DE1543126C - Process for the preparation of polythiourea derivatives - Google Patents

Description

The invention relates to a process for the preparation of polythiourea derivatives, which thereby is characterized in that epoxides are reacted with a sulfur-containing compound, which is formed by condensation of compounds of general formula have the following general formula:

or

H ₂ N [—RNHCSNH—] _m H.
H ₂ NCSNH [—RNHCSNH—] _m H.

H ₂ N [—RNHCSNH—] _m H.

Here R is the rest

H ₂ NCSNH [—RNHCSNH—] _m H.
where R is the remainder

- (CH ₂ ) .-

or

[(CH ₂ ) NR '- (CH ₂ )] "

-C (CH ₂ ) NR '(CH ₂ )] "-

and R 'is hydrogen or alkyl radicals and η and m are integers, has been obtained with alkylenepolyamines, alkylenediamines or mixtures thereof.

The polythiourea derivatives are prepared according to the invention from a precursor, which follows called "polythiourea". The polythioureas include, for example following groups of connections:

a) instead of an active hydrogen atom, monosubstituted thioureas (RHNCSNH ₂ ),

b) dithioureas,

c) Polythioureas with chains or chain-like bonds, including crosslinking links fall, and

d) mixtures of these compounds.

The polythiourea derivatives prepared according to the invention are at room temperature or else liquid at elevated temperature. They are made by reacting polyamines such as diamine, with thioureas, α, ω-dithioureas, Carbon disulfide or esters of thiocarbonic acid, diisothiocyanate, dithiocarbamate and others known substances. As starting materials for the production of the polythiourea derivatives Polyamines used according to the invention belong to the following groups of compounds:

a) Alkylenedioamine compounds:
Ethylenediamine, tetramethylenediamine, hexamethylenediamine or nonamethylenediamine.

b) polyalkylene diamine compounds:
Diethylenetriamine, triethylenetetramine, tetraethylene pentamine, hexamethylene heptamine, di (hexamethylene) triamine, tri- (hexamethylene) tetramine, tetra (hexamethylene) pentamine or hexa- (hexamethylene) heptamine.

c) Other diamines and polyamines.

The polythioureas used as starting materials for the preparation of the polythiourea derivatives by the process according to the invention are obtained by condensation of polyamines, e.g. B. diamine produced with a sulfur derivative of carbonic acid with removal of ammonia. These polythioureas, mixtures of which are also suitable, R 'stands for hydrogen or alkyl radicals, and m and η are positive integers.

From the various studies of polythioureas, e.g. As the amine values, the molecular weights and elemental analysis shows that the compounds prepared by reaction of thiourea with nonamethylenediamine in equimolar amounts at 16O ⁰ C and with a reaction time of 15 minutes, have the following composition:

H ₂ NCSNH (- C ₉ H ₁₈ NHCSNH -) ₂ C ₉ H ₁₈ NH ₂

The molecular weight of this product increases due to the condensation when the reaction is a is carried out for a long time. Another polythiourea produced by reacting thiourea with dimethylene triamine in equimolar amounts' at 150 to 160 ° C with a reaction time of 60 minutes has the following composition:

H ₂ NCSNHC ₂ H ₄ NHC ₂ H ₄ Nh ₂

The molecular weight of this product increases only a little, even if the reaction takes a long time is carried out.

The polythioureas react with one or more epoxy residues in liquid Form added epoxy compound. The polythioureas can be converted into the liquid by heating Form can be transferred, while liquid substances are used without this pretreatment be able. It is also possible to use solid polythioureas in the form of solutions. Suitable Solvents are e.g. B. methanol and methanol-ethanol mixtures. The solutions are then with a liquid epoxy compound added.

Epoxy compounds suitable for the preparation of the polythiourea derivatives according to the invention include, for example, the following groups of compounds:

a) epihalohydrins, e.g. B. epichlorohydrin,

b) alkylene oxides, e.g. B. ethylene oxide, propylene oxide,

c) monoepoxy compounds, e.g. B. monoglycidyl ether,

d) diepoxy compounds, e.g. B. diglycidyl ether,

e) other polyepoxy compounds, e.g. B. epoxy resins.

The epoxy compounds can be made using the following methods:

a) Reaction of epihalohydrins with phenols, alcohols and acid amides.

b) Implementation of compounds containing double bonds with peracids, ζ. Β. Peracetic acid, Perbenzoic acid or hydrogen peroxide.

c) Reaction of glydicyl with diisothiocyanate.

d) Reaction of glycidyl methacrylate with vinyl monomers.

These epoxy compounds can be used as follows:

a) Gaseous epoxy compounds can be added to the polythiourea solutions at normal pressure or elevated pressure be blown in. ·

b) Solid epoxy compounds can be found in the polythiourea solutions dissolved or added to these solutions.

c) Liquid epoxy compounds are used without this' pretreatment and the polythio-

. urea solutions added.

It is believed that the epoxy radicals ring opening with one or more NH radicals of the polythiourea react, whereby the polythiourea derivatives of the method according to the invention are formed.

It has been found that there are two types of essential reactions in the process of the invention can take place, which can be represented, for example, as follows:

a) = NH + CH ₂ -CH ₂ -> N (-CH ₂ CH ₂ O -) "H

b) = NH + CH ₂ CH-R-CH CH ₂

\ ₀ / \ ₀ /

- ^ = N-CH ₂ -CH-R-CH-CH ₂ -N =

OH OH

where —R— stands for the bifunctional radicals and η is a positive integer.

The reaction of the polythioureas used with the epoxy compounds generally proceeds exothermic, even if it is carried out in an open vessel and at room temperature. Preferably the temperature is controlled so that polythiourea derivatives with desired properties are obtained will. In the following working examples, the reaction time was very short. Further Alkali compounds are preferably added to the reaction solutions as a catalyst, if epihalohydrin is used as an epoxy compound. These catalysts can be used in a simple manner usual procedures, e.g. B. by extraction, can be removed again.

The epoxy compound can be added to the polythiourea solution at room temperature. It is advantageous to use elevated temperatures of for example 60 to 13O ⁰ C, while still higher temperatures are not connected to any further advantage.

The polythiourea derivatives prepared according to the invention have various salient properties :

I. In liquid form

a) High viscosity, solubility in solvents such as methanol, stability and low odor development at room temperature;

b) high cation activity due to the presence of nitrogen residues in the molecules, as well as surface activity by the presence of hydrophobic residues and polarized residues in the molecules;

c) instant curing of epoxy resins even at room temperature; .

d) Polycationic coagulation ability.

II. In solid form

a) Insolubility in solvents such as methanol, stability, low odor development, good flexibility, high strength and heat resistant

speed; . . ;

b) Diversity of technical application possibilities through the ability of the instantaneous

-Hardening.

It is possible to change the properties of the manufactured products by changing the type and proportions to change the input materials. This is due to the properties of the products largely on the nature of the bonds between the NH radicals of the polythiourea and those used in the Epoxy compound depending on existing epoxy radicals. In this way it is possible to get liquid to manufacture solid products.

The polythiourea derivatives prepared according to the invention can be used for a variety of purposes, e.g. B. as hardening and vulcanizing agents, fungicides, algae killers, surfactants, coatings and adhesives.

In the following examples, parts are parts by weight.

B e i s ρ i e 1 1

A mixture of 316 parts of nonamethylenediamine and 152 parts of thiourea was heated for 60 minutes with stirring in flowing nitrogen to 160 ⁰ C. The released by-products, such as ammonia gas, hydrogen sulfide (trace amounts), were removed with the nitrogen. After cooling the mixture, 380 parts of a polythiourea were obtained. The product obtained was in the form of a transparent, viscous liquid at room temperature and a viscosity of 6500 cP at 25 ° C.

The product obtained was insoluble in water, benzene, toluene and xylene and was insoluble in dilute hydrochloric acid, Acetic acid, soluble in methanol, diethylenetriamine and ethylene glycol.

B ei s ρ i e 1 2.

An exothermic reaction was found when 39 parts of phenylglycidyl were added dropwise to 100 parts of the polythiourea prepared according to Example 1 with stirring at 35.degree. After the addition, the mixture was kept for 1 hour at 8O ⁰ C, wherein the Polythioharnstoffderivat was formed which was stable at room temperature and the mold was a transparent and viscous liquid with a faint odor of ammonia. In the chemical tests, almost the same properties were found for the product as for the polythiourea derivative prepared according to Example 1.

An exothermic reaction was also found when 13 parts of the polythiourea derivative at room temperature

temperature were added to 30 parts of epoxy resin, the reaction of 4,4-dihydroxydiphenylpropane made with epichlorohydrin and had an epoxy equivalent of 190. The reaction mixture began to harden after 2 to 3 minutes. A stable substance was obtained.

B e i s ρ i e 1 3

An exothermic reaction took place when 15 parts of epoxy resin, which had been prepared by reacting 4,4-dihydroxydiphenylpropane with epichlorohydrin and had an epoxy equivalent of 190, were added dropwise to 100 parts of polythiourea according to Example 1 with stirring at 25 ° C. After the addition, the reaction was carried out at 80 ° C. for 1 hour, a polythiourea derivative being obtained. The product obtained was liquid at room temperature and had a viscosity of 15,000 cP ^{at 25 ° C.}

The product was stable at room temperature and had only a faint ammonia odor. The product had almost the same properties as the product obtained according to Example 1. It was diluted in Hydrochloric acid, aqueous acetic acid, glycol and methanol soluble and soluble in water, benzene, ethyl acetate, Pyridine and trichlorethylene are insoluble.

The polythiourea derivative was then mixed with the same amount of the above epoxy resin mixed. Immediately after mixing, the mixture was applied to two steel panels with a doctor blade 1 130 mm 25 mm (after pickling, washing with water and drying) in one layer thickness applied from 1 mm. Two sheets were then glued together and at room temperature for 24 hours held. The following properties were determined in the physical tests:

Tensile strength 100 kg / cm ²

Heat resistance 150 ° C

The same exothermic reaction was observed when the polythiourea derivative obtained according to Example 1 mixed with 20, 13 and 7 parts of the above-mentioned epoxy resin in comparative tests would. In all cases the mixtures began to solidify after 10 minutes. Stable and tenacious Substances were obtained.

B e i s ρ i e 1 4

A mixture of 122.3 parts of hexamethylenediamine and 76 parts of thiourea was under the im Example 1 treated conditions, wherein 162 parts of a polythiourea were obtained, which is in the form of a syrup and has a viscosity of 160OcP at 25 ° C and an amine number of 320 mg KOH / g. To 100 parts of this product were 8.5 parts of phenyl glycidyl ether were added with stirring, a polythiourea derivative being obtained. The reaction was carried out for 1 hour. The derivative obtained had a 10% dilute hydrochloric acid solution only had a faint ammonia odor and was stable.

The solution of the polythiourea derivative in hydrochloric acid (10%) was then diluted with water to form a 0.1% aqueous solution. 1 g of this solution was stirred into 1000 g of a 5% strength diatomite suspension. (Turbidity value 50 °.) A clear solution was obtained within 3 minutes (turbidity value 2 °). The polythiourea derivative prepared according to this example had the same effect as a coagulant as 80 to 100 g of aluminum sulfate (Al ₂ (SOJ ₃ · 18H ₂ O).

Example5.

In the manner described in Example 4, a 35% strength solution in methanol of 100 parts of according to Example 4 prepared polythiourea derivative reacted with 5.2 parts of epichlorohydrin with stirring.

ίο The exothermic reaction was a 33% Solution of the polythiourea derivative in methanol formed.

The product obtained was stable and had only a faint ammonia odor. The methanol, solution was diluted with water to a 0.1% solution. 20 g of this solution were in 1000 g Industrial water (absorption at 420 m μ 49.8%) is stirred in. It became clear within 15 minutes Solution obtained (absorption at 420 ηΐμ 95.5%).

In a comparative experiment, 1000 g of the same colored industrial water were mixed with 180 g of aluminum sulfate under the same conditions as in Example 5. A permeability of 80% (absorption at 420 πΐμ) was achieved, which was worse than the value achieved with the product according to the invention.

Examples

A mixture of 387 parts of diethylenetriamine [(H ₂ NC ₂ HJ ₂ NH] and 282 parts of thiourea was reacted under the same conditions as in Example 1 (except for the reaction time of 1 hour) to give 545 parts of a reaction product which had the form of a transparent, viscous liquid, the viscosity of which was 350 ° C. 15 parts of phenylglycidyl ether were stirred into this product, during which an exothermic reaction took place Liquid had a viscosity of 15,000 cP at 25 ° C. The polythiourea derivative obtained had only a weak ammonia odor and was stable.

Example 7

Under the conditions mentioned in Example 1, a mixture of equimolar parts of hexamethylenediamine was obtained and ammonium rhodanate to obtain a reaction product which contains the In the form of a light yellow, transparent and viscous liquid, which at 30 ° C had a viscosity of 9500 cP. To 100 parts of this solution was added an epoxy resin obtained by reacting 4,4-dihydroxypropane was made with epichlorohydrin and was the equivalent of 190 grams of epoxy. the Treatment of this mixture gave a polythiourea derivative in the form of a viscous liquid. The product was tested as a hardening agent. To do this, it became 70 parts of a viscous liquid epoxy resin given by reacting a primary copolymer of a phenolic resin with alkaline epichlorohydrin, 5 parts of toluene and 20 parts of titanium oxide powder at 30 ° C was. After mixing well, concrete structures were covered with the material. The coating Formed a semi-solid after 15 minutes and had a stable, tough, white surface after 12 hours:

Claims (1)

Example 8 A mixture of 292 parts of triethylenetetramine and 72 parts of thiourea was reacted for 60 minutes. whereby 324 parts of polythiourea were obtained. The product was a at room temperature yellowish, transparent, viscous liquid (viscosity 200 cP at 15 ° C). To 100 parts of the mixture were 20 parts of phenyl glycidyl ether were added with stirring, an exothermic reaction taking place. After the In addition, the reaction was carried out for 1 hour, whereby 120 parts of polythiourea derivative were obtained became. The product was a yellowish, transparent, viscous solution and at room temperature turned out to be stable. Claim: Process for the production of polythiourea derivatives, characterized thereby net that epoxides are reacted with a sulfur-containing compound, which is formed by condensation of compounds of the general formula H ₂ N [- RNHCSNH -] _m H. H ₂ NCSNH [- RNHCSNH -] _m H.
where R is the remainder - (CH ₂ ), - - [(CH ₂ ) NR '(CH ₂ )] "- and R 'is hydrogen or alkyl radicals and η and m are integers, has been obtained with alkylenepolyamines, alkylenediamines or mixtures thereof. 109 549/519