DE1189713B - Process for the production of polycondensates - Google Patents

Description

Process for the production of polycondensates It is already known monomeric condensation products by reacting halotriazines with a sulfone or carboxylic acid containing a primary amino group. It is further known to use diamines for the production of polycondensates, the triazine rings connected with NH - R - have NH groups, where R is a sulfo-substituted aryl or aralkyl group. Finally, the reaction is also similar described between polyamines and halotriazines to produce polycondensates, which have triazine rings associated with - N - (CH2) n - N groups.

The products obtainable by these known processes have the lack of sufficient resistance at higher temperatures and lack of firmness and so z. B. not as a hard shape or for use would be used for brake chucks.

The invention relates to a process for the preparation of polycondensates by reacting 1 mol of a dihalo-s-triazine of the formula in which X is chlorine or bromine atoms and R is an alkyl, aryl, substituted aryl or a disubstituted amino radical, with 0.6 to 1.2 mol of an amine at temperatures of 200 to 400 ° C, which is characterized in that the amine is compounds of the formula used, in which R1 is primary, secondary or tertiary amino radicals, alkyl, aryl or substituted aryl radicals and the radicals R1 are identical or different, but the compounds have at least one primary amino radical or two secondary amino radicals.

Dihalo-s-triazines can be used in a particularly advantageous manner use that in situ by the reaction of cyanuric chloride or bromide with equimolar Amounts of a secondary amine have been prepared in a known manner.

If it is desired that the polycondensate be substantially linear is built up, so for every mole of dihalo-s-triazine 1.0 to 1.2 moles of the nitrogen-containing Compound or mixtures thereof used.

Crosslinked polycondensates can be prepared by reacting the dihalo-s-triazine with an amino-s-triazine in amounts sufficient to produce branching. Preferably, each mole of dihalo-s-triazine is mixed with 0.6 to 0.8 moles of an aminos-triazine of the general formula in which each Z denotes an amino or an NHR group or an NR2 group, with at least three replaceable hydrogen atoms in the groups Z, reacted.

Examples of aminos-triazines are 2-amino-4,6-diphenyl-s-triazine, 2-phenyl-4,6-dianilino-s-triazine, benzoguanamine and melamine.

Examples of nitrogen-containing compounds used in the manufacture Branched polycondensates that can be used are 2 - amino - 4 - anilino - 6 - phenyl - 5 - triazine, trianilinos-triazine, benzoguanamine and melamine.

The dihalo-s-triazine can be 2-phenyl-4,6-dichloros-triazine. Optional the dihalo-s-triazine can and can be a disubstituted amino-dihalo-s-triazine in situ by reacting cyanuric chloride or bromide with an essentially equimolar Amount of a secondary amine to be produced.

Such a secondary amine is preferably diphenylamine or carbazole.

The invention also includes such procedures in which mixtures of the dihalos-triazines and the nitrogen-containing compounds to the reaction be brought to give polycondensates with different properties.

All of the reactions described above can be carried out in a suitable solvent be carried out in the form of solutions with or without the use of a base, to react with the halogen-hydrogen formed during the reaction.

The preferred procedure is heating to temperatures from 200 to 400 ° C from a mixture of the dry reactants in an inert Atmosphere until connection is formed.

The heating is preferably continued in this temperature range, until the evolution of halogen-hydrogen is essentially complete.

The polycondensates are obtained on cooling.

The polycondensates as produced by the process of the invention are stable at high temperatures and are used in many applications Suitable for the plastics industry. Polycondensates, which contain NH2 or - NH groups, are valuable conversion components for epoxy resins.

The products have a variety of uses, e.g. B. for surface coatings, for casting processes, for adhesives and for molding processes. They generally have high thermal stability and high heat resistance.

Polycondensates containing NH2 groups can be produced by reaction hardened with formaldehyde or a substance that produces formaldehyde. As this is common in plastics technology, can cause hardening before it Heating other materials are added to the properties of the hardened Modify material; these materials include fillers, extenders, Plasticizers and reinforcing agents.

By adding materials such as asbestos, moldings can be made, which can be used as brake pads. Linear polycondensates can be precipitated from solutions in organic solvents to make films to give, which can be stored at higher temperatures and tough, firm form adherent coatings on metal.

Example 1 A mixture of 1.87 g benzoguanamine and 4.52 g phenyl dichloro-s-triazine was left on in a dry nitrogen atmosphere for 11/2 hours 320 "C heated. As soon as the evolution of hydrogen chloride ceased, a hard, yellow, branched, resinous product obtained.

Example 2 A mixture of 1.87 g benzoguanamine and 2.26 g phenyl dichloro-s-triazine was heated to 230 "C for 4 hours in a nitrogen atmosphere.

A pale yellow resin was obtained on cooling.

Example 3 A mixture of 3.69 g of cyanuric chloride, 1.87 g of benzoguanamine and 3.34 g of carbazole was heated in a nitrogen atmosphere and the temperature slowly increased from 230 to 3900 C over a period of 12 hours. A yellow one branched resin was obtained.

Example 4 A mixture of 1.84 g of cyanuric chloride, 1.38 g of melamine and 1.67 g carbazole was heated to 300 "C for 7 hours. After development of hydrogen chloride had ceased, a pale yellow resin was obtained.

Example 5 1.84 g of cyanuric chloride, 2.24 g of benzoguanamine and 1.67 g Carbazole were heated together to 350 ° C. over a period of 5 hours. Hydrogen chloride was developed, and a green-brown, opal, resinous product was obtained.

Example 6 2.26 g of phenyl dichloro-s-triazine and 1.51 g of melamine were obtained Heated to 350 "C for 6 hours under dry nitrogen. Hydrogen chloride was added and a pale yellow resin was obtained.

Example 7 A mixture of 0.9 g benzoguanamine, 3.4 g 2-phenyl-4,6-dichloro-s-triazine and 1.3 g of aniline hydrochloride was in a glass tube in a nitrogen atmosphere Heated at 2600 C for 20 hours.

Hydrogen chloride evolved and upon cooling gave a yellow resin.

Example 8 A mixture of 7.5 g of phenyl dichloro-s-triazine and 11.8 g triphenylmelamine was in a nitrogen atmosphere for 15 hours at 180 to 190 "C. A pale yellow solid was obtained which had a softening point of 2600 C.

Example 9 A mixture of 3.68 g of cyanuric chloride, 3.74 g of benzoguanamine and 3.38 g of diphenylamine were added in a dry nitrogen atmosphere for 20 hours Long heated to 260 "C. A yellow resin with a softening point of 260" C was obtain.

Example 10 A mixture of 3.68 g of cyanuric chloride, 2.52 g of melamine and 3.38 g of diphenylamine was added in a dry nitrogen atmosphere for 14 hours long at Heated to 300 "C. A yellow resin was obtained.

The polymer was then made by reaction with hexamethylenetetramine networked.

Claims (2)

Claims: 1. Process for the preparation of polycondensates by reacting 1 mol of a dihalogenotriazine of the formula in which X is chlorine or bromine atoms and R is an alkyl, aryl, substituted aryl or a disubstituted amino radical, with 0.6 to 1.2 moles of an amine at temperatures from 20 ° C. to 400 ° C., thereby characterizing n et that, as amine, compounds of the form used, in which R1 is primary, secondary or tertiary amino radicals, alkyl, aryl or substituted aryl radicals and the radicals R1 are identical or different, but the compounds have at least one primary amino radical or two secondary amino radicals. 2. The method according to claim 1, characterized in that one dihalo-s-triazines used in situ by the reaction of cyanuric chloride or bromide with equimolar Amounts of a secondary amine have been prepared in a known manner. Documents considered: German Auslegeschrift No. 1,040,786; German Patent No. 892 751; U.S. Patent No. 2,467,523.