DE1220132B - Process for the production of nitrogen-containing polyadducts - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C08g

German class: 39 c -15

Number: 1 220 132

File number: F 42586IV d / 39 c

Filing date: April 10, 1964

Opening day: June 30, 1966

It has been found that valuable nitrogen-containing polyadducts are obtained when organic Cyanic acid esters of the general formula

R (OCN) ₁₅

in which R is an aromatic or araliphatic hydrocarbon radical, optionally interrupted by heteroatoms or keto groups, and χ is an integer from 1 to 6, with polyvalent primary or secondary amines, which may contain halogen atoms, sulfonic acid residues or keto groups and whose hydrocarbon structure is optionally interrupted by heteroatoms, implements.

The following can be used as polyvalent cyanic acid esters, for example:

1,3- or 1,4-dicyanatobenzene; 1,3- or 1,4- or 1,5- or 1,6- or 1,7- or 1,8- or 2,6- or 2,7-dicyanatonaphthalene; 1,4- or 1,5-dicyanatoanthraquinone; 1,3,5-tricyenatobenzene; 1,3,5- or 1,3,6- or 1,3,7-tricyanatonaphthalene; 2,2 'or 3,3'- or 4,4'-dicyanatodiphenyl, 2,2'- or 4,4'-dicyanatodinaphthyl- (l, l '), l-methylO.S-dicyanatobenzene; 1-methyl-2,5-dicyanatobenzene; 4-acetyl-1,3-dicyanatobenzene; 4,4'-dicyanatodiphenylmethane;

4,4'-dicyanatodiphenylmethyl methane; 4,4'-dicyanatodiphenyldimethyl methane; 1,1-bis (4-cyanatophenyl) cyclohexane; 2,2'-dicyanatodinaphthyl- (l, l ') ^-met h ^an I 4,4'-dicyanatodiphenylethane;4,4'-dicyanatostilbene;4,4'-dicyanatodiphenylether;4,4'-dicyanatobenzophenone; 4,4 "-dicyanatodiphenyl sulfone.

Mixtures of polyvalent cyanates can also be used.

The polyvalent cyanic acid esters can be prepared from the corresponding phenols with cyanogen halide in the presence of a base at temperatures up to 65 ^° C. according to older proposals (e.g. German patent specification 1 195 764, French patent specification 1 389 079, German Auslegeschrift 1 201 839).

As polyvalent primary or secondary amines, which optionally contain halogen atoms, sulfonic acid residues or contain keto groups and their hydrocarbon structure is optionally interrupted by heteroatoms can be aliphatic, cycloaliphatic, araliphatic, aromatic, heterocyclic or cyclic amines in question.

The following amines may be mentioned as examples: 1,2-diaminoethane; 1,2- or 1,3-diaminopropane; 1,2- or 1,3- or 1,4- or 2,3-diaminobutane; 1,2- or 1,3- or 1,4- or 1,5- or 2,3- of 2,4-diamifiopentane, the corresponding diaminohexanes, -heptanes, -octanes, -nonanes, -decanes, -undecanes, Process for the production of nitrogenous
Polyadducts

Applicant:

Paint factories Bayer Aktiengesellschaft,

Leverkusen

Named as inventor:

Dr. Hans-Dieter Schminke, Cologne-Mülheim;
Dr. Wilhelm Göbel, Cologne-Flittard;
Dr. Ernst Grigat, Cologne-Stammheim

-dodecane, -hexadecane, -octadecane, 1,4-diaminobutene, 1,4-diamino-2-methylbutane, 1,5-diamino-2,2-dimethylpentane; 1,5-diamino-2,2,4-trimethylpentane; Di- (j3-aminoethyl) thioether; Di (γ-aminopropyl) ether; Di (γ-aminopropyl) thioether; Butylene glycol dipropyl ether-ß), cü'-diamine; Di (co-aminohexyl) thioether; Bis (2-aminoethyl) amine; Dipropylene (1,2) triamine; Tripropylene- (1,2) -tetramine; Bis (3-aminopropyl) amine; Bis (3-aminopropyl) methylamine; Ν, Ν'-dimethyldiaminoethane -1.2; N, N '- diethyldiaminoethane -1.2; 1-amino-3-methylaminopropane; Piperazine; N-2-aminoethyl piperazine; 4-aminopiperidine; ω, ω'-diamino-1 ^ 3- (or -1, 4) -dimethylbenzene; ct>, a / -Diamino-l, 4- (or 1,2) -dimethylcyclohexane; co, C (> '- diamino-1,4-diethylbenzene; co, co'-diamino-l, 4- (or -l, 5) -dimethylnaphthalene, ω, ω'-diamino-di-n-propylbiphenyl; 1.2- or 1,3- or 1,4-diammocyclohexane; 1-methyl

2,4-diaminocyclohexane; 1-ethyl-2,4-diaminocyclohexane; 4,4'-diaminodicyclohexyl methane; 4,4'-diaminodicyclohexylmethyl methane; 4,4'-diaminodicyclohexyldimethyl methane; 4,4'-diamino-2,2'-dimethyldicyclohexylmethane;4,4'-diamino-3,3'-dimethyldicyclohexylmethane;4-aminobenzylamine; 2- (4'-aminophenyl) -1-aminoethane; 1- (3'-aminophenyl) -l-aminoethane; 3- (3'- or 4'-aminophenyl) -1-aminopropane; 3- (3'- or 4'-aminophenyl) -l-aminobutane; Tetrahydronaphthylenediamine-1,5 or -1 _S 4; Hexyhydrobenzidine-4,4'-diamine;Hexahydrodiphenylmethane-4,4'-diamine; 1,2-, 1,3-, 1,4-diaminobenzene; 1-methyl-2,4- (or 2,3- or 3,4- or 2,6- or 2,5- or 3,5) -diaminobenzene; 1,3-dimethyl-2,4- (or -4,6) -diaminobenzene; 1,4 - dimethyl - 2,5 - diaminobenzene; 1-ethyl-2,4-diaminobenzene; l-isopropyl ^^ - diaminobenzene; Diamino diethylbenzene; Diisopropyl diaminobenzene; l-chloro-2,4-diaminobenzene; * 1,3-dichloro

609 587/447

2,4- (or -4,6) -diaminobenzene, 1,4-dichloro-2,5-diaminobenzene; 4,4'-diaminoazobenzene, 4,4'-diaminobenzolazonaphthalene, 2,4- (or -4,4 ') -diaminodiphenyl ether, ethylene glycol diphenyl ether-2,2'-diamine; Diethylene glycol diphenyl ether - 2,2'-diamine; N, N'-dimethylphenylenediamine-1,3 or -1,4; N-methylphenylenediamine-1,4; 1,3- or 1,4- or 1,5- or 1,6- or 1,7- or 1,8- or 2,6- or 2,7-naphthylenediamine; 1,1'-dinaphthyl-2,2'-diamine;4,4'-diaminodiphenylamine;4,4'-diaminodiphenylamine sulfonic acid- (2), 2,4'- or 4,4'-diaminodiphenyl;3,3'-dimethyl-4,4'-diaminodiphenyl; 2,2- or 3,3'-dichloro-4,4'-diaminodiphenyl;2,4,4'-triaminodiphenyl;4,4'-diaminodiphenylmethane;4,4'-diaminodiphenylmethylmethane;4,4'-diaminodiphenyldimethylmethane;2,2'-dimethyl-4,4'-diaminodiphenylmethane, 2,5,2 ', 5'-tetramethyl-4,4'-diaminodiphenylmethane; 1,1-di (4'-aminophenyl) cyclohexane; 1,1-di (4'-amino-3'-methylphenyl) cyclohexane; 3,3'-diaminobenzophenone;2,4-diaminodiphenylethane-1,2; 4,4 ', 4 "-triaminotriphenylmethane;4,4'-diamino-2,2',5,5'-tetramethyltriphenylmethane;4,4'-diamino-2,2 \ 5,5'-tetramethyl-2"-chlorotriphenylmethane; fluorenediamine-ljV ^ o-diaminoanthraquinone; 9-ethylcarbazole-3,6-diamine; pyrene-3,8-diamine; chrysene-2,8-diamine; benzidine-4,4'-diamine; diphenyl sulfide-2, 4-diamine; diphenyl disulfide-4,4'-diamine;diphenylsulfon-4,4'-diamine;diphenylmethanesulfon-4,4'-diamine; 4-methyl-3-aminobenzenesulfonic acid- (4'-aminophenyl) - ester ; 4 - methyl - 3 - aminobenzenesulfonic acid-4'-amino _T 3'-methylanilide; di- (4-aminobenzenesulfonyl) ethylenediamine-3,3'-dimethoxy-4,4'-di-aminodibenzylthiether, 4,4 '-Dimethoxy-3,3'-diaminobenzenethioethyleneglycol;3,3'-dimethoxy-4,4'-diaminodibenzylsulfone; 1 - methyl - 2,4,6 - triaminobenzene; 1; 3,5-trimethyl-2,4,6 -triaminobenzene; 1,3,7-triaminonaphthalene; 2,4,4'-triamino-diphenylmethane;3-methyl-4,6-4'-triaminodiphenylmethane;4,4'-dimethyl-2,2', 5.5 '-tetraaminodiphenylmethane; melamine.

Polyethers with amino end groups can also be used, as can polyesters, polyester amides or polyamides with these end groups.
Mixtures of polyvalent ones can also be used

ίο amines are used.

The reaction is expediently carried out in such a way that the polyvalent cyanic acid esters and the polyvalent ones Amines, preferably in a solvent, combined. You react without adding anything else

Matter with each other. In most cases, the reaction occurs at room temperature or even below, for example at 0 ^° C. In other cases, a temperature increase of up to 100 ° C can be advantageous.

As a solvent, for. B. aliphatic and aromatic, optionally halogenated or nitrated Hydrocarbons such as benzene, toluene, chlorobenzene, nitrobenzene, ligroin, chloroform, carbon tetrachloride, Nitromethane as well as esters and

Amides, e.g. B. ethyl acetate, dimethylformamide; Ketones e.g. B. acetone, methyl ethyl ketone; Ether, e.g. B. Diethyl ether, dioxane, diethylene glycol mono- (or di) ethyl ether; Alcohols e.g. B. methanol, ethanol, Isopropanol; Nitriles, e.g. B. acetonitrile or dimethyl

sulfoxide. . '

In the reaction according to the invention, the components are linked to form higher molecular weights Plastic bodies via isourea ether groups

—R — N-

MR')

(R ')
H

NH NH

ι;

C-O-Ar-O-C-N-R-N

MR')

NH

- C — O -

a. Such compounds are not yet known. When using bifunctional raw materials one linear products, while with the use or concomitant use of tri- and multifunctional amines or / and trifunctional and polyfunctional cyanates crosslinked plastics are obtained.

In general, the components are used in equivalent amounts. However, it can also use the Cyanate component can be used in excess if the end product contains free cyanate groups should, the amine component can be used in excess if there are free amino groups in the end product are desired.

The isolation of the end products can, in cases where the product fails, by suction, in other cases can be done by pouring the reaction solution into a solvent in which the end product is insoluble, so it precipitates and can be suctioned off. There are z. B. water, methanol, ethanol called. It is also possible to remove the solvent. If the product contains sulfonic acid groups, after pouring the reaction solution into water, it can be obtained by salting out.

The plastics obtained by the process according to the invention can be according to known, on the Plastics sector generally used deformation methods for a wide variety of everyday objects process with valuable physical and chemical properties.

You can z. B. knead, roll, press using higher temperatures and pressures or spray and deliver shaped structures of various kinds. But there is also the possibility of their processing from solutions, in particular into lacquer coatings, films and foils. These substances can be used on their own or with a wide variety of additives, such as z. B. plasticizers, fillers, pigments, antistatic substances, flame retardants and polymeric compounds are processed.

They can also be made with wood flour, natural and synthetic fibers and fabrics as well as with carbon black, including conductivity carbon black.

The unmodified plastics produced according to the invention deliver after the optionally below Curing of highly cross-linked, crystal-clear plastics with a very hard surface. They show very good adhesion to metal, wood, glass and plastics and have a very good chemical resistance. By incorporating the substances listed

they offer a range of properties that is varied in the most diverse ways.

example 1

To a solution of 8.6 g of piperazine in 100 ml of dimethylformamide is added dropwise at 60 ⁰ C in the course of 15 minutes a solution of 28 g of 4,4'-Dicyanatodiphenyldimethylmethan in 100 ml of dimethylformamide. The mixture is stirred for 10 minutes, then the clear solution is poured into 1 liter of water. The white precipitate is filtered off with suction, washed with water and dried in a drying cabinet. Yield 33.7g. Mp 120 to 13O ⁰ C. molecular weight (in chloroform). 1050th

The IR spectrum shows that for the isourea ether grouping characteristic band at 6.1 μ.

The solvent and the remaining viscous residue can also be distilled off in vacuo crystallize by rubbing with water.

Are obtained analogously from 14 g of 4,4'-Dicyanatodiphenyldimethylmethan and 4.3 g of piperazine with the use of dioxane as the solvent 16.3 g of a product of melting point 13O ⁰ C.

Example 2

8.6 g of piperazine are dissolved in 100 ml of acetone. For this purpose one drips at the boiling point within A solution of 16 g of 1,4-dicyanatobenzene in 100 ml of acetone for 30 minutes. A white one falls immediately granular precipitate. The mixture is stirred for 30 minutes, filtered off with suction and washed with acetone. yield 18.2 g. Mp. 109 to 111 ° C.

If chloroform is used as the solvent, 8 g of 1,4-dicyanatobenzene and 4.3 g of piperazine 10 g of a yellowish product with a melting point of 132 to 133 ° C.

Example 3

8.6 g of piperazine are dissolved in 100 ml of dimethylformamide and heated to 60 ⁰ C. A solution of 16 g of 1,3-dicyanatobenzene in 100 ml of dimethylformamide is added dropwise to this. After stirring for 15 minutes, the solution is poured into 1 liter of water, filtered off with suction and washed with water. Yield 10g. Mp. 103 to 130 ^° C.

Example 4

Dissolve 4.3 g of piperazine in 100 ml of dimethylformamide and heated to 90 ⁰ C. In the course of 45 minutes to 10.5 g of solid transmits naphthylene-1,5-biscyanat and stirred at the same temperature for a further 30 minutes. The undissolved material is filtered off and the solution is allowed to run into 1 liter of water. After suctioning off, washing and drying, 9 g of a product which ^{melts at 107 °} C. are obtained.

Example 5

To a solution of 11.6 g of hexamethylenediamine in 100 ml of acetone are added dropwise within 20 minutes at 20 to 25 ⁰ C a solution of 28 g of 4,4'-Dicyanatodiphenyldimethylmethan in 100 ml of acetone. The precipitated product is filtered off with suction, washed several times and dried. Yield 31.5g. Melting point 80 ° C.

Example 6

Analogously to Example 5, from 28 g of 4,4'-Dicyanatodiphenyldimethylmethan and 6 g of ethylenediamine, 18.5 g of a product which begins to melt at 48 ⁰ C.

Example 7

Dissolve 86 g of piperazine and 116 g of hexamethylenediamine in 21 dimethylformamide and leave this in A solution of 560 g of 4,4'-dicyanatodiphenyldimethylmethane over the course of 70 minutes at room temperature add dropwise in 1.21 dimethylformamide. The ίο filtered solution is poured into water and sucks off the colorless precipitate. Yield 573g. Mp. 110 ° C.

Example 8

11.2 g of hexahydro-l, 4-phenylenediamine are dissolved in 100 ml of dimethylformamide and heated to 6O ⁰ C. A solution of 28 g of 4,4'-dicyanatodiphenyldimethylmethane in 100 ml of dimethylformamide is added dropwise over the course of 30 minutes, the mixture is stirred for a further 30 minutes and the solution is poured into 11% of water with vigorous stirring. The dry product begins to melt at 98 ^0C. Yield 36 g.

Example 9

Analogously to Example 8, 4,4'-dicyanatodiphenyldimethylmethane is obtained from 28 g and 11 g of p-phenylenediamine 37 g of a product with a melting point of 125 ° C.

B e i s ρ i e 1 10

To a solution of 11.3 g of 4,4'-Diaminodiphenyldimethylmethan in 50 ml of dimethylformamide is added dropwise at 20 to 25 ⁰ C a solution of 14 g of 4,4'-Dicyanatodiphenyldimethylmethan in 50 ml of dimethylformamide. The mixture is left to stir for 30 minutes and the solution is then poured into 1 liter of water. The precipitated product is filtered off with suction, washed with water and dried. Yield 23.5g. Melting point 125 ⁰ C.

B e i s ρ i e 1 11

Analogously to Example 10, 4,4'-dicyanatodiphenyldimethylmethane is obtained from 28 g and 13 g of N- (2-aminoethyl) piperazine with a yield of 32 g of a product with a melting point of 85 ° C.

Example 12

7.75 g of piperazine and 9.4 g of a tetrahydrofuran polymer with terminal CH ₃ -NH groups (molecular weight 940) are dissolved in 100 ml of dimethylformamide. A solution of 28 g of 4,4'-dicyanatodiphenyldimethylmethane in 100 ml of dimethylformamide is added dropwise to this solution at room temperature in the course of 12 minutes. After 30 minutes, the reaction mixture is allowed to run into water and the precipitated product is filtered off with suction. Yield 40.1g. Mp. 120 ° C.

B e i s ρ i e 1 13

13.3 g of dipropylene- (1,2) -triamine are dissolved in 20 ml of acetone. For this purpose, a solution of 28 g of 4,4'-Dicyanatodiphenyldimethylmethan in 70 ml of acetone at 25 to 30 ⁰ C within 15 minutes. The mixture is left to stir for 15 minutes and the solution is poured into 1 liter of water. The precipitated colorless product melts after drying at 95 ° C. Yield 33 g.

'Example 14

To a solution of 14.5 g of bis (3-aminopropyl) methylamine in 20ihl Dimethytformamid added dropwise in the course vöü 10 minutes at 25 to 3O ⁰ G, a solution of 28 g of 4,4'-DicyanatadipBenyldimethylniethan in 8OmL dimethylformamide * The in Pouring the precipitated product into water is initially a bit greasy, but becomes hard when it is triturated. Yield 39 g, melting point 90 ° G.

Example 15

12.6 g of 2,2'-dichloro-4,4'-diaminodiphenyl are dissolved in 100 ml of dimethyl sulfoxide and heated to 80 ° C. A solution of 14 g of 4,4'-Dieyänatodiphenyldimethylmethän in 70 ml is left within 5 minutes Dimethyl sulfoxide run in and stir for a further 60 minutes at the same temperature, after cooling At room temperature the clear solution is poured into 1 liter of water to which a little common salt has been added. The yield is 19.5 g. Melting point 157 ° C.

Example 16

21.2 g of 4,4'-diaminobenzophenone are dissolved in 150 ml of dimethylformamide. At 80 ⁰ C a solution of 28 g of 4,4'-Dicyanatodiphenyldimethylmethan under stirring iii 70 ml dimethylformamide. The mixture is left to stir for 30 minutes and poured into water. The dry product melts at 160 ° C. Yield 43 g.

Example 17

Analogously to Example 16, 7.9 g of naphthylenediamine (1.5) are allowed to react with 14 g of 4,4'-dicyanatodiphenyldimethylinethane. Yield 16 g, melting point 160 ^° C.

Example 18

A solution of 21 g of 4,4'-dicyanetodiphenyldimethyl methane in 150 ml of methanol is allowed to run in at 50 ° C. in the course of 5 minutes to a solution of 14.5 g of 4,4'-4 "-triaminotriphenylmethane in 250 ml of methanol. after 30 minutes, the precipitated product is filtered off and washed with methanol. yield 28 g, mp 16O ⁰ C.

Example 19

A solution of 22.4 g of 2,6-diaminotoluene-4-sulfonic acid sodium in 200 ml of formamide is mixed with a solution of 28 g of 4,4'-dicyanatodiphenyldimethylmethane in 100 ml of dimethyl formamide. The mixture is heated for 1 hour at 8O ⁰ C, poured into 21 water and salted out at 6O ⁰ G NIIT 150 g of sodium chloride; the end. The air-dry product is washed with alcohol. Yield 30 g, melting point 360 ° C.

Example 20

At 80 ° C is added dropwise within 10 minutes to a solution of 20.7 g of 4,4'-diaminostilbendisulfonsaufem- (2.2 ') Sodium in 250 ml of dimethylsurfoxide a solution of 14 g of 4,4'-dicyanatodiphenyldimethylmethane in 70 ml of dimethyl sulfoxide and stirred for 30 minutes at the same temperature. After pouring the product is salted out in 1.5 liters of water at 50 ° C. and washed with alcohol. Yield 14 g, Melting point> 360 ° C.

Example 21

A solution of 28 g of 4,4'-Dl cyanatodiphenyldimethylmethane in 100 ml of dimethylformamide is added dropwise to a solution of 21.8 g of 4,4'-diaminodiphenyl sulfide in 65 ml of dimethylformamide over the course of 15 minutes. After stirring for 1 hour, the reaction mixture is poured into water. Yield 45 g, melting point 151 ^° C.

Example 22

Analogously to Example 21 is obtained from 24.8 g of 4,4'-Diaminodiphenylsulf one and 28 g of 4,4'-Dieyanatodiphenyldimethylmethan at 6O ⁰ C 50 g of a product melting 105-150 ° C.

Example 23

A solution of 10 g of 2,2'-dicyanato-3,3 ', 5,5'-tetramethyldibenzyl ether in 100 ml of dimethylformamide is added dropwise to a solution of 2.56 g of piperidine in 50 ml of dimethylformamide ° C. After stirring for 1 hour, the solution is added dropwise to 1.5 liters of water. Yield 11 g, melting point 100 ° C.

Example 24

A solution of 30 g is added dropwise to a solution of 8.6 g of piperazine in 100 ml of dimethylformamide 4j4'-dicyanatodiphenyl sulfone in 180 ml of dimethylformamide. After stirring and pouring for 1 hour 20.9 g of a product with a melting point of 96 ° C. are obtained in water.

B e i s ρ i e 1 25

A solution of 10.1 g of 2,4-dicyanatoacetophenone in 50 ml of acetone is added dropwise to a solution of 5.8 g of hexamethylenediamine in 60 ml of acetone. The internal temperature rises to 46 ⁰ C; After the usual work-up, a product with a melting point of 123 ° C. is obtained.

The product prepared analogously from 2,4-Dicyanatoäcetophenon and hexahydro -p-phenylenediamine melting at 15O ⁰ C; if piperazine is used as the diamine component, the reaction product has a melting point of 119 to 124 ° C.

Claims (1)

Claim: Process for the production of nitrogen-containing polyadducts, characterized in that that one organic cyanic acid esters of the general formula R (OCN) ₃ ; in which R is an aromatic or araliphatic, optionally with heteroatoms or keto groups interrupted hydrocarbon residue and χ means a whole number from 1 to 6, with polyvalent primary or secondary amines, optionally halogen atoms, sulfonic acid residues or contain keto groups and their hydrocarbon skeleton optionally by heteroatoms is interrupted.