LU82867A1 - NEW DEVICES FOR THE EMISSION OF INSECTICIDE VAPORS - Google Patents

Description

i! - 1 - i CAS 2-12774 / AFR 114/1 + 2 i

New devices for emitting insecticide vapors

The present invention relates to formulating devices usable in or on a heating appliance and intended for the emission of insecticidal vapors.

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In a previous application filed on March 21, 1980, Applicant I described a device, intended for the emission of insecticidal vapors

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j and usable in or on a heating device, characterized in that | that it consists of several different solid compositions juxtaposed each comprising an active substance on insects absorbed in an absorbent mass material, said active substance i being, in at least one of the compositions chosen from pyrethrinoids.

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1 Now, it has now been found by the Applicant that the substance! active can also be advantageously chosen from new compounds here called isopyrethrinoids and constituted by esters i of suitably substituted alkanoic acids.

: i ‘i The invention therefore relates to a device, intended for the emission of vapors | »Insecticides and usable in or on a heating device, charac-

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preferred in that it consists of several solid compositions jl | different juxtaposed each comprising an active substance on insects absorbed in an absorbent mass material, said active substance being, in at least one of the compositions, chosen from among the isopyrethrinoids constituted by the esters formed between the alcohols used for the preparation of pyrethroids known to specialists, and acids, in their racemic or optically active form, defined by the formula:! i i j s - 2 -

R

A - C - CO - OH I

R ’in which R represents a light alkyl, light alkenyl or cyclopropyl residue, R’ being a hydrogen atom or else R and R * together represent a divalent propano-1,3 residue; A represents an aromatic nucleus, chosen from benzene, furan and thiophene, optionally carrying one or two substituents chosen from »bromine, chlorine, fluorine and the alkyl and alkoxy residues contained *. nant one to four carbon atoms or A represents a naphthyl residue or a dibromo-3,3 propene-2 yl or dichloro-3,3 propene-2 yl residue.

Among the acids thus defined, there may be mentioned in particular the following: Isopropyl 2-phenyl-2 Phenyl-isocaproic 2-cyclopropyl-2-phenyl-acetic (4-chloro-phenyl) -2 propionic (4-chloro-phenyl) -2 butyric (chloro-4 phenyl) -2 isovaleric (4-chloro-phenyl) -2 isocaproic (4-chloro-phenyl) -2 3,3-dimethyl butyric (4-chloro-phenyl) -2 butene-3 oic (4-chloro-phenyl) -2 pentene- 4 oique * Cyclopropyl-2 (4-chloro-phenyl) -2 acetic Phenyl-1 cyclobutane-carboxylic (chloro-4 phenyl) -l cyclobutane-carboxylic (Fluoro-4 phenyl) -2 isovaleric (Bromo-4 phenyl) -2 isovaler (2,4-dichloro-phenyl) -2 isovaleric (4-methylphenyl) -2 isovaleric (4-methoxyphenyl) -2 isovaleric (4-chloro-2-methylphenyl) -2 isovaler \ · - 3 -

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£ (Furyl-2) -2 isovaleric (Thienyl-2) -2 isovaler Cyclopropyl-2 (furyl-2) -2 acetic Cyclopropyl-2 (thienyl-2) -2 acetic (Naphtyl-2) -2 isovaler Cyclopropyl-2 (naphthyl-2) -2 acetic Dichloro-5,5 isopropyl-2 pentene-4 oique Dibromo-5,5 isopropyl-2 pentene-4 oique Dichloro-5,5 cyclopropyl-2 pentene-4 oique 'Dibromo-5,5 2-cyclopropyl-4-pentene

5,5-Dichloro-2-tert-butyl-4-pentene-oic

Such acids and their esters are described, in particular, in Japanese patents 54,144,332 and 55,009,049, in German patent ΐ 2,925,337, in American patent 4,164,415, in European patents 6,630 and 7,421 , in the British patent 1,514,557 and in the French patents 2,359,813 and 2,376,118.

Among the alcohols which can be combined with said acids ·

I to form isopyrethroids, there may be mentioned, in particular, the following: S 3-ethyl-2-methyl-4-oxo-2-cydopentene 3 3 allyl-3 methyl-2-oxo-4 cyclopentene-2 ol

Imethallyl-3 methyl-2 oxo-4 cyclopentene-2 ol crotyl-3 methyl-2 oxo-4 cyclopentene-2 ol j (3-methyl-propene-2 yl) -3 methyl-2 oxo-4 cyclopentene-2 ol § ' (2-chloro allyl) -3 2-methyl-4-oxo-2-cyclopentene | (3-chloro allyl) -3 methyl-2 oxo-4 cyclopentene-2 ol j furfuryl-3 methyl-2 oxo-4 cyclopentene-2 ol ij phenyl-1 propyne-2 ol || | j (3-chloro-phenyl) -l propyne-2 ol | j (3-fluoro-phenyl) -l propyne-2 ol j! it (3-trifluoromethyl phenyl) -! propyne-2 ol | i i | (thieny 1-2) -1 propyne-2 ol îj (furyl-2) -l propyne-2 ol: ί I î! 1 - 4 - 4-phenyl butene-2 ol (3-methylphenyl) -4 butene-2 ol (2-methylphenyl) -4 butene-2 ol (2,3-dimethylphenyl) -4 butene-2 ol ( 2-methoxyphenyl) 4 butene-2 ol (2-chloro-phenyl) -4 butene-2 ol (3-chloro-phenyl) -4 butene-2 ol (2,3-dichloro-phenyl) -4 butene-2 ol (bromo -3 phenyl) -4 butene-2 ol phenyl-4 butyne-2 ol (furyl-2) -4 butyne-2 ol (thienyl-2) -4 butyne-2 ol methyl-5 hexene-5 yne-2 ol methyl -5 hexadiene-2,5 ol dimethyl-5,6 heptene-5 yne-2 ol 2-methyl benzyl alcohol 3-methyl alcohol benzyl 4-methyl alcohol benzyl 2,3-dimethyl alcohol benzyl 2,4-dimethyl benzyl alcohol 2,5-dimethyl benzyl 2,6-dimethyl benzyl alcohol 3,4-dimethyl benzyl alcohol 3,5-dimethyl benzyl alcohol 2,4,5,6-trimethyl alcohol benzyl 4-allyl alcohol benzyl 4-allyl-2-dimethyl alcohol, 6 benzyl alcohol methallyl-4 benzyl alcohol (butene-3 yl) -4 benzyl alcohol vinyl-4 benzyl alcohol cyano-4 benzyl alcohol trifluoromethyl-4 benzyl alcohol nitro-4 benzyl alcohol 3-methyl furfuryl 5-methyl furfuryl alcohol i - 5 - 3,5-dimethyl alcohol furfuryl 4,5-dimethyl alcohol furfuryl 5-allyl alcohol furfuryl 5-propargyl furfuryl alcohol | alcohol (2-methyl-furyl-3) methyl I alcohol (2,5-dimethyl furyl-3) methyl I alcohol (trimethyl-2,4,5 furyl-3) methyl! methyl alcohol (5-allyl-furyl-3) i methyl alcohol (5-allyl-2-furyl-3) methyl alcohol (methyl-2-propargyl-5 furyl-3)! * tetrahydrophthalimidomethanol | (benzyl-5 furyl-3) methanol (alphacyanobenzyl-5 furyl-3) methanol j (alphamethynylbenzyl-5 furyl-3) methanol phenoxy-3 benzyl alcohol i phenoxy-3 alphacyanobenzyl alcohol * i phenoxy-3 alphamethynylbenzyl alcohol phenoxy alcohol- 3 alphapropargylbenzylic | ethyl (3-phenoxy-phenyl) -2 alcohol.

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The isopyrethrinoids thus formed include in particular the substances known under the names of fenpropanate and fenvalerate.

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One or more of said compositions may optionally contain, in addition, an inert adjuvant chosen from diluents, thickening agents, perfumes, synergists, colorants, stabilizers. bright, attractants and repellents.

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When all the compositions do not each contain a substance j j; active selected from isopyrethroids, it can, for example, i be chosen from synergists, insect repellents,! insect attractants and known insecticide compounds other than isopyrethrinoids.

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An insecticidal compound other than an isopyretrinoid may be, for example, an organochlorine compound whose vapor pressure at 25 ° C is "6, greater than 1.10 torr or an organophosphorus compound whose vapor pressure at 25 ° C is greater than 5.10 ^ torr, or a pyrethrinoid As nonlimiting examples of suitable organochlorine compounds, mention may be made of hexachlorocyclohexane and its gamma isomer known as lindane, chlordane and heptachlor.

As nonlimiting examples of suitable organophosphorus compounds, mention may be made of dichlorvos, carbophenothion methyl, I trichlormetafos-3, fenchlorphos, demethion, phorate,! demeton-methyl, naled or dibroma, chlorthion, thiometon, I demeton, chlormephos, pirofos, acetofosmethyl, bromophos, dichlorfenthion, acetofos, mevinphos and, more generally, the compounds mentioned in French patent 2292430 from Ciba-Geigy AG. As nonlimiting examples of suitable pyrethroids, there may be mentioned in particular the esters formed between a cyclopropenecarbo-xylic acid such as tetramethyl-2,2,3,3 cyclopropane carboxylic acid, or chrysanthemic acid or acids (butano-2 , 2 or dibromo-2,2 or dichloro-2,2 or difluro-2,2 vinyl) -3 dimethyl-2,2 cyclopro-panecarboxyliques, in their racemic or resolved forms (d and / or 1, cis and / or trans)) and the alcohols previously cited in connection with isopyrethroids.

'' Such pyrethroids are, for example, those known by the following common names: allethrin, bioallethrin, S-bioallethrin, cinerin, furethrin, dimethrin, benathrin, kadethrin, prothrin (or furamethrin), proparthrin, tetramethrin, bio-reshrine , phenothrin, d-phenothrine, permethrin, biopermethrin, cypermethrin, bromethrin, decamethrin and fluorethrin.

The synergists, when there is at least one in one of the compositions, are chosen from benzodioxoles, polyether ethers. · - 7 - ί · chlorinated and N-alkyl norbomene-5 dicarboximides-2,3.

Suitable benzodioxoles are, for example, safrole, isosafrole, cyano-5-benzodioxole-1,3, 5-ethynyl-benzodioxole-1,3, hydroxy-methyl-5-benzodioxole-1,3, cyanomethyl-5 benzodioxole-1,3, di-chloro-5,6 benzodioxole-1,3, chloro-5 cyano-6 benzodioxole-1,3, bromo-5 cyano-6 benzodioxole-1,3, chloro-5 cyanomethyl-6 benzodioxole-1,3, chloro-5 hydroxy-6 benzodioxole-1,3, chloro-5 hydroxymethyl-6 benzodioxole-1,3, chloro-5 ethynyl-6 benzodioxole-1,3 .

The suitable polychlorinated ethers are, for example, octa-chloro-1,1,1,2,6,7,7,7 oxa-4 heptane and hexachloro-1,1,2,6,7 , 7 oxa-4 j heptadiene-1,6.

Suitable 2,3-N-alkylnorbomene-2,3-dicarboximides are, for example, those in which the alkyl residue is an isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methyl butyl, isohexyl, 2-methyl hexyl, ethyl- 2 butyl or isodecyl.

The insect attractants, when there is at least one in one of the compositions, are chosen from all those known to those skilled in the art * such as, for example, fruit aromas, caramel, aromas of cheese, meat, amino acids, pollen extracts, thymol, skatole, indole, engenol, paraformaldehyde, hexamethylene. tetramine, ammonium carbamate, alipha- amines! , ticks, papain, pancreatin, aliphatic acids, vanillin, 3-chloro-3-methyl-butene-1, 3-chloro-methyl-3-butene-2 and heavy alkenes comprising 20 to 27 carbon atoms such as (cis) -tricosene-9.

Insect repellents, when there is at least one in one of the compositions, are, for example, dialkyl succinates, malleates and fumarates, alkyl mandelates, Ν, Ν-dialkylbenzamides and toluamides, cyclopropane carbonamides, alkanoyl-1 a hexahydro- - δ - benzofurans, alkanoates of dioxa-3,6 decyl, citronellal and its dialkylacetals and alkylhexane-diols.

The diluents, when there is at least one in one of the compositions, are chosen from liquid or solid organic compounds having a solvent power with respect to the insecticidal compound. The diluents used preferably have a vapor pressure at least equal to that of the active substance which accompanies it; better still, this vapor pressure is higher than that of the active substance.

Among the suitable diluents, mention may in particular be made of those chosen from the following chemical families: 1) The monoesters formed between the alkanols and the monocarboxylated hydrocarbons such as, for example, alkyl acetates such as those of hexadecyl or octodecyl , alkyl butyrates and isobutyrates such as those of dodecyle, tetradecyl, hexadecyle or octadecyle, alkyl hexanoates, alkyl octanoates, alkyl decanoates, laurates, undecanoates, undecenoates and alkyl myristates such as those of hexyl, octyl, decyl or dodecyl, palmitates oleates and alkyl stearates such as those of propyl, butyl, isobutyl, amyl, hexyl or octyl and alkyl benzoates, phenylacethtes and phenylpropionates such as those of hexyl, octyl, decyl or dodecyl.

2) The diesters formed between the alkanols and the dicarboxy- hydrocarbons. such as, for example, dialkyl adipates such as dioctyl adipate, dinonyl adipate, didecyl adipate and didodecyl adipate, dialkyl sebaçates such as dibutyl sebaçate, sebaçate dipentyle, dioctyl sebaçate, didecyl sebaçate, dialkyl azelates such as dioctyl azelate and dedececyl azelate, dialkyl phthalates such as dibutyl phthalate, dioctyl phthalate, didecyl phthalate, bis (undecyl) phthalate, bis (dodecyl) phthalate, bis (tridecyl) phthalate, bis (tetradecyl) phthalate and diketyl phthalate.

- 9 - 3) The diesters formed between phenols, alkylsubstituted or unsubstituted and dicarboxylated hydrocarbons such as, for example, | ! | diaryl phthalates such as diphenyl phthalate and dicresyl phthalates, 4) The diesters formed between cycloalkanols, substituted or unsubstituted alkyl and dicarboxylated hydrocarbons such as, for example, dicyclohexyl phthalate, bis (methylcyclohexyl) phthalates , bis (trimethylcyclohexyl) phthalates and bis (tetramethylcyclohexyl) phthalates, 5) The diesters formed between phenylalkanols and l dicarboxylated hydrocarbons such as, for example, dibenzyl sebacate, dibenzyl azelate and bis sebacates (phenylpropyle), * 3 6) The diesters formed between the alkanediols and the hydrocarbons | monocarboxylates such as, for example, 2,2,4 trimethyl diisobutyrate | pentanediol-1,3, '7) The triesters formed between phenols, substituted or unsubstituted alkyl, and phosphoric acid such as, for example, phosphate; of triphenyl, phosphate of tris (4-terbutylphenyl) and phos phates of tricresyl, "! 8) The triesters formed between the alkanols and phosphoric acid such as,! for example, trioctyl phosphate, tridecyl phosphate and tricodecyl phosphate, 9) Polyalkylene glycols such as, for example, polyethylene glycols and polypropylene glycols, {| - 10 - 10) Fatty alcohols such as, for example, hexadecanol, octadecanol and octadecene-9 ol, 11) Fatty acids such as, for example, lauric, myristic, palmitic, stearic and ol acids, 12) Alkanes containing at least 18 carbon atoms, such as, for example, octadecane, eicosane, docosane and tetracosane, and their mixtures known as petrolatum oil, ♦ paraffin oil, oil heavy, diesel) fuel oil, road oil, valve oil, fuel oil, petroleum jelly, petrolatum, slack wax, paraffin, microwax, ozocerite and ceresin, 13) Alkanones containing at least eighteen carbon atoms such as, for example, caprinone, laurone, myristone, palmitone and stearone, 14) Alkenones containing at least eighteen carbon atoms such as, for example, heneicosadiene-1,20 one-11 and oleone.

The thickening agents are, for example, metal salts of fatty acids, such as aluminum or magnesium mono-, di- and tri-stearates, or salts of fatty acids and amines, such as dioleate hexadecyl-aminopropylene-amine, octadecyl-aminopropylene-amine or octadecenyl-aminopropylamine-amine, or modified montmorillonites, such as ammonium salts of dimethyldi- (heavy alkyl) -bentonite.

The stabilizers, when there is at least one in one of the compositions, are chosen from all those known to those skilled in the art such as, for example, phenolic compounds such as resorcinol, pyrogallol, hydroquinone, 2-tertiobutyl-4-methoxyphenol and 2,6-ditertiobutyl-4-methyl-phenol, bisphenolic compounds such as bis (hydroxyphenyl) ethane, bis (hydroxyphenyl) methane, bis (hydroxyphenyl) propane, bis (tertiobutyl-3) 5-ethyl-2-hydroxyphenyl) methane and bis (3-tert-butyl-4-hydroxyphenyl) methane and! - (0,0-dialkyl (hydroxybenzyl) phosphonates such as 0,0-diethyl (4-hydroxy-ditertiobutyl-benzyl) phosphonate.

The absorbent mass materials can be chosen from cellulose paper and cardboard composed of wood fibers, cereal fibers, alfa fibers, cotton fibers, waste paper, asbestos fibers,! '' of glass fibers, wool fibers and / or polymer fibers and among the terracotta, sintered aluminas and ungrained porcelain.

ÎThe material constituting the mass material may also contain fillers chosen from organic powders, mineral powders, pigments, dyes and binders.

Mass materials can adopt all known forms such as p and that of plates and blocks.

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The plates can be any round, oval, square, rectangular, triangular, or polygonal, their total surface can be just as few square centimeters as several square decimetres and their thickness can vary from 0.1 to 6 millimeters.

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The blocks can be cubic, prismatic, cylindrical, of elliptical cut or any polyhedral, their total surface being able to vary from a few square centimeters only to several square decimetres.

A solid composition according to the invention is obtained by impregnation! | mass absorbent material by the liquid mixture of others! constituents of the composition (active substance and optionally! adjuvants). The impregnation can be done by pouring the liquid mixture on the absorbent material or by soaking the latter in the liquid, the soaking possibly being followed by a spin; this operation can be mechanized using, for example, a metering pump or a constant-flow spray boom; it is also possible to use a roller wringer at a pressure adjusted so as to allow the retention of liquid in the desired proportion; you can also use a centrifugal wringer at a set speed for the same purpose. An industrially interesting method of impregnation consists, for example, in the use of strips of great lengths, impregnated continuously and then cut to the desired dimensions. Impregnation can also be carried out by placing the absorbent material under vacuum in the presence of the liquid mixture.

The impregnation can also be carried out automatically by a machine comprising one or more injection syringes and a conveyor belt scrolling under them the absorbent materials to be impregnated.

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It is also possible to use a solution of the liquid mixture in a volatile solvent, the latter then being evaporated.

The solid compositions constituting the device are preferably two or three in number. They can be simply placed one next to the other without physical means of joining or, on the contrary, constitute a united whole.

When the device is a single unit, the solid compositions can be linked by any known means such as an adhesive, a cement or a stapling, nailing, embedding or metallic or plastic crimping system.

The device can also consist of a single absorbent mass material in which the active ingredients chosen, possibly accompanied by an inert adjuvant, have been absorbed, separately, and each in a separate zone. In this case, one zone may be left i - 13 -! i i mass material without impregnation so as to constitute a separation between the active materials; it is also possible to establish in this zone i an impenetrable barrier by means of a prepreg with a material! having the function of eliminating the absorbent state of the conventional material.

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A barrier can thus be formed, for example, by means of a vegetable, animal, paraffinic or isoparaffinic wax, deposited in the liquid state at the place where the barrier is to be produced; the wax l! is absorbed in the liquid state and forms, after cooling, a | impassable separation for active ingredients.

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Another material which can be used to make a barrier consists, for example, of an alkaline silicate in concentrated aqueous solution i and then dried.

Similarly, a solution of natural or synthetic resin in a volatile solvent can be used which is then removed by drying.

| ! A particularly advantageous method consists in creating the insitu barrier using a polymerizable material chosen from monomers, prepolymers and combinations of compounds capable of reacting with one another to give polymeric resins.

i I As interesting monomers, it may be mentioned, in particular, styrene, i! * methyl acrylate, ethyl acrylate, dimethyl maleates, | diethyl, dipropyl and dibutyl and cyanacrylic esters.

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The prepolymers are chosen, for example, from polyesters such as those formed between dicarKoxylic acids, such as adipic, sebacic, azelaic, maleic, phthalic or tetrahydrophthalic acids, and polyols such as ethylene and propylene. glycols, polyethylene and polypropylene glycols, glycerol and pentaerythrol.

ii '1 • i il When a monomer or prepolymer is used, it can favorably be added to it an accelerator and / or a polymerization catalyst at the time of the treatment of the absorbent mass material or, better, to be supplied separately. this accelerator and / or catalyst in the treated area before, during or after the treatment.

As an accelerator, mention may in particular be made of the cobalt or vanadium salts and the dialkylanilines; as polymerization catalyst ”, mention may in particular be made of carboxylic peracids, their esters and their salts and acyl, alkyl, cumene or ketone peroxides.

To promote the polymerization, it is also possible to operate at a temperature above ambient, such as, for example, between 40 and 80 ° C. during the treatment or to subject the treated area to this temperature after the treatment. The treated area can also be subjected to infrared radiation, ultra violet radiation, ultrasound, microwaves or gamma rays.

Of course, combinations of several prepolymers or of prepolymer (s) and of monomer (s) can be used to give particular characteristics to the polymers formed.

As associations of compounds capable of reacting with one another, there may be mentioned, in particular, those leading to the formation of epoxy, epoxy-ester and epoxy-phenolic resins, those leading to the formation of aminoresins such as urea-formaldehyde or melamine resins -formol and those leading to the formation of polyurethane resins.

The mixing of these compounds can be done just before application to the absorbent mass material; it is also possible to deposit each of the compounds at the same time or in turn on said material so as to allow the mixture to be carried out in situ.

- 15 -:! f .1 The devices in accordance with the invention have the advantage, in equal amounts of materials and under the same heating conditions, of providing insecticidal vapors more effective than those emitted by known devices in which the active substances used are mixed into one composition.

A feature of the devices according to the invention is to allow; to choose, for each of the solid compositions, an evaporation surface in relation to the active substance present and therefore I to make it possible to adjust separately the quantity evaporated of each of the active substances.

Another feature of the devices according to the invention is that it ’; allow, using a suitable heating device, a heating

Ide each of the solid compositions at a different temperature in relation to the active substance present and therefore allow, here too, to adjust separately the amount of substance evaporated from each of the active substances.

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Claims (24)

1. Device, intended for the emission of insecticidal vapors and usable in or on a heating device, characterized in that it consists of several different solid compositions juxtaposed each comprising an active substance on insects absorbed in a mass absorbent material, said active substance being, in at least one of the compositions, chosen from iso-pyrethroids constituted by the esters formed between the alcohols used for the preparation of pyrethroids and the acids, in their racemic or optically active form, defined by the formula RA - C - CO - OH R 'in which R represents a light alkyl, light alkenyl or Icyclopropyle residue, R' being a hydrogen atom, or else R and R 'together represent a divalent propano-1,3 residue; A represents an aromatic nucleus, chosen from benzene, furan and thiophene, optionally carrying one or two substituents chosen from bromine, chlorine, fluorine and the alkyl and alkoxy radicals containing one to four carbon atoms or alternatively A represents a naphthyl residue or a dibromo-3,3 propene-2 yl or dichloro-3,3 propene-2 yl residue. * 2. Device according to claim 1 characterized in that the solid compositions are two or three in number. 3. Device according to any one of claims 1 and 2 characterized in that at least one of the solid compositions contains an inert adjuvant chosen from diluents, thickening agents, perfumes, synergists, dyes, stabilizers , attractants and insect repellents. - 17 - l i 4. Device according to any one of claims 1 to 3 characterized in. that in each of the solid compositions, the active substance is chosen from isopyrethroids. 5. Device according to any one of claims 1 to 3 | characterized in that in one of the solid compositions, the active substance I is chosen from synergists, insect attractants, I * insect repellents and insecticidal compounds other than j * isopyrethroids. 6. Device according to claim 5 characterized in that the i active substance is an insecticidal compound chosen from -6 organochlorine compounds whose vapor pressure at 25 ° C is greater than 1.10 torr, organophosphorus compounds whose vapor pressure at 25 ° C is greater than 5.10 ^ torr, and the pyrethroids. 7. Device according to claim 5 characterized in that the active substance is a pyrethroid chosen from esters of chrysanthemic acid or (2,2-butano-vinyl) -3-dimethyl-2,2-cyclopropane-carboxylic acid or 2,2-dibromo-vinyl acid-3-2,2-dimethyl cyclopropane-carboxylic or 2,2-dichloro-vinyl-2,2-dimethyl cyclopropane-carboxylic or acid ( difluoro- 2.2 vinyl) -3 dimethyl-2,2 cyclopropane-carboxylic or tetra-methyl-2,2,3,3 cyclopropane-carboxylic acid in their racemic forms “r our resolved (d and / or 1, cis and / or trans). 8. Device according to claim 7 characterized in that the pyrethronoid is chosen from the substances known under the names of allethrin, bioallethrin, S-bioallethrin, cinerin, furethrin, dimethrin, benathrin *, kadethrin, prothrin (or furamethrin), proparthrin , tetramethrin, resmethrin, bioresmethrin, phenothrin, d-phenothrin, permethrin, biopermethrin, cypermethrin, bromethrin, decamethrin and fluorethrin. - 18 - 9. Device according to any one of claims 1 to 8 characterized in that at least one of the solid compositions contains an isopyrethrinoid chosen from Fenvalerate and fenpropanate. 10. Device according to any one of claims 1 to 9 characterized in that the isopyrethrinoid is present in a proportion * between 2 and 15 percent of the total weight of the composition * which contains it. 11. Device according to any one of claims 1 to 10 characterized in that the absorbent mass material is chosen from cellulose paper and cardboard composed of wood fibers, cereal fibers, alfa fibers, fibers of cotton, waste of old paper, asbestos fibers, glass fibers, wool fibers and / or polymeric fibers and among the terracotta, sintered aluminas and non-stretched porcelain. 12. Device according to any one of claims 1 to 11! [characterized in that the absorbent mass material is a plate! whose thickness is between 0.1 and 6 millimeters. 13. Device according to any one of claims 1 to 12 characterized in that the solid compositions are simply placed "one against the other without physical means of solidarisâtion. 14. Device according to any one of claims 1 to 12 characterized in that the solid compositions are joined together by a place chosen from adhesives, cements and stapling, nailing, embedding or metallic or plastic crimping. ) i ί • s' S - 19 - 15. Device according to any one of claims 1 to 12 \ characterized in that the compositions are formed by a single J i absorbent mass material in which each of the active substances, optionally accompanied by an inert adjuvant, is absorbed on a different part of the surface. 16. Device according to claim 15 characterized in that the different impregnated surfaces are separated by a free zone „of active substance. 17. Device according to claim 16 characterized in that the free zone of active substance is impregnated with a material having the function of eliminating the absorbent state of the bulk material. 18. Device according to claim 17 characterized in that said material is chosen from waxes, alkali silicates, natural resins and synthetic polymer resins. 19. Device according to claim 18 characterized in that said material is a polymeric resin formed in situ from a polymerizable material chosen from monomers, prepolymers and associations of compounds capable of reacting with each other to give polymeric resins. I " 20. Device according to claim 19 characterized in that I the polymerizable material is a monomer chosen from styrene, acrylic esters, maleic esters and cyanide: acrylic esters. 21. Device according to claim 20 characterized in that the polymerizable material is a prepolymer chosen from polyesters formed between dicarboxylic acids and polyols. ! I: Μ j j - 20 - i i 22. Device according to claim 19 characterized in that the polymerizable material is a combination of selected compounds! among those leading to the formation of resins of the epoxy, epoxy-ester, epoxy-phenolic, urea-formaldehyde, melamine-formo1 and polyurethane type. 23. An insect control pig, by the emission of insecticidal vapors, using a heating apparatus and characterized in that it uses a device consisting of several different solid compositions juxtaposed each comprising a substance | active on insects absorbed in a mass absorbent material,: said active substance being, in at least one of the compositions, chosen from isopyrethroids. 24. A method according to claim 23 using a device as defined by any one of claims 2 to 22. 0