NO5987A - Process for the preparation of vinyl sulfoxides - Google Patents

Abstract

There are described novel diarylvenyl sulfoxides of the formula wherein R 1 is hydrogen, C 1 -C 4 alkoxy, arylalkoxy, halogen or amino; R 2 is hydrogen, C 1 -C 4 alkoxy, arylalkoxy, halogen or amino; and R 3 is a thermally labile or acid labile C 2 -C 10 alkyl, C 4 -C 10 alkenyl or aryl (C 1 -C 10 alkyl) group. Processes for the preparation of these compounds are further described.

Description

Process for granulating water-insoluble powdery substances such as metal salts and the like*

Many for. specific chemicals are used for technical purposes

in solid powder form. Thus, e.g. water-insoluble metal salts and pigments in solid form on a large scale in industry"

especially in the plastics industry, or eg* sulphur, especially for vulcanization purposes or for pest control.

The salts, especially the metal soaps, often serve as lubricants, hydrophobic agents, preservatives, stabilizers and many other purposes.

Metal salts, especially soaps, can be formed by the smelting method

by heating the fatty acids with a metal oxide (e.g. zinc oxide with stearinous acid), whereby salts are then mostly formed in the form of tough melts that are difficult to dose.

By reacting the oxides or hydroxides and acids

in a solvent, these are mostly present in circuit ldp.

When using high-boiling solvents such as e.g. "softening agents" leads directly to dust-free metal soap pastes which as such can be used, for example, to stabilize chlorine-containing polymers. It is also known to react oxides, hydroxides or carbonates on the one hand and acids on the other hand on a carrier material.

The precipitation method used for the production of metal soaps mainly produces exceptionally light, voluminous products. This method is frequently used in the production of stearates and palmitates of aluminium, calcium»lead, zinc and magnesium. The starting point is the fatty acids which are first transferred to the water-soluble soap of sodium, potassium or ammonium.

These water-soluble soaps are then reacted with solutions of alkaline earth or heavy metal salts to water-insoluble metal soaps in the narrower sense, thus, for example, sodium stearate can be reacted with calcium chloride to form calcium stearate and common salt.

The collected metal soap is then centrifuged or filtered. is freed by long washing from all impurities and two r res tii at the end.

Water-soluble metal salts can be obtained, in addition to using double reaction in suitable solvents during isolation of insoluble products, generally also by hydrolysis of a water** soluble metal salt or by reaction of a metal salt that is in itself insoluble in water to another water-insoluble salt of the same metal using catalytically active acids such as those e.g. from the preparation of polybasic lead sulphates and lead phosphates from lead slip suspended in water with sulfuric acid' or phosphoric acid in the presence of a catalyst.

Many metal salts, almost all metal soaps and pigments

"As they are extremely fine, voluminous powders", they tend to have a very strong consistency. This stdv seems very uncomfortable when using the products, and all the more so as precisely the most important of these unsolvable® products are toxic. In particular, when basic lead salts are used, including lead soaps, poisonings have always been established in the persons employed in the processing. Other very important industrial salts, respectively sepsis, are no less poisonous. Thus, the salts and soaps of cadmium and barium are physiologically exceptionally problematic. Physiological concerns are also present in the resorption of zinc, strontium» copper» chromium» mercury» tin and the soaps and salts of many other metals. In the case of basic soaps of certain metals»especially the basic salts of lead»above all the polybasic lead sulfates and lead phosphites»lead fumarates, phthalates»salicylates and other basic lead compounds, it is also very difficult to disperse the relevant salts homogeneously and sufficiently quickly in other masses » especially when mixing in plastic masses.

Even in the case of physiologically completely harmful substances, the dust load for the people employed in this way is an exceptionally tedious problem. It is very difficult to keep facilities clean and dust-free and to dose the products exactly. Moreover, many of these have water-soluble or -'- sparingly soluble substances tendency to bridging and eir for processing in automatic dosing systems not suitable.

People have long tried to circumvent the described difficulties by transferring the substances such as metal salts, soaps and pigments into dough-like paste form and then with products that are nevertheless used in the final product, e.g. in the plastics industry with plasticizers, in the rubber industry with mineral oils. Attempts have also been made to add the metalloeps and metallalts in small amounts of plasticizers to bind the dust.

Delivery in paste form has the disadvantage that larger amounts of plasticizer must be transported, which burdens shipping costs and these mostly viscous pastes are difficult to weigh and dose. Also, the softener or mineral oil interferes with general applicability.

The production of so-called weakly dusting products has also not led to satisfactory results because a small amount of softening agent is not effective and the larger amount of lead allows for aggregations to occur which then allow poor distribution. Hard lumps are formed which when using the products leads to difficulties. There have also been repeated attempts to tablet© the suitable compounds or granulate them in one way or another. TaMetering and granulation are in principle possible, but this leads to products that are even more difficult to distribute than the normal starting compounds available in powder form , as the mechanical processing is essential.

It has now been found that it is possible to transfer in a surprisingly simple way "hardly soluble or insoluble powdery chemicals" in particular metal salts including metal soaps and inorganic pigments into a non-dusty, easy-to-handle and doseable form that does not hinder applicability.

The invention therefore relates to the production of granulated products on the basis of poorly water-soluble or insoluble clay"

water-dispersible chemical substances such as metal salts, particularly metal soaps and pigments which tend to form dust and where, according to the invention, the substances are precipitated from their suspension

in an aqueous medium at temperatures above approx. 60°C in the presence of poorly soluble in water or insoluble organic compounds with a molecular weight above ISO»preferably above 200 and a softening point below 100°C» isolate the precipitate and dry. Often exhibit these

compounds a long-chain aliphatic residue. ,\ Particularly suitable are '"'"here fatty alcohol©ster0fatty acid°esters of polyhydric alcohols»(acids of polyhydric alcohols with fatty acid esters, alkylester0ester wax»

fatty acid esters and fatty acid alkanolamides, fatty acid nitrites, alkylphenols, fatty acid ketones, mixtures of mineral oils and liquid pa raffins with metal soaps, fatty anhydrides of high fatty acids, and mixtures containing mineral oils or liquid paraffins, etc., which have a softening point below lOO C.4^

Here, fatty alcohols also mean functional derivatives thereof, e.g. fatty alcohols. Among the esters, alkylene glycol esters including polyalkylene glycol esters also fall in particular, whereby the alkylene ester is mostly ethylene. Here, of course, it is also possible to use® such esters which give the end product special properties £„ e.g. stabilizing effect for plastics.

The method according to the invention finds further use

for granulation of water-heavy or insoluble powdery substances that can be dispersed in water. In addition to being used on metal salts, pigments, sulfur, etc., it can also be used on plastics such as polyvinyl chloride, polyalkylenes such as polyethylene, polyacrylic compounds as well as mixed polymers on the aforementioned basis.

Here, the granulation of the emulsions retained from the production according to the emulsion ion method can be carried out directly.

As starting products, the fully precipitated and washed as well as possibly dried metal soaps or dried metal soaps produced according to the melting method®, another water-insoluble metal salt or pigment can also be used.

In a simple way, the implementation of the procedure can

happen so that. the compound in the presence of which the substances must be combined" is added to an aqueous suspension of the substances. Of course, it is also possible to combine the substances obtained in a sandy or organic carrier with the compounds obtained in an aqueous or organic carrier in whose presence the precipitation occurs and adds the possibly still necessary amount of water they require.

It is also possible to stir the solid substances into the compounds of the relevant type contained in a carrier, as well as the uptake by means of water of solid® mixtures of these substances and diss® compounds and then cause the precipitation.

It is advantageous to proceed in such a way as to store them

to temperatures above 60°C only after the union of the substances with the compounds in whose presence the precipitation occurs.

For the most part, work is done so that the compounds in the vicinity of which the precipitation occurs are used in an amount of 3 - 25%, preferably 10°20% by weight, calculated on the basis of the material from which the sisal is granulated.

The granulation method according to the invention is also of significant advantage in terms of method technology. The filling of a teved products presents great ©.- apparafcive difficulties. Above all, the shock load requires the precautions to avoid this,, a rather

large apparatus supply. already from the manufacture of the products. The facilities for ff room positioning of the granules will now be fairly simple and significantly cheaper. The granulated substances, especially the metal soaps and salt©, can be separated from water and washed much more easily than the powdered products. The granules contain on average approx. 50% of the amount of water for the powdered or filter cake products present. They can dry much easier and faster and do not need to be painted. Complicated filling devices are no longer necessary, so that the entire pre-steeling process® also becomes very significantly cheaper. The drying thus takes place so easily, quickly and smoothly that the products can already be partially extracted with a normal windpipe ring, in ready-to-sell form within 24 hours.

Products obtained according to the method of the invention also exhibit such advantageous properties. Thus, during practical testing of products manufactured according to the method of the invention, it has become clear that when using e.g. metal salts'and sep©f to granule form. the effect is significantly improved. Many of these metal salts are known to be used as stabilizers. Surprisingly, it turned out that the stabilizers in granule form are more effective than the difficult-to-distribute corresponding stabilizers in powder form, and that the need for additional lubricants is significantly less.

Thus, the application of e.g. a basic lead sulphate in granule form o which was granulated in the presence of approx. 15% of a distearic acid ester of pentaerythrito wood. the production of rudder a significantly more beautiful surface<g>l&ns, better mechanical values and Increase of the ejection. The reduction in mechanical values is possibly also due to the fact that the sulphate in its own gliding = effect is more favorable than normal sulphate, that the additions of lubricants required for dispersing the sulphate in the plastic are smaller, and because by reducing the amount of lubricant an improvement is achieved of the mechanical values, especially the shear strength and cold impact strength. It is known that basic lead sulphates and especially basic lead phosphites are in themselves more difficult to distribute in the plastic, when they are produced according to the usual method.

You therefore need relatively large amounts of dispersants.

These dispersants are very often substances

which reduce the mechanical values of the plastics produced with these.

Many pigments, including titanium dioxide, phthalicyanine blue, soot, Prussian blue, and iron red oxide pigment, are very difficult to disperse, so that with some of these, expensive coating methods are included in the purchase to achieve a better dispersibility. Here, the method according to the invention had to bring with it a significant improvement of the current technique, as according to the new method an influence on the pigment power is avoided.

The method is particularly applicable for the production

of compounds that find use as stabilizers, lubricants, pigments»rubber additives in the manufacture of plastics, rubber articles, linoleum, paints and varnishes and in many other branches of industry. Fillers, paper aids and numerous other products can also be produced using this method.

©J-jejnpel. X

lOO g tetrabasic lead sulphate is suspended in 200 ccm of water

and heated with good stirring to over 60°. 15 g of triethylene glycol stearic acid diester are then added. At approx. 90°

a granule forms from the suspension, which is filtered off and briefly dried.

Example _ Z_.....

100 g of titanium dioxide is suspended in 300 ccm of water

and heated with good stirring to approx. 95° and added at this temperature with 15 g of trimethylolpropanediol ester. 1 within 5 minutes, the granules separate, which are filtered off and dried.

Eczema gel = æ3

100 g of zinc oxide are suspended in 200 ccm of water and heated to 85° with good stirring. At this temperature, a

mixture of white oil and 10 g of sorbitol monostearin dioleate. After 5 minutes, the granules separate, which are dried and wrapped shortly afterwards.

Example=4

100 g of freshly precipitated calcium carbonate is suspended in 200 ccm of water and 15 g of stearic acid diethynolamide is added. After approx. 5 minutes, the granules separate at 95°.

ExampleJ>

lOO g of barium cadmium laurate is suspended in the same way

in 200 ccm of water and added at 90° with 15 g of pentaerythritol mono°oleate. After 5 minutes, the granules stand out, which are then dried briefly.

Claims (5)

1„ Procedure for granulation of poorly soluble or insoluble in water. powdered substances, characterized by allowing the substances to separate from their suspension in an aqueous medium - at temperatures above 60 oC in the presence of poorly water-soluble or insoluble organic compounds with a molecular weight above 1500, preferably 200, and a softening point below lOO oC isolate the precipitate and then dry. 2. Method according to claim 1, characterized in that fatty alcohol esters are used as compounds in the presence of which the precipitation occurs, "acids of polyhydric alcohols with fatty acid esters, alkyd esters, ester waxes, fatty acid amides and fatty acid alkanolamides, fatty acid nitriles, alkylphenols, fatty acid ketones, mixtures of mineral oils and liquid paraffins with metal soaps" fatty acid anhydrides of fatty acids and mixtures containing mineral oils or liquid paraffins and which have a softening point below 100°C 3. Method according to claim 1 or 2, characterized in that the compounds in whose presence the salts resp. the pigments together, an aqueous suspension of the salts or the pigments. 4. Method according to claims 1-3, characterized in that the heating to temperatures above 60°C is first carried out after the union of the salts or the pigments with the compounds in whose presence the precipitation occurs. 5. Method according to one of claims 1-4, characterized in that the compounds in the presence of which the precipitation occurs are used in an amount of 3 to 25, preferably 10 to 20 percent by weight based on salt or pigment.