 g of hydrogen cyanide in 157 ml N-methylpyrrolidone and a solution of 307 g of hexamethylene diisocyanate and 152 g of diphenylmethane diisocyanate in 1000 ml of N-methylpyrrolidone were simultaneously to 500 ml of N-methylpyrrolidone and 25 ml of the same solvent, saturated with sodium cyanide. The temperature rose to 85 ° C, and a further 600 ml of N-methylpyrrolidone were added to the very viscous solution. Then 48 g of triethylamine were and later 500 ml of further solvent added to the solution for hydrolysis dilute. Then 250 ml of 37% hydrochloric acid were slowly added to the reaction solution, the Temperature between 40 and 45 ° C was maintained.

The interpolymer was precipitated in water. The dry product had an inherent viscosity of 0.45 and melted at 111 ° C.

Example 11

A solution of 72 g of hydrogen cyanide in 148 ml of N-methylpyrrolidone was mixed with a solution of 334 g of diphenylmethane diisocyanate and 225 g of hexa-

Example 13

A solution of 58.8 g of hydrogen cyanide in 158 ml of N-methylpyrrolidone and a solution of 275 g of hexamethylene diisocyanate and 137 g of diphenyl ether diisocyanate in 1000 ml of N-methylpyrrolidone were added to 100 ml of N-methylpyrrolidone and 25 ml of this solvent saturated with sodium cyanide. The temperature rose to 86 ⁰ C. After addition of 44 g of triethylamine, the reaction solution with 600 ml N-methylpyrrolidone was diluted Thereafter, 230 ml 37% hydrochloric acid was slowly added at a temperature of 30-45 ° C

The product was precipitated in water. The dry polymer had an inherent viscosity of 0.98 and melted at 118 ° C.

The following examples show that a characterized by the iminoimidazolidinedione rings, heterocyclic, polymer precursor dissolved again and into a polymer according to the present invention Invention can be hydrolyzed.

Example 14

100 g of poly (hexamethylene-4-imino-13-imidazolidine- 2 ^ -dione-13-diyl), which had been prepared by reacting hydrogen cyanide with hexamethylene diisocyanate in the presence of added cyanide ions and had a molecular weight of 0.21, was dissolved in 1500 ml of N-methyl pyrrolidone Then <" 50 ml of 37% hydrochloric acid was added dropwise .

The reaction solution was poured into water to precipitate poly (hexamethylene-13-imida ^ ulidintrion-13-diyl). This had an intrinsic viscosity of 0.19 and melted; 55 ⁰ C. The polymeric preliminary product,

which has been hydrolyzed and the hydrolyzed polymer according to the invention are represented by those in the following The structures shown in the reaction equation are:

O C.

C C

NH

Il c

- (CH ₂ ),; -

The polymer formed had the same structure as the polymer prepared in Example 2.

In the above examples, aqueous hydrochloric acid was used for the hydrolysis, but the Hydrolysis can also be carried out by other methods, as the examples below show.

25th

Example 15

A solution of 54.3 g of hydrogen cyanide in 175 ml of N-methylpyrrolidone and a solution of 524 g 4,4'-methylenebis (cyclohexyl isocyanate) in 800 ml of N-methylpyrrolidone became 1000 ml of N-methylpyrrolidone and 25 ml of the solvent, saturated with sodium cyanide, are added. The temperature rose to 70 ° C. Later 20 g of triethylamine were added. After stirring for 90 minutes, the viscous solution was 2000 ml Diluted solvent. Thereafter, 200 ml of 30% strength aqueous sulfuric acid were slowly added to the reaction solution added.

The polymer was precipitated in water. After drying it melted at 228 ° C. This example shows that other acids than hydrochloric acid can be used for the hydrolysis.

Example 16

A polymer was prepared by reacting 36.6 g of hydrogen cyanide with a mixture of 182 g of hexamethylene diisocyanate and 68 g of 4,4-Diphenyläthei diisocyanate in 2200 ml of N-methylpyrrolidone by the method of Example 19. The polymer was hydrolyzed by adding a solution of 150 ml of 37% hydrochloric acid in 300 ml of N-methylpyrrolidone. The addition required only 15 minutes, and the temperature of the reaction solution rose from 45 to 50 ^° C.

The product was precipitated in water and obtained as a colorless polymer, which at the same bo Temperature as the polymer of Example 19 melted (118 ° C). It had an inherent viscosity of 0.28.

This example shows that a solution of hydrochloric acid in N-methylpyrrolidone with subsequent precipitation in water can also be used instead of aqueous HCl _b 5.

From the foregoing it is evident that, according to this invention, completely new heterocyclic Polymers are obtained, depending on their exact composition and their molecular weight have very different properties, which make them suitable for a wide range of uses do. The polymers according to the invention are useful for the production of films, fibers, foams, Moldings and the like films made from the polymers according to the invention can be cast from solutions or be molded under heat and pressure. The polymers are also used for laminates and for making electrical Suitable for isolators. Their high heat resistance allows them to be used at high temperatures.

The polymers have adhesive properties to glass and metal and show good toughness and Bond strength when used as adhesives in the manufacture of laminates.

The polymers can also be cast into films from their solutions, and fibers can be made from them can be prepared by extruding the polymers into a precipitation bath. Coatings and fibers can also be obtained from the polymers by hot melt processes.

Some of the polymers can easily be formed into precisely dimensioned, smooth moldings when heated of high heat resistance and good mechanical strength.

The heat-resistant polymers can be used as components in circuit breakers, wire and cable insulation, Sockets, laminated electrical components, television components, circuit carriers, instrument housings, Movie projector parts, tool housings, engine housings, fuel canisters and tank liners as well as in high temperature laminates and other high temperature applications. aside from that They can be used as an insulating varnish for wires motors, electrical equipment and transformers be used. The polymers can also be used as high-frequency capacitors and as interlayer insulation be used in transformer coils

The polymers of the invention are solids at room temperature. Their melting point is between 55 ° C and 300 "C. Mixed polymers according to the invention can be produced whose melting points is within a predetermined range. The desired melting point is within that given above The range is set by varying the molar ratio of the monomers used to one another will. The melting point of a mixed polymer lies: almost exactly between the melting points of the homopoly polymers from the individual monomers.

Test report

For the purpose of comparing the polymers known from FR-PS 20 05 695 with the bean example according to the invention 1 of FR-PS 20 05 695

(Experiment E 0775-56)
The procedure is generalized by the following

The examples of FR-PS 5 reactions C and D were used to achieve the desired polymers

20 05 695 reworked

Product:

H ₃ N-

-CH ₂ -

-NH ₂

HOO

N-C-C-OEt + 2EtOH

VN-C-C-OEt + OCN ^ f "^

(D)

The procedure corresponded to the procedure described in the French patent specification, however half of the amounts specified there were used.

The apparatus used consisted of a two liter, three necked round bottom flask equipped with a stirrer, nitrogen inlet tube, thermometer and a 38 cm high Vigreaux distillation column and condenser. In the presence of dry nitrogen, 198 g of 4,4'-methylenedianiline and 730 g of diethyl oxalate were mixed. The solution was stirred and heated at 135-140 ° C for 2 hours. During this time, 92 ml of ethyl alcohol were distilled off. The temperature was raised to 200 ⁰ C, and excess diethyl oxalate was removed by distillation. Finally, vacuum was applied for about 10 minutes to remove the last traces of diethyl oxalate and ethyl alcohol from the bis (ethyl oxamate).

Then 250 ml of freshly distilled, anhydrous cresol and 257.5 g of diphenylmethane-4,4'-diisocyanate were added added to the hot melt. The mixture was stirred for 24 hours while maintaining the temperature at 20 ° -210 ° C. While during this time a further 400 ml of dry cresol were added. The dark brown reaction mixture was Poured into shallow bowls to cool. A viscous mass with the consistency of hardness formed Road tar. Part of the mass was broken into a powder in ethyl alcohol.

The product had a relative viscosity of 1.24 (1.0 g in 100 ml of phenol-1,1,2,2-tetrachloroethane - 60: 40% by weight - at 25 ° C).

Example 3 of FR-PS 20 05 695
(Experiment E-0775-62)

Example 1 described above was repeated using N-methylpyrrolidone as the solvent in place of cresol. The reactions were the same as described as C and D above.
The bis (ethyloxamate) was prepared as in

s> Experiment E-0775-56 described prepared. The molten product was diluted with 250 ml of N-methylpyrrolidone. Subsequently, 257.5 g of diphenylmethane-4,4'-diisocyanate were added and the solution was stirred for 24 hours at 200-208 ⁰ C. During this time, 100 ml of condensate (mostly ethyl alcohol) were collected and a further 400 ml of N-methylpyrrolidone were added to the reaction mixture. About half of the dark brown reaction solution was poured into water to precipitate the product. The other half of the reaction solution was used in the procedure described below as Experiment E-0775-63. The solid product had a relative viscosity of 1.27 (Ig product in 100 ml phenol / 1,1,2,2-tetrachloroethane-60: 40% by weight

w 25 ° C). A portion of the solid was dissolved in N-methylpyrrolidone dissolved and poured into acetone to reprecipitate the polymer. This turned it into acetone Soluble low molecular weight material is eliminated and the relative viscosity of the product is increased 1.33 increased.

(Experiment E-0775-63)

μ The second half of the reaction solution obtained above in experiment E-0775-62 was admixed with a few drops of water ^{while it was being stirred and heated to 200-205 D C.} It was 1 hour in the presence of refluxing water under re-

b5 river heated. Then the viscous, dark brown Reaction solution in a Waring mixer poured into excess water to make a brown To precipitate powder. The relative viscosity was 1.40

17 18

(1.0 g of polymer in 100 ml of the phenol / tetrachoroethane solution described in experiment E-0775-62 at 25 ° C.).

Properties of the products produced according to the experiments described above and comparison

this with products according to the invention.

solubility

The solubilities of the products in various solvents were determined by each about 0.1 g of product was added to every 5 ml of solvent. The solubilities are at 25'C If the solid is determined after 15-18 hours did not dissolve, was heated to the boiling point of the solvent. If it then dissolved, the solution became chilled to see if precipitation has occurred. The results obtained from these investigations show that the products according to FR-PS 20 05 695, as they were prepared above, and the Products according to the invention have different solubilities in different solvents. There are significant differences in the solubility of the products in cresol, dimethylformamide, Cyclohexanone and the solution of 60 wt .-% phenol and 40 wt .-% 1,1,2,2-tetrachloroethane.

Since the relative viscosities of the prepared according to the experiments described above Products are relatively low (see Table I), their insolubilities in various solvents are not attributed to effects of the high molecular weight, but must be due to differences in the Molecular structure can be traced back.

Film properties

None of the products made according to the experiments described above yielded self-supporting films when made from N-methylpyrrolidone solutions were poured. The films formed were too brittle to remove from the plate on which they were cast were to be replaced. In contrast, the polymers according to the invention, as from the attached Table I shows films with excellent mechanical properties.

Thermogravimetric analyzes

The thermogravimetric analyzes were carried out on a Dupont instrument, model 990, for thermogravimetric Analyzes (TGA) carried out, with a heating rate of 10 ° C per minute in one Nitrogen atmosphere was applied. The results obtained from the thermogravimetric analyzes are from the accompanying curves (Figs. 1-5) as well as from the attached table II. The thermogravimetric analysis of the products curves obtained from experiments E-0775-56 and -62A

40 show that the products lose at a much lower temperature (300-325 ⁰ C) than the products of this invention catastrophic weight.

Reprecipitate E-0775-62A by mixing an N-methylpyrrolidone solution of the product with it Acetone removed some of the low molecular weight materials soluble in acetone; H. highly volatile impurities, but did not lead to an increase in the overall stability of the product.

Table I.

Polymers Film properties "inh. "rrl. Tf)
⁰ C T _B )
kg / cm ² £ - ^c )
% train
module train
strength
kg / cm ² colour Structure*) Mole
behaves
nis 0.24 1.127 55 387 25-50 450 color
Come on R ₁ = R ₂ = (CH ₂ J ₆
(Example 1) 1/1 0.33 236 770 11.3 22050 763 yellow R, = R ₂ = methyl
lenbis- (cyclohexyl)
(Example 15) 1/1 0.57 1.330 247 882 12-13 amber Rl = diphenylmethane 4/1 0.85
0.44 1.530
1.246 169
111 903
805 7-12
4.2 yellow
bright R ₂ = - (CH ₂ J ₆
(Example 8) 1/1
1/3 green 0.44 1.246 239 1036 9-10 amber R1 = diphenyl ether 3/1 0.61 1.357 169 896 11-12 yellow R ₂ = (CH ₂ ) ,, 1/1 0.9 1,568 108 763 5-6 bright- 1/3

continuation

19th

20th

Polymers
Structure*)

Film properties

Mol- / 7, " _Ä

relationship

Tg>) ° C

Tb ) kg / cm-

Tensile module

Train color

strength

kg / cm ²

Ri = R ₂ = diphenylmethane according to experiment:

E-0775-56 1/1

E-0775-62
E-0775-62
E-0775-63
Explanations for Table I.

0.215 1.24 0.239 1.27 0.285 1.33 0.336 1.4

*) T, = glass transition temperature

^b ) T ° _B = tear strength

^c ) £,% = elongation at break

/, "/, U. Ι," ι - Inherent and relative viscosity of the poly (parabanic acids) in dimethylformamide at 25 ° C. and a concentration of 0.5 g of polymer per 100 ml.

Table II Structure*) 0 O Thermogravi- Weight Polymer Λ Α metric analysis loss -R ₁ -NNR ₂ N Mole from at J y J behaves 10% at game O OO nis ⁰ C **) R ₁ = R ₂ = (CH ₂ J ₆ R, / R ₂ 405 R ₁ = R ₂ = (CH ₂ J ₆ 400 Ri = (CH ₂ J ₆ 1/1 380 1 R ₂ = diphenylmethane 1/1 2 Ri = (CH ₂ J ₆ 1/1 385 4th R ₂ = diphenylmethane R ₁ = (CH ₂ J ₆ 1/4 400 7th R ₂ = diphenyl ether R ₁ = (CH ₂ J ₆ 1/1 410 9 R ₂ = diphenyl ether R, = R ₂ = methylene 3/1 400 13th bis (cyclohexyl) Explanations for Table II 4/1 15th ♦) N
I. O

**) Temperature at which the polymer loses 10% of its weight when it is ^{heated in a nitrogen atmosphere at a rate of 10 °} C. per minute.

For this purpose 4 sheets of drawings

Claims (1)

Patent claims: 1. Polymeric triketoimidazolidines, labeled through the following structural units: _r— N -