DE1092197B - Process for the production of resinous paint raw materials - Google Patents

Description

GERMAN

It is known to convert phenols with phosgene into the corresponding chlorocarbonic acid esters using basic condensing agents that can be converted into crystallized urethanes with amines or polyamines.

It is also known to phenols with terpene hydrocarbons by means of suitable condensation agents such as To convert boron fluoride glacial acetic acid to higher molecular weight phenols. Depending on the raw materials chosen and the working conditions observed, one can choose to do so monomeric viscous or polymeric hard terpene phenolic resins, in which one more or less large part of the phenolic hydroxyl groups is present in reactive form. These products are definitely phenolic, which means that they can only be used to a limited extent as paint raw materials. In addition The terpene phenolic resins usually have very low melting points.

It is also already known to produce high molecular weight polyurethanes by using dichlorocarbonic acid esters certain aliphatic glycols with diamines in the presence of acid-binding agents or in excess Amine condensed. Here, polyurethanes are usually obtained in the form of powdery masses, which according to the usual cleaning and drying are white high-melting powders.

It has now been found that you can light, clear and resinous paint raw materials from chlorocarbonic acid esters and Can produce amines if the reaction product of terpene phenols or their partial Reacts hydrogenation products and phosgene with stoichiometric amounts of amines or polyamines and non-hydrogenated reaction products partially hydrogenated.

As terpene phenols, which are suitable as precursors for the present process, are, for. B. called: Condensation products of unsaturated terpenes such as pinene, camphene, limonene, dipentene, terpinene, sesquiterpene, polyterpenes, aliphatic terpenes or mixtures of terpenes with preferably monooxybenzenes and their derivatives (e.g. up to a terpene content of 80%, but possibly higher) such as isopropyl, butyl, amyl, diisobutyl, dodecylphenol, substituted phenols such as halophenol, monooxynaphthalenes, oxydiphenylmethane and others, as well as polyoxybenzenes such as pyrocatechol, resorcinol, hydroquinone, pyrogallol, phlorioxlucinyl, dioxynaphthalene derivatives, dioxynaphthalene derivatives. Such products can be relatively easily with and without inert solvents, e.g. B. hydrocarbons, such as benzene, toluene, xylene, hexane, heptane, technical hydrocarbon mixtures such as gasoline, etc., with phosgene, under pressure or under atmospheric pressure at temperatures between -10 and + 30 ° C to convert the corresponding chlorocarbonic acid esters, if the hydrochloric acid formed with alkalis, e.g. B. Soda, Sodium Hydroxide, Method of Manufacture
of resinous paint raw materials

Applicant:

Farbwerke Hoechst Aktiengesellschaft

formerly Master Lucius & Brüning,

Frankfurt / M., Brüningstr. 45

Dr. Josef Kaupp and Dr. Helmut Gruber,

Gersthofen via Augsburg,
have been named as inventors

Calcium hydroxide, sodium bicarbonate, calcium carbonate, potassium carbonate, potassium bicarbonate, etc., or better nor with tertiary amines such as dimethylaniline, pyridine, trimethylamine, triethylamine or triphenylamine and works with an excess of phosgene in order to avoid carbonate formation. These chlorocarbonic acid esters now form with approximately stoichiometric amounts of amines or polyamines, particularly completely with With the help of basic condensing agents such as sodium bicarbonate, calcium carbonate, soda, etc. did not crystallize, hard resins that can be used in paint technology. As examples of the amine and polyamine components may be mentioned: aliphatic, primary and secondary amines and polyamines such as methylamine, propylamine, Butylamine, octadecylamine, ethylenediamine, hexamethylenediamine, propylenediamine, butylenediamine, diethylenetriamine, Diethylamine, dipropylamine, dipropylenetriamine, aromatic primary and secondary amines and Polyamines such as benzidine, aniline and derivatives, diphenylamine, phenylenediamine, ditoluylamine, triaminobenzene, Naphthylamine, di- and triaminonaphthalene, hydroaromatic amines such as 4,4'-diamino-dicyclohexylmethane, Abietylamine et al. m.

The resins prepared according to the invention are distinguished by light color, clarity and a greatly increased melting point compared to the starting product, still have antioxidant properties and are used as paint raw materials and plasticizers are much cheaper to use because there are no more reactive hydroxyl groups in the Molecule are present.

In addition, the resins obtained in this way still have very good solubility properties in organic Solvents as in benzene and its homologues. When adding the stoichiometric amount of amines or

009 630/437

Polyamines, the acid number can be kept below 3 without aftertreatment, which is economically important is.

Especially light products are obtained when one atm by known methods using Raney nickel or nickel kieselguhr at pressures between 100 and 200, and temperatures of about 150 ⁰ C or below atmospheric pressure, the starting product (terpene phenol) in the melt or in solution by partial hydrogenation ( up to 50%, but optionally higher, based on the aromatic ring). Products that are just as bright can be obtained by partial hydrogenation of the end product.

The examples are intended to explain the process in more detail.

example 1

244 parts (1 mol) of viscous isobornyl cresol resin, prepared by a known process from a cresol mixture and camphene and subsequent distillation, are converted into a benzene solution of 1.2 mol of phosgene at 5 to together with 121 parts (1 mol) (or less) of ao dimethylaniline 10 ⁰ C added dropwise. The resulting dimethylaniline hydrochloride is washed out with water and the dimethylaniline is recovered. The benzene solution of the chlorocarbonate formed is, after drying, treated with the equivalent amount of 30.5 parts of ethylenediamine [ ¹ I ₂ mol) and 80 to 90 parts of sodium bicarbonate and heated under reflux for 2 hours. After filtration of the solution and evaporation of the solvent, a clear, light-colored resin with a melting point of 70 to 80 ° C. ultimately remains.

Example 2

306 parts (1 mol) of chlorocarbonic acid ester of the type mentioned in Example 1 are mixed with 287.4 parts (1 mol) of abietylamine in gasoline solution with the addition of 70 to 80 parts of sodium bicarbonate and heated to the boil for a few hours. The hereby resulting resin was atmospheres in gasoline solution by a known method by means of hydrogen and Raney nickel under pressure at about 15O ⁰ C and 150 to about 20% hydrogenated to give a bright, clear resin with a melting point about 80 ° C arose.

Example 3

442.5 parts (1 mol) of diisobornyl cresol resin with a melting point of about 40 ° to 45 ° C. are hydrogenated to about 30% in the melt using Raney nickel in an autoclave. In analogy to Example 1, the viscous chlorocarbonic acid ester is shown here. A solution of 921 parts ( ¹ J ₂ mol) of benzidine with the addition of a little bicarbonate is added dropwise to its solution in toluene, and the reaction mixture is brought to the boil for a few hours. The pale, clear resin produced in this way has a melting point of 104 to 110 ^° C., acid number 0.88.

Example 4

306 parts (1 mol) of the viscous chlorocarbonic acid ester mentioned in Example 1 are dissolved in toluene, together with 80 parts of sodium bicarbonate, presented and slowly added 31 parts of methylamine. It occurs a strongly exothermic reaction. After about 4 hours of post-reaction, it is filtered and the solvent or the unreacted chlorocarbonate was removed by distillation. It remains a solid, light, clear resin from Melting point 32 to 40 ° C back.

Claims (1)

PATENT CLAIM: Process for the preparation of resinous paint raw materials from chlorocarbonic acid esters and amines, characterized in that the reaction product of terpene phenols or their partial hydrogenation products and phosgene are reacted with stoichiometric amounts of amines or polyamines and unhydrogenated reaction products are optionally partially hydrogenated. Considered publications:
German patent specification No. 912 863. © 009 630/437 10.60