FI57338C - FOER BEKAEMPNING AV SKADEDJUR ANVAENDBARA PRODUKTER MED DEPOT-GASVERKAN - Google Patents

Description

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Federal Republic of Germany Förbundsrepubliken Tyskland (DE) P 2U50677.2 "(71) Bayer Aktiengesellschaft, Leverkusen, Federal Republic of Germany Förbundsrepubliken Tyskland (DE) (72) Wolfgang Behrenz, OveFath-Steinenbriick, Krefeld

Federal Republic of Germany-Förbundsrepubliken Tyskland (DE) (7U) Oy Kolster Ab (5U) Pesticide preparations with a stored gas effect - För bekämpning av skadedjur användbara produkter med depot-gasverkan

The invention relates to novel preparations for controlling pests which have a stored gas effect. The new preparations consist of the formula CH 0 f J ^ P-O-CH = CCl? dimethyl 2,2-dichlorovinylthiophosphate according to ch3o as an automatic gas phase active gasifier, as well as solid carriers.

The use of dimethyl 2,2-dichlorovinyl phosphate (DDVP) as a self-gassing agent in pest control has long been known. A wide variety of substances, macromolecular thermoplastic, hard and soft flexible active substances or natural substances such as wood, cardboard, asbestos, lime, gypsum, beeswax and montan wax have been proposed as carriers for the latter field of action. Examples of suitable carriers further include natural rubber and synthetic rubber, polyolefins such as polyethylene, polypropylene and copolymers of ethylene and propylene, polyacrylates and mixed polyacrylate of methyl acrylate, ethyl acrylate and methyl methacrylate; polyvinyl compounds such as polystyrene, polyvinyl toluene, polyvinyl acetate, polyvinyl and polyvinylidene halides such as polyvinyl chloride, polyvinyl fluoride, polyvinylidene ester and polyethyl chloride, cellulose propionate, cellulose butyrate, cellulose nitrate, in addition, suitable carriers are, for example, unsaturated polyesters, epoxides, polyurethanes, phenol-formaldehyde, urea and melamine-formaldehyde resins.

Particularly preferred carriers are polymers and copolymers of vinyl chloride (cf. German Patent Publication DT-AS 1 230 259) and unsaturated polyester systems (cf. DT-AS 1 69h 2 0 0 and German Publication Publication DT-OS 2 231 099); in addition, polymeric acrylates and polymeric vinyl compounds such as polystyrene.

In addition to the active ingredient, these preparations often contain, depending on the nature of the carrier, excipients such as plasticizers, stabilizers, evaporation regulators and fillers. Suitable plasticizers are, for example, dioctyl phthalate, alkoxysulfonic acid carbyl ester, trioctyl phosphate, triphenyl phosphate, dibutyl adipate, chloroparaffin, diisononyl phthalate, di-2-ethylhexyl ladipate, di-2-ethylhexyl, di-2-ethyl Suitable stabilizers include, for example, phenols, amines or lower nitrogen-containing heterocyclic compounds, further azo and hydrazo compounds, acid anhydrides, epoxides and elemental sulfur (DT-OS 2 1U5 318); in addition, substances commonly used to stabilize macromolecular substances, such as, for example, organic cadmium and lead compounds as thermal stabilizers for polyvinyl chloride.

Suitable evaporation regulators are, for example, palmitic acid ethyl ester, myristic acid isopropyl ester, di-n-butyl phthalate, 2-chloronaphthalene, camphor, benzoic acid, biphenyl, isobutylbenzoate and others, such as those described in e.g. German Patent D OSS? 1 951+ 501, 2 026 119 and 2 028 226.

Fillers may include, for example, glass, sisal, hemp, nettle, coconut and game fibers; in addition, titanium dioxide, iron oxides, kaolin, quartz and other inert minerals.

These preparations are most often used in the form of shaped bodies, such as sheets, slabs, strips, rods, spheres, foams, strips, films, tablets or granules. If, in use, such a shaped body is brought into the living or bedroom of a house or placed in the neck of a domestic animal, the DDVP contained in the preparation is gradually released into its vapor pressure or using heat sources, e.g. (cf. DT-AS 1230 259 »British patent GB-PS 1 015 933; South African patent 62/371; DT-AS 1 69b 2k0; DT-OSS 19 9 1 0h6 and 2 231 099; DT-AS 1 802 681 +).

The moldings may then be used either directly or surrounded by guards (enclosures) that can be fully or partially opened or closed to interrupt the delivery of the DDVP from time to time or to control the amount of material to be released.

5 The problem with using DSVPs in these self-acting gasifiers is now that the delivery of the affected area must be controlled so that, on the one hand, enough room air is released to ensure the killing of the parasites, but on the other hand, people and enclosures are not harmed. Substances that are less toxic to mammals than DDVP therefore represent a major technological advance, especially for this purpose.

Or, in addition to DDTP, South African Patent 62/371 also describes combinations with a large number of other phosphoric acid esters and with corresponding thiophosphates, with the exception of DBVP, no other compound has gained practical importance in this regard. As for thiophosphates, it is stated in JDT-AS 1,230,239 that they are less compatible with the macromolecular substance than in the case of thiophosphates. phosphoric acid esters. Furthermore, it is generally known that thiophosphoric acid esters have a lower insecticidal ability than the corresponding phosphates. The worse insecticidal effect of dimethyl 2,2-dichlorovinylthiophosphate, hereinafter briefly referred to as thio-DDVP, compared to DDVP, is demonstrated by the following comparative experiment1

The aerosol-test

My test animals are Musea domestlca

Solvent Acetone

In order to obtain an appropriate effect, the area of action is mixed with the given solvent in a series of different concentrations.

A wire cage with about 23 experimental animals is hung in the middle of a 1 m 2 counting chamber. After the chamber is resealed, 2 ml of the active ingredient preparation is dusted. The condition of the experimental animals is continuously monitored through the glass walls from the outside and the time required to stun 30 i »animals is observed.

The amount of time taken, the amounts of use and the time after which 30 i »of the animals have gone on their backs, (LT ^ 0) are shown in Table 1 below.

table 1

The aerosol-test

Area of application Application rate LT-q mg / m * DDVP 1 10 · 37 "thio-BDVP 1 19 '15'1 2 13'37" 3 11'40 "4 9'20” «57338

Therefore, it is not surprising that the above publication provides an example of the use of thio-DDVP and that the area of influence is mentioned as an example of rain flux within the list.

Thus, it has been found that thio-DDVP can be advantageously used as an active ingredient in DDVP as a active ingredient in luminaires having a stored caustic effect when used in combination with kiltalp carriers as a self-acting gas phase-acting gassing agent for pest control.

Such preparations include, but are not limited to, thio-DDVPx and acromolocyclic thermoforming, bad elastic or hard forging material (duronaarla) or natural materials such as wood, cardboard, asbestos, lime, gypsum, feldspar, feldspar, felt, felt.

In addition to the preservative, the the finished guarantees, depending on the nature of the base and the substance, also contain the aforementioned auxiliaries, such as plasticizers, stabilizing agents, volatilization control agents, substances which prevent or promote it, and fillers. The talcum is used in the form of shaped pieces such as sheets, slabs, strips, rods, balls, foams, strips, films, tablets, necklaces or slits. We may be surrounded by coatings that allow for the delivery of an adjustable full or reduced range of influence. Particularly advantageous for the use of thio-DDVP according to the invention is the lower toxicity of the degradation results and possible by-products of the domain of action to warm-blooded animals, as can be seen from the following Table 2s 1 »^ lylrlfft 9 U> 50 Rats t

Acute oral toxicity DDVP 62 mg / kg thio-DDVP 773 mg / kg LC50 Rat Rat

Acute inhalation toxicity, when DDVP 340 mg / n? (4-hour exposure) thio-DDVP> 477 mg / n5 + + animals in this experiment at the highest possible concentration tolerated asymptomatically.

5 57338

The preparations according to the invention, which are based on thio-DDVP as a self-acting gassing agent and on solid carriers, can be used for controlling a wide variety of pests. Thio-DDVP for use as an active ingredient according to the invention is known from the literature and can be prepared according to the method described in German Public Procurement Publication DT-OS 2 238 921.

The following examples further illustrate the invention and in which "parts" mean parts by weight.

Examples 1 and 2 each use as a carrier a mixture of U1 + 0 parts of unsaturated polyester (prepared by polycondensation of 205.8 parts of maleic anhydride, 725, 2 parts of phthalic anhydride, 5, 6.6 parts of 1,2-propanediol and 0.265 parts of hydroquinone with an acid number of k2) and 2H0 parts of styrene (polyester blend 1).

In Examples 3 and U, a mixture of 730 parts of unsaturated polyester (prepared by polycondensation of 262.8 parts of maleic anhydride, 926.8 parts of phthalic anhydride, 612 parts of 1,2-propanediol, 359.6 parts of dipropylene) is used as the carrier. 0.21 parts of hydroquinone with an acid number of 3.9) and 350 parts of styrene (polyester blend 2).

Example 1 A homogeneous premix is prepared from 680 parts of a polyester blend 1, 390 parts of thio-DDVP, 230 parts of an alkane sulfonic acid aryl ester and 27 parts of maleic anhydride. Add a portion of a 10 # solution of dimethylaniline in toluene and prepare a casting sheet having a glass fiber content of 26 # by heating for about 30 minutes at 80-100 ° C in a closed mold with a fiberglass mat (600 g / m). The plate is then cut into shaped pieces measuring 8 x 25 can. The active ingredient content is 20 g.

Example la (Comparative example)

As described in Example 1, however, using DDVP as the active ingredient, shaped bodies having dimensions of 8 x 25 cm and an active ingredient content of 20 g are prepared.

Example 2 A homogeneous premix is prepared from 630 parts of · polyester blend 1 and U50 parts of thio-DDVP. Add 36 parts of benzoyl peroxide in a phthalate plasticizer (50- #), and prepare a casting sheet with an asbestos content of 3.5% by weight by heating n.

30 minutes at 80-100 ° C in a closed mold filled with granular asbestos particles. The plate is then cut into shaped pieces measuring 8 x 25 cm and having an active ingredient content of 38 #.

6 57338

Example 3 A homogeneous premix is prepared from 665 parts of polyester blend 2 and U75 parts of thio-DDVP. Add 38 parts of benzoyl peroxide in a phthalate plasticizer (50%) and prepare a casting sheet with a tissue content of 26% by weight by heating for about 30 minutes at 80-100 ° C in a closed mold with polyacrylonitrile fiber fabric (280 g / l). m). The plate is then cut into shaped pieces measuring 8 x 25 cm and each having an active ingredient content of 2 kg.

Example 3a (Comparative example)

In the same manner as in Example 3, but using DDVP as the active ingredient, a homogeneous premix and shaped bodies of the same size containing the same range of effect are prepared.

Example U

A homogeneous premix is prepared from I + 38 parts of polyester blend 2 and 299 parts of thio-DDVP. Add 26 parts of benzoyl peroxide in a phthalate plasticizer (50 /?) And prepare a casting sheet with a tissue content of 26% /? By heating for about 30 minutes at 80-100 ° C in a closed mold with jute tissue (150 g / l). m. The plate is then cut into shaped pieces measuring 8 x 25 cm and each containing 25 g of active substance.

Example Ua (Comparative Example)

In the same way as in Example U, but using DDVP as the active ingredient, a homogeneous premix and shaped bodies of the same size with the same active ingredient content are prepared.

Example 5 8 x 25 cm shaped moldings are made from 3 mm thick cardboard and impregnated with thio-DDVP. The proportion of active substance in the cardboard is 30 g.

Example 6

The shaped body made according to Examples 1 and 1a is each placed in a finely made mesh cover and hung in the middle of similar 50 m rooms on the ceiling. U weeks later, 200 Musca dcmes-tica flies are counted in the room. In the room with the shaped body according to Example 1, the flies died after 2 hours, and in the room with the shaped body according to Example 1a, only after 3 hours.

Example 7

The shaped body prepared according to Examples 3 and 3a is each placed

O

to a net-like enclosure and hung in equal rooms of Uo nr from ceiling to red. Immediately thereafter (0) and after 4, 8 and 12 weeks, 200 flies of Musca domestica are released into the room. Flies do not come into direct contact with shaped bodies. One hour after the introduction of the flies, the percentage of animals that have fallen on their backs is determined. The results obtained are shown in the following Table 3: «'i * 7 57338

Tan Iti If Ien *

The age of 56 animals on the back of the shaped bodies, weeks after 1 hour

DDYP thio-DDVP

0 80 100 4 70 95 8 60 90 12 20 50

Example 8

The shaped body prepared according to Example 4 d * 4 * is each placed in an open-porous housing and hung open in the room. After 2 weeks, the mold prepared according to Example 4 is first introduced into a 45 m 2 room and released from 300 Muso domestioa flies. Determine the time after which 100 ^ flies are on their backs. The room is then thoroughly ventilated and the same experiment is performed on moldings made according to Example 4a. The results obtained are shown in Table 4>

Table 4

Shape The time after which, from the example, 100 pounds of animals are on their backs 4 2 hours 4 »5 hours

Claims (9)

8 57338 Pesticide preparations having a stored gaseous effect, characterized in that they consist of dimethyl-2,2-dichlorovinylthiophosphate of the formula CH3 ° J NP-O-CH = CCl_ / d CH30 as a self-acting gas phase gasifier and solid carriers. Preparations according to Claim 1, characterized in that thermoplastic active substances are used as carriers. Preparations according to Claim 1, characterized in that thermosetting plastics are used as carriers. Preparations according to Claim 1, characterized in that elastomeric substances are used as carriers. Preparations according to Claim 1, characterized in that natural substances, such as cellulose, keratin, asbestos, lime and gypsum, are used as carriers. Preparations according to Claims 1 and 5, characterized in that cardboard, wood or felt is used as natural substance. Preparations according to Claims 1 to 6, characterized in that mixtures of different carriers are used. Preparations according to Claims 1 to J, characterized in that the combination additionally contains auxiliaries and / or fillers, such as plasticizers, stabilizers, anti-evaporation or promoter substances, glass or textile fibers, pigments, colorants, perfumes and quartz. Formulations according to Claims 1 to 8, characterized in that they are provided with covers for adjustable full or reduced release of the active ingredient.