FR2461456A1 - SYSTEMIC INSECTICIDE COMPOSITIONS WITH CONTROLLED DIFFUSION, PROCESS FOR THE PREPARATION THEREOF AND USE THEREOF - Google Patents

Abstract

SYSTEMIC INSECTICIDE COMPOSITION CONSTITUTED BY A RIGID OR FLEXIBLE HOMOGENEOUS MASS COMPRISING: A.OXIME CARBAMATE OF FORMULA: (CF DRAWING IN BOPI) R REPRESENTING AN RX- OR RXC (R) (R) GROUP - IN WHICH X REPRESENTS AN ATOM OF SULFUR OR A SULPHONYL REMAINDER, R AND R REPRESENT INDEPENDENTLY FROM ONE THE OTHER A HYDROGEN ATOM OR A METHYL OR ETHYL REMAINDER, R BEING CHOSEN FROM THE REMAINS METHYL, ETHYL, ISOPROPYL AND TERTIOBUTYL; B. A POLYVINYL CHLORIDE HAVING A MOLECULAR MASS GREATER THAN 10,000; C. A REGULATING AGENT CHOSEN FROM HYDROPHOBIC DILUENTS; AND D. OPTIONALLY AN ADDITIONAL REGULATORY AGENT CHOSEN FROM HYDROPHILIC THINNERS AND PULVERULENT FILLERS. THIS COMPOSITION, WHEN PLACED IN CONTACT WITH WET SOIL OR WATER, REGULARLY RELEASES DETERMINED QUANTITIES OF ACTIVE SUBSTANCE FOR A LESS OR LESS LAPS OF TIME.

Description

- 1 -

  SYSTEMIC INSECTICIDE COMPOSITIONS WITH CONTROLLED DIFFUSION

  PROCESS FOR THEIR PREPARATION AND USE

  The present invention relates to systemic insecticidal compositions which make it possible to obtain a controlled diffusion of the active agent in water or in soil, at the same time as the processes

  to obtain said compositions.

  The compositions targeted by the present invention contain a polymeric support and a systemic insecticidal substance of the

family of oxime carbamates.

  It is known to enclose active agents in a polymer matrix to allow slow diffusion in water or in the soil: thus, aicidal compositions (ANON, Chem.

  Eng. News, 1972, 50, no. 23, 68; CARDARELLI & BILLE, Rep. 1, Proj.

  121, Creative Biol. Lab., Baberton, 1976), fungicides (Br. Am.

  3,269,900 and 3,278,371), nematicides (CARDARELLI & FELDMESSER, Proc.

  Control Rel. Pest. Symp., Dayton, 1975, 386), herbicides (Br. Am.

  3,269,900 and 3,343,941; Br. Brit 1,502,441; Br. Canad. 846,785; Br.

  Franc. 2,016,818; YOUNG & NELSON, Sp. Study 31.004.69 / 70, Dept. Army, approx. Hyg. Ag., 1969; BARNES & WHITLAW, Proj. 31.004.69 / 70, Dept. Army

  Approx. Hyg. Ag, 1970; HARRIS & COLL., Weed Sci., 1973, 21, 318; SIN-

  CLEAR, Approx. Sci. Technol., 1973, 7, 955; CARDARELLI, Control Rel. Pest.

  Formul., CRC Press., 1976), molluscicides (CARDARELLI, Control Rel.Pest Pest.RTM., CRC Press, 1976) and antibacterials (Br.Americ.

258; Br. 2,016,818).

  With regard to insecticides, this process is less used. Compositions comprising a polymer and dichlorvos are known (MILES & COLL, J. Agr Food Chem, 1962, 10, 240) but 2 - these are intended for release into the atmosphere of the agent.

insecticide that is volatile.

  They are unusable in water and in the soil because this active substance is very easily and very rapidly hydrolysed. Such compositions based on other organophosphorus compounds such as azuiphos, bromophos, chlorpyrifos, demeton, diazinon, dimfox, dimethoate, fenitrothion, fenthion, malathion, mevinphos, monocrotophos, the naled, the

  parathion, temephos and trichlorfon or with organo-

  such as aldrin, dieldrin, endrin, heptachlor, iso-

  lindane and methoxychlor (Br.Am. 3,269,900 and 3,590,119; Br. Canada 846,785; Br. Fr. 2,016,818; CLEMENTS & ROGERS, Proc. 35th Ann. Conf. Calif. Mosq. Control, Ass., 1967, p.109, WHITLAW & EVANS, J. Econ, Entom., 1968, 61, 889, SCHULTZ & COLL, Mosq News, 1969, 2, 38, MILES & WOEHST, Pest. Res., Adv Chem., 1969, 86, 183, Mc DONALD & DICKENS, Mosq News, 1970, 30, 563, NELSON & COLL, J. Econ Ent., 1970, 63, 1870 and 1973. , 33, 403;

  MILLER & COLL., Mosq. News, 1973, 33, 148; ROBERTS & COLL., Mosq.

News, 1973, pp. 155 and 165).

  Aryl or heteroaryl carbamates such as dioxacarb, isolan, dimetilan, carbofuran and various substituted phenyl carbamates have also been used (Br.Am. 3,269,900; Br. Brit. 1,502

  441; Br. Canad. 846,785; Br. 2,016,818 and 2,279,336).

  None of these substances are of interest for oxime carbamates

  vis-à-vis plants; they can not be used in

  According to the invention, their release in water or soil is much too low as demonstrated in one of the experiments. On the contrary, oxime carbamates diffuse very easily from the compositions according to the invention; in addition, they act from the roots of plants, spread in all

  their vital parts and thus protect them from insect attacks.

2461 456

  There are known compositions using aldicarb and

  a polymeric support (Br Fr. 2 279 236, STOCKES & COLL., J. Agr.

  Food Chem., 1973, 21, 103), but this substance is extremely toxic.

  (LD 50 = 0.9 mg / kg) which makes it very dangerous to

  and takes away much of their interest. Also known are compositions based on aldicarb comprising a paper support and a coating of polyethylene glycol (CIBA-GEIGY, Br. Brit. 1 477 261) but,

  besides their great toxicity, their industrial implementation is

  cate, their use is difficult in spreading machines and

  their application on the sites to be treated is not easy, especially

in the presence of wind.

  Granules constituted by a polybasic support have also been used.

  and in an oxime carbamate such as methomyl (French Br.2016 818) but in this type of heterogeneous granule, the polymer acts by absorption and the amount of storage active substance depends on the specific surface area of said polymer which must therefore be porous this results in concentration limits and adjustment difficulties in

the Liberation.

  It has now been found by the Applicant that it is possible

  to produce homogeneous compositions containing a polyvinyl

  oxime carbamate much less toxic than aldicarb and

  that these compositions make it possible to obtain a diffusion of said carbamide

  mate, in water or in the earth, at a controlled rate.

  The invention therefore relates to the systemic insecticidal compositions constituting

  formed by a rigid or flexible homogeneous solid mass comprising A - an insecticidal material, B - a polyvinyl chloride having a higher molecular weight

at 10,000,

  C - a regulating agent chosen from hydrophobic diluents, D optionally, a complementary regulating agent chosen from hydrophilic diluents and pulverulent fillers,

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- 4 -

  said compositions being characterized in that the insect material

  ticide A consists of an oxime carbamate of formula

R RO ---- H - CH3 (I)

  in which R 1 is selected from the monovalent groups R'X- and R'-XC (R ") (R '") - in which X represents a sulfur atom or a sulphonyl residue, R' represents an ethyl residue of methyl, R "represents a hydrogen atom or an ethyl or methyl residue and R represents a hydrogen atom or an ethyl or methyl residue and R" 'represents a hydrogen atom or an ethyl or methyl residue, R being chosen from ethyl groups; isopropyl, methyl and tert-butyl. The systemic insecticidal materials defined above are described, in particular, in CIBA-GEIGY patents (FR 2,150; US Pat. No. 3,832,400), Consortium flee Elektrochemische Industrie (US Pat. No. 3,816,532), Diamond Shamrock Corp. (US 3,875,232), Dupont de Nemours & Co (US 3,576,834; 3,639,633; 3,647,861) and Kumiai Chemical

Industry Co. (JP 72.17 993).

  Among these, there may be mentioned, for example, the best known hereafter: (N-methylcarbamoyloxyimino) -2-methylthio-2-ethane (METHOYL) (N-methylcarbamoyloxyimino) -2-methylthio-3-butane (BUTOCARBOXI) E ( N-methylcarbamoyloxyimino) -2-methylsulfonyl-3-butane (BUTOXYCARBOXIMOE) (N-methylcarbamoyloxyimino) -2-dimethyl-3,3-methylthio-1 butane

(Thiofanox).

  The insecticide material that is preferred in the compositions

  according to the invention is the BUTOCARBOXY defined above.

  The insecticidal material A is preferably contained in a proportion by weight of between 5 and 50 parts per 100 parts of composition; even better, this proportion is between 10

and 40 parts.

  The polyvinyl chloride B is preferably contained in a proportion by weight of 20 to 70 parts per 100 parts of composition; even better, this proportion is between 30

and 50 parts.

  The addition of a regulating agent chosen from hydrophobic diluents makes it possible to vary, depending on their nature and quantity, the rate of release of the insecticidal material; this regulating agent must be chemically inert towards the insecticidal material. The hydrophobic diluents are chosen from the compounds

  have no hydrophilic function and are known in the plastics industry.

  ticks as having plasticizing properties. These compounds are,

  for example, low molecular weight polymers, paraffins

chlorinated and heavy esters.

  This regulating agent is preferably contained in a proportion by weight of 15 to 70 parts per 100 parts of composition; better

  still, this proportion is between 20 and 55 parts.

  Examples of low molecular weight polymers include those from the homopolymerization or copolymerization of the following monomers: (1) Homopolymerization: vinyl acetate, isobutylene and chlorinated ethylene: (2) Copolymerization: acrylonitrile / butadiene , diethyl / butadiene fumarate, ethyl acrylate / butadiene, vinyl acetate / ethylene, vinyl acetate / ethyl acrylate, vinyl acetate / dimethyl maleate, vinyl acetate / allyl acetate, vinyl chloride / styrene, vinyl chloride / allyl chloride and chloride

vinyl / vinyl acetate.

  The polyesters, preferably neutralized by esterification with an alkanol, such as those from the following condensations: glycerol / sebacic acid, may also be mentioned,

  glycerol / azelaic acid, glycerol / phthalic acid, propylene

  glycol / adipic acid and propylene glycol / sebacic acid.

  As examples of heavy esters, the following can be cited:

  (1) Monoesters formed between alkanols and alkaline acids

  or, for example, laurate, myristate, palmitate, stearate, undecanoate and ethyl oleate, isopropyl,

butyl or isobutyl.

  (2) Diesters formed between alkanols and dicarboxylic hydrocarbons such as, for example, dialkyl adipates such as dioctyl adipate, dinonyl adipate, dialkyl sebates such as dibutyl sebate, dipentyl and dioctyl sebacate, dialkyl azelates such as dioctyl azelate, dialkyl phthalates such as dibutyl phthalate, dioctyl phthalate, didecyl phthalate, bis (undecyl) phthalate, phthalate of bis (dodecyl), bis (tridecyl) phthalate, bis (tetradecyl) phthalate and

dicetyl phthalate.

  (3) The diesters formed between the alkylsubstituted or unsubstituted phenols and the dicarboxylated hydrocarbons such as, for example, diaryl phthalates such as diphenyl phthalate

and dicrésyl phthalates.

  (4) Diesters formed between cycloalkanols, substituted or unsubstituted alkyls, and dicarboxylic hydrocarbons such as, for example, dicyclohexyl phthalate and debt phthalates (methylcyclohexyl). - 7 -

  (5) The diesters formed between phenylalkanols and hydro-

  dicarboxylic carbides such as, for example, dibenzyl sebacate.

  (6) The diesters formed between alkanediols and monocarboxylic hydrocarbons such as, for example, trimethyl diisobutyrate

2,2,4-pentanediol-1,3.

  (7) Triersters formed between alkylsubstituted or unsubstituted phenols and phosphoric acid such as, for example, triphenylphosphate, tris (terbutyl-4-phenyl) phosphate and

tricresyl phosphates.

  (8) The triesters formed between alkanols and phosphoric acid

  as, for example, trioctyl phosphate.

  Hydrophilic diluents, acting as complementary regulating agents, may be present in a proportion by weight of 0 to 50 parts per 100 parts of composition. They are selected from miscible compounds, soluble or dispersible in water

  and physically compatible with the insecticidal material A, chlo-

  polyvinyl chloride and the hydrophobic diluent.

  As examples of hydrophilic diluents, the following may be mentioned: (1) Polymers and copolymers of vinyl alcohol such as polyvinyl alcohol and polyvinyl alcohol / acetate copolymer

of polyvinyl.

(2) polyvinylpyrrolidones.

  (3) Alkanediols such as 2,2-dimethylpropanediol-1,3,

  propylene glycol, butylene glycol, diethyl-2,2-propanediol-1,3.

  (4) polyalkanediols such as polyethylene glycols, polypropylene

  glycols and polybutylene glycols, (5) alkane-triols, such as glycerol, and their mono-esters formed with alkandic or alkenic acids. (6) Esters formed between aliphatic hydroxy acids and light alkanols such as trimethyl citrate, triethyl citrate,

tripropyl and tributyl.

  (7) The condensation products of propylene oxide or ethylene on alkylphenols, such as butyl, hexyl, heptyl, octyl, nonyl and dodecylphenols, on fatty alcohols, such as decanol, dodecanol, tetradecanol, hexadecanol, octadecanol and octadecenol, and on vegetable oils, such as

  palm, peanut, coconut, rapeseed, soya and castor oil.

  The pulverulent fillers are chosen from those inert with respect to water or, on the contrary, from those that are soluble or dispersible in water depending on whether it is desired to slow down or accelerate the

  diffusion rate of the active ingredient.

  Examples of pulverulent fillers are carbon black, rock powders such as slate, clay, marble, kaolin, talc, silica or atapulgite, organic salts such as acetates, propionates, citrates, adipates, maleates, sebacates, palmitates and stearates of magnesium, zinc, calcium and sodium, mineral salts such as calcium and magnesium silicates and carbonates and sodium or potassium chlorides sodium or calcium sulphates, potassium nitrate and potassium or ammonium phosphates; it can be cited also the sodium salts or

24 61456

  Calcium alkylarylsulfonic acids, cellulose and its derivatives such as methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, carbohydrates such as cereal flours, starch, dextrin and sugars, amino acids such as glutamic acid, casein and protein hydrolysates and the various organic pigments or

  minerals known to those skilled in the art.

  The compositions according to the invention are in homogeneous solid masses, compact, rigid or flexible, whose form is not critical. This can be for example, that of plates,

  leaves, ribbons, tubes, chopsticks or granules.

  The structure of the mass constituting the composition is not, either, critical; this structure can be for example, compact,

  fibrous, alveolar or spongy.

  When placed in contact with the soil or water, the compositions according to the invention release 50% of insecticide material in a very regular manner, in a period ranging between about 2 and 200 days. The yield of the compositions according to the invention relative to the total amount of insecticidal material included in the composition is excellent since almost all the material

  insecticide is released after a longer or shorter time.

  The compositions according to the invention can be prepared

following several methods.

  According to a first method, at a room temperature, the components are mechanically mixed using a polyvinyl chloride powder. According to the proportions of the constituents,

  a dry powder or a fluid paste is obtained, ie "plastisol".

246 1,456

- 10 -

  The dry powder is converted to a homogeneous solid mass by molding, extrusion, injection or casting as in the case of ordinary plastic powder. In the case of a fluid paste, it is heated to gelification and cooling results in a homogeneous solid mass; the diffusion rate of the active ingredient does not vary significantly according to the

  temperature and / or duration of heating.

  According to a second method, it is dissolved in a volatile solvent

  components A, B and C of the composition, the fillers

  when present, may be suspended in agitation. After evaporation of the volatile solvent, which can be done at a higher or lower temperature and under a more or less reduced pressure, the mixture is set in mass and results in a homogeneous mass retaining only a small portion

solvent.

  According to a third method, the polyvinyl chloride is dispersed in the state of sol in the mixture of constituents A and C previously heated. By cooling, we obtain a

homogeneous solid mass.

  According to a fourth method, constituents A and C are introduced into vinyl chloride or into a liquid semi-polymer of this compound. Polymerization is carried out according to

  methods known to those skilled in the art after addition of a catalyst.

  lyst. According to a fifth method, a solid mass of polyvinyl chloride having optionally the desired form for the final composition is placed in the liquid mixture of the constituents A + C. All or part of the constituent C can initially be found in

2 4 6 145 6

- i1 -

  polyvinyl chloride. If the composition is to contain a powdery filler, it is initially incorporated into the polyvinyl chloride. The active ingredient A and the adjuvant C, when the latter is mixed with the active ingredient, penetrate into the mass of polyvinyl chloride; this penetration requires a time that is inversely proportional to the temperature

  at which the operation takes place.

  According to a variant of this process, the mass of polyvinyl chloride and the constituents A + C are introduced into a packaging container impervious to said mixture, the internal volume of which is adapted so that the liquid mixture is in contact with the maximum surface area of the polyvinyl chloride mass. The penetration is during the storage period and the package contains a composition according to the invention at

  when it is open for employment.

  The interest of the compositions according to the invention is illustrated

  by the experiments that follow.

  246 i 45 6 - 12 Experiment 1: A mass of polyvinyl chloride was used

  plasticized with dibutyl phthalate and having a plastic content

  proud was close to 36% by weight. This mass was shaped, by extrusion, into a tube whose outer and inner contours of the cross-section were lenticular; the outside width was 28 mm and the greatest thickness was 3.2 mm for a length of 45 mm; the width of the interior walls

  was 20 mm; the weight of such a mass was 7.65 grams.

  Such masses have been unitarily enclosed in a sealed bag emptied of air before its closure and containing, as the case may be, one of the following liquids (quantities in grams):

Table I

  After storage for one month at a temperature of 40 ° C., the sachets were opened to deliver, in all cases, a mass whose homogeneous composition was as follows (percentages by weight):

Table II

  Composition 1B 1C_ Pure Butocarboxime 5 3.5 2.5 Dibutyl phthalate 1.5 2.5 Composition 1A 1B | C utocarboxime 39.5 27.7 19.8 Polyvinyl chloride 38.7 38.7 38.7 Dibutyl phthalate 21.8 33.6 41.5

- 13 -

  Experiment 2: Polyvinyl chloride in fine powder for plastisol was used which was mixed with technical butocarboxime, titrating 83% purity, and dioctyl phthalate in the following proportions: Technical butocarboxime: 20% by weight Chloride of polyvinyl: 40% by weight Dioctyl phthalate: 40% by weight The resulting fluid paste was cast in Petri dishes to a thickness of 2 mm and these were placed in temperature-controlled ovens for varying periods of time. between 5 and

  minutes and at temperatures varying between 115 and 135 C.

  In all cases, a homogeneous plastic mass was obtained and the contents of active ingredient, determined by the analysis, were noted

  as follows in percentages of pure active ingredient.

Table III

  These same analyzes made it possible to establish that only the volatile impurities of the technical matter had been lost

during heating.

  Experiment 3: Three series 3A, 3B and 3C of heating time were prepared 115 C 120 C 125AC 130 C 135 C minutes 16.6 16.6 16.6 16.6 16.7 minutes 16.6 16.7 16 , 7 16.7 16.7 minutes 16.7 16.7 16.7 16.7 16.7 minutes 16.7 16.7 16.7 16.7 16.7 minutes 16.7 16.7 16.8 16.8 16.8

2 46 145 6

- 14 -

  compositions according to the invention using the process described

  in Experiment 2 operating at 1250C for 15 minutes.

  The compositions thus prepared had the shape of discs 32 mm in diameter and 12 mm in thickness and were constituted as follows (values in percentages by weight):

Table IV

  The discs thus made have a vase filled with water and, periodically,

  spent in the water was measured.

  were each suspended in a quantity of active ingredient The following table summarizes the values thus recorded (percentages of active substance diffused with respect to the active ingredient introduced into the composition and weight of material

active in milligrams).

  Compositions 3A 3B 3C Technical butocarboxime 10 20 40 Polyvinyl chloride 45 40 30 Dioctyl phthalate 45 40 30 Weight of each disc 8,53 8; 19 7,80 (grams) 246i456

- 15 -

Table V

  Experiment 4: 4A, 4B and 4C disks were used such as those described in Experiment 3 and respectively

the same compositions.

  These discs were each placed in sand whose water content was close to 20% and periodically the percentages

  scattered active ingredient were measured.

  The results of the measurements are summarized in the table below.

Table VI

  Maturities of measures 3A 3B 3C i% mg% mg% mg day 12 102 13 211 19 593 9th day 16 137 18 295 25 774 th day 24 206 26 429 37 1160 day day 36 309 41 676 53 1647 day 114 49 417 54 881 56 2068 194th day 61 518 65 1068 77 2412 Deadlines 4A 43B 4C% Z mg Z mg z mg Ms. day11 | 93 13 | 237 | 14 440 Same day 22 188 27 496 31 967 114th day 34 292 38 695 42 1317 194th day 43 365 47 869 51 1604. 246 i456

- 16 -

  Experiment 5: A composition was prepared as follows (percentages by weight): Technical Butocarboxime Polyvinyl Chloride 40 Dioctyl Phthalate 40 The method described in Experiment 2 was used (15 minutes at 125 ° C); discs with a diameter of 90 mm, varying in thickness, were obtained:

Table VII

  These discs were each placed in sand whose water content was close to 20% and periodically the percentages

  scattered active ingredient were measured.

  The results of the measurements are summarized in the table below.

Table VIII

  Compositions 5A 5B 5C 5D 5E Thickness in mm 1 2 3 5 7 Weight in grams 6, 8 13.8 20.9 34.8 48.9 Measurement times 5A 5B I 5C 5D 5E% mg% I mg Z mg. mg 8th day 19.2 260 13.2 364 9.0 375 8.4 525 7.8 763 th day 37, 1 505 25.7 709 19.7 824 16.8 117C 14.4 1407 22nd day 54.5 741 37.1 1024 2847 1200 24.5 1705 1.0 2054 29th day 65.2 887 46.7 1289 36.5 1526 30.5 2123 5.7 2515th day 80.8 1100 62.9 1736 51.5 2153 43.7 304035.1 3433 th day 89.8 1220 76.6 2115 67.0 2800 55.9 3890 5.3 4430

  __ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ __ _ _ _ _ _ _ _ _ _ _ _ _ _ -.... -. L - -. - I

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  Experiment 6: The procedure was as in Experiment 2 (15 minutes at 125 ° C.) to prepare the following compositions 6A to 6D which were in the form of discs 90 mm in diameter and 1.5 mm in thickness ( values in percentages by weight):

Table IX

  The discs were each placed in sand with a water content of about 20% and periodically times of active material were measured and weighted. whose

the percentages

that their

  The results of the measurements are summarized in the table below.

Paintings

  Compositions 6A 6B 6C 6D Technical Butocarboxime 20 20 20 20 Polyvinyl Chloride 60 50 40 30 Dioctyl Hthalate 20 30 40 50 Weight (grams) 13, 83 13.75 13.76 13.56 Timing of 6A 6B 6C 6D measurements% mg % mg% mg% mg 8th day 0.4 11 8.4 231 18.0 495 19.8 537th day 3.0 83 15.0 412 32, 8 890 37.7 1023 22nd day 6.6 183 22, 8 628 45.5 1251 55.7 1512 29th day 9.0 249 26.9 740 54.5 1501 67.7 1835 th day 7.9 495 41.3 1137 71.0 1954 86.8 2355 th day 5, 1,693 54.5 1497 81.1 2232 98.0 2659

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  Experiment 7: The procedure was as in Experiment 2 (15 minutes at 125 ° C.) to prepare the following compositions 7A and 7B which were in the form of discs 90 mm in diameter and 2 mm in thickness (values in FIG. percentage by weight):

Table XI

  The discs were each suspended in a vase filled with water and, periodically, the percentages of active ingredient

broadcast were measured.

  The results of the measurements are summarized in the table below.

Table XII

  Experiment 8: The procedure was as in Experiment 2 (15 minutes at 125 ° C.) to prepare the following compositions 8A and 8B, which were in the form of discs 32 mm in diameter and 12 mm in thickness (percentage values by weight): Compositions 7A 7B Technical butocarboxime 20 Polyvinyl chloride 40 40 Dioctyl phthalate 35 20 Tris (2-butoxy-ethyl) phosphate Weight (grams) 13, 63 13.52 Measurement times 7A 7B% | mg% _mg 2nd day 12 323 20 512 th day 50 1330 53 1450 12th day 74 2025 83 2273

_ _ .. _1-

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- 19 -

Table XIII

  (a) Polyvinyl acetate, 30% hydrolyzed to polyvinyl alcohol and having a viscosity of 98 centipoise in 4% solution

in water at 20 C.

  The discs were each suspended in a vase filled with water and, periodically, the percentages of active ingredient

  spent in the water were measured.

2O

  The results of the measurements are summarized in the table below.

Table XIV

  Experiment 9: The procedure was as in Experiment 2 (15 minutes at 125 ° C.) to prepare the following compositions 9A to 9F which were in the form of discs 90 mm in diameter and 2 mm in thickness (values in FIG. percentages by weight): Compositions 8A 8B Technical butocarboxime 40 40 Polyvinyl chloride 25 25 dioctyl hthalate 25

PVA Copolymer (a) 10 -

  Polyethylene glycol 400 - 10 Weight (grams) 8,45 9,54 Deadlines 8A L_ 8B | % mg Z% mg day 18,2 615 17,5 670 31st day 53,2 1800 46,4 1770 93rd day 81,4 2750 66,3 2530 173rd day 98,2 3320 82,4 3145

- 20 -

Table XV

  (a ') Polyvinyl acetate, 50% hydrolyzed and having a viscosity of 98 centipoise

in water at 20 C. (a ") Polyvinyl acetate hydrolysed to 70% and having a viscosity

88 centipoises

in water at 20'C.

  polyvinyl alcohol in solution at 4% polyvinyl alcohol in solution at 4% The discs were placed each in a vase filled with water and, periodically, the percentages of active ingredient diffused

have been measured.

  The results of the measurements are summarized in the table below.

Table XVI

  Compositions 9A! 9B 9C 19D 19E 9F Technical butocarboxime 20 20 20 20 20 Polyvinyl chloride 37 37 34 34 30 30 Dioctyl phthalate 37 37 34 34 30 30

PVA polymer (a ') 6 - 12 - 20 -

  PVA polymer (a ") - 6 - 12 - 20 Weight (grams) 13.60 13.57 13.58 13.60 13, 63 13.63 Time limits 9A 9B 9C 9D 9E 9F measurements% mg% mg% mg % mg% mg% mg 2nd day 15 410 22 590 16 440 27 736 18 496 33 897 th day 28 755 30 817 29 782 48 1314 34 924 61 1668 12th day 49 1340 51 1390 53 1445 77 2090 63 1712 91 2473

- 21 -

  Experiment 10: The procedure was as in Experiment 2 (15 minutes at 125 ° C.) to prepare the following compositions 10A to 10E which were in the form of discs 90 mm in diameter and 2 mm in thickness (values in percentages by weight):

Table XVII

  The discs were each suspended in a vase filled with water and, periodically, the percentages of active ingredient

broadcast were measured.

* The results of the measurements are summarized in the table below.

Table XVIII

  Experiment 11: The procedure was as in Experiment 2 (15 minutes at 125 ° C.) to prepare the compositions 11A and 11B. Compositions 1OA 1OB 10C 10OE Butocarboxime Technical 20 20 20 20 Polyvinyl chloride 40 40 40 40 40 Dioctyl phthalate Polyethylene glycol 400 5 - 10 - 20

  Ethyltriethylene glycol -5 - 20 -

  Weight (grams) 13.57 13.51 13.61 13.32 13.50 Timeouts of 10A 0LB 10C 10D 10E measurements% mg% mg% mg% mg% mg 2nd day 11 295 13 353 13 354 13 341 40 1045 3rd day 17 466 - - 19 512 - - 87 2354 th day 26 714 43 1160 33 904 46 1230 100 2690 12th day 48 1308 64 1707 56 1532 71 1886

- 22 -

  following in the form of 90 mm discs of

  diameter and 2 mm thick (values in percentages by weight).

Table XIX

  The discs were each suspended in a vase filled with water and periodically the percentages of active ingredient diffused were measured.

  The results of the measurements are summarized in the table below.

Table XX

  Measured time 11A llB% mg% mg 2nd day 13 350 20 550 day 49 1350 52 1430 12th day 74 2030 76 2080 Experiment 12: The procedure was as in Experiment 2 (15 minutes at 125 C) to prepare the compositions 12A to 12F which were in the form of discs 90 mm in diameter and 2 mm thick (values in percentages by weight): Compositions 11A 11B Technical Butocarboxime 20 20 Polyvinyl Chloride 40 40 Dioctyl Phthalate 35 20 Citrate tributyl 5 20% (grams) 13.68 13.59

- 23 -

LXI Table

  The discs were each suspended in a vase filled with water and, periodically, the percentages of active ingredient

broadcast were measured.

  The results of the measurements are shown in the table below.

after.

Table XXII

  Experiment 13: The procedure was as in Experiment 2 (15 minutes at 125 ° C.) to prepare the following compositions 13A to 13F which were in the form of discs 90 mm in diameter and 2 mm thick (percent values by weight): Compositions 12A 12B 12C 12D 12E 12F Technical butocarboxime 20 20 20 20 20 20 Polyvinyl chloride 37 37 34 34 30 25 Dioctyl phthalate 37 37 34 34 30 25

Corn pastry 6 - 12 - 20 -

  Starch - 6 - 12 - 30 Weight (grams) 13.55 13.60 13.64 13.56 13.70 13.52

Sequencing i2A 12B 12C 12D 12E 12-

  Z mg 2 mg mg mg Z mg mg 2nd day 16 427 17 467 16 431 19 512 16 436 43 1170 3rd day - - 20 545 - - 26 703 - - 52 1410 day 36 980 30 822 43 1167 41 117 52 1418 80 2158 12th day 61 1660 53 1438 70 1914 79 151 96 636 10 2690

- 24 -

Table XXIII

  The discs were each suspended in a vase filled with water and, periodically, the percentages of active ingredient

broadcast were measured.

  The results of the measurements are summarized in the table below.

  Table XXIV Experiment 14: The procedure was as in Experiment 2 (15 minutes at 125 ° C.) to prepare the following compositions 14A and 14B which were in the form of discs 90 mm in diameter and 2 mm in thickness ( percentages by weight): Compositions 13A 13B 13C 13D 13E 13F Technical butocarboxime 20 20 20 20 20 Polyvinyl chloride 37 37 34 34 30 30 Dioctyl phthalate 37 37 34 34 30 30

Methylcellulose 6 - 12 - 20 -

  Sodium salt of carboxymethylcellulose - 6 - 12 - 20 Weight (grams) 13,56 13,55 13,56 13,49 13,6 13,48 Time limits 13A 13B 13C 13D 13E 13F measures Z mg Z mg Z mg Z mg Z mgZ mg 2nd day 13 347 15 412 15 400 25 680 17 463 43 1163 3rd day - - 22 602 - - 33 888 - - 54 1452 day 37 1006 36 971 39 052 43 1155 65 1772 87 2346 day 12 60 1636 53 1432 70 906 79 2126 00 2706 100 2679

2 4 6 1456

- 25 -

Table XXV

  The discs were suspended, each in a vase filled with water and, periodically, the percentages of active ingredient

broadcast were measured.

  The results of the measurements are summarized in the table below.

Table XXVI

  Experiment 15: The procedure was as in Experiment 2 (15 minutes at 125 ° C.) to prepare the following compositions 15A and 15B which were in the form of discs 90 mm in diameter and 2 mm in thickness (values in FIG. percentages by weight): Compositions 14A 14B Technical butocarboxime 20 20 Polyvinyl chloride 37 25 Dioctyl phthalate 37 15 Casein 6 40 Weight (grams) 13.56 13.76 Measurement times 14A 14B% mg% mg 2nd day 13 350 16 446 day 35 - 943 43 1191 day 12 56 1510 80 2213

- 26 -

Table XXVII

  Compositions | 15A 15B Technical Butocarboxime 20 Polyvinyl Chloride 50 Dioctyl Hentate 30 34 PVA (a ") - 12 (a") Polyvinyl acetate 70% hydrolyzed and having a viscosity of 88 centipoise

in water at 20 C.

  polyvinyl alcohol in 4% solution at p The discs were cut into four equal quarters having

  each weighing about 3.5 grams.

  Each district was placed in the open field in a limonous land.

  Stony clay at a depth of 7.5 centimeters. Rainfall

  average metry during the period of the experiment was to

3.15 millimeters a day.

  Periodically, one quarter was removed from the soil and the remaining amount of butocarboxime was measured by analysis to determine the

quantity diffused into the soil.

  The results of the measurements are summarized in the table below.

  The results of the measurements are summarized in the table below.

246i'456

- 27 -

Table XXVIII

  Expiry date 15 A 15B% nig% mg 8th day 5 36 21 150 th day 9 62 40 278 th day 12 85 59 414 36th day 19 130 71 495 th day 26 184 83 579

64th day 31 218 - -

  71st day - - 92 646 78th day 39 276 94 660

- 28 -

  Experiment 16: Seven series of compositions 16A were prepared at

  16G according to the invention using the method described in the ex-

  feeding 2 and operating at 125 C for 15 minutes.

  The preparations thus prepared had the shape of discs of mm diameter and 2 mm thickness and were constituted as follows (values in percentages by weight):

Table XXIX

16A 16 6C 16D 16E 16F 16G

  Technical butocarboxime 20 20 20 20 20 20 Polyvinyl chloride 38 38 38 38 38 38 38

Dioctyl phthalate 42 - - - - - -

  Dioctyl Adipate - 42 - _ 10 10 -

  Dioctyl sebacate - - 42 - - - -

  Tricresyl phosphate - - - '42 - - -

  Triethyl citrate - - - - 32 _ -

Tributyl citrate - - - - - 32 -

  Tris (butoxy-2 - - - - - - ethyl) phosphate Average weight of a disc 13.29 13.16 13.25 13.45 13.42 13.57 13.0 (grams) The discs thus produced were each placed in sand with a water content of about 16.7% and periodically

  percentages and weights of diffused active ingredient were measured.

  The results of the measurements are shown in the table below.

after.

246 1,456

- 29 -

Table XXX

  9th day 35th day 60th day% Mg mg% mg% mg

16A 18.1 480 52.1 1385 62.1 1650

16B 24.1 635 51.7 1360 65.0 1710

16C 26.4 700 48.1 1275 60.0 1590

16D 13.8 370 35.3 950 46.7 1255

16E 22.0 590 43.4 1165 47.1 1265

16F 25.1 680 54.9 1490 66.5 1805

16G 52.4 1365 82.3 2145 89.8 2340

  Experiment 17: Three series of 17B and 17C according to the invention were prepared using compositions 17A, the method described

  in Experiment 2 and operating at 125 ° C. for 15 minutes.

  The preparations thus prepared had the shape of discs 90 mm in diameter and 2 mm thick and were constituted as follows (values in percentages by weight):

Table XXXI

  The discs thus made were sand whose water content was close to each placed in

16.7% and, periodically

17A 17B 17C

Butoxycarboxime 20 - -

Methomyl - 20 -

  Thiofanox - - 20 Polyvinyl chloride 38 38 38 Dioctyl phthalate 42 42 42 Average weight of a disc 13.95 13.84 13.93 (grams)

- 30 -

  the percentages and weights of the active ingredient

been measured.

  The results of the measurements are summarized in the table below.

Table XXXII

  Experiment 18: Seven series of compositions 18A were prepared at

  18G using the method described in Experiment 2 (15 minutes).

  at 1250C) and using insecticidal substances

  foreign to the scope of the invention.

  The preparations thus prepared had the shape of discs 90 mm in diameter and 2 mm thick and were constituted as follows (values in percentages by weight): 9th day 35th day 60th day% mg% mg% mg

17A 0.6 17 2.3 64 5.1 142

17B 24.7 685 52.4 1450 65.6 1760

17C 4.5 125 17.0 475 21.7 605

- 31 -

Table XXXIII

  Carbaryl (b) Chlorpyrifos (c) Diazinon (d) Fenthion (e) Malathion (f) Naled (g) Temephos (h) Polyvinyl chloride Dioctyl phthalate Average weight of a disc (grams)

13.95 113.38

13.98 113.94

14.02 113.861 13.96

  (b) Alphanaphthyl N-methylcarbamate (c) O-Diethyl Thiophosphate and O- (3,5,6-trichloro-2-pyridyl)

  (d) O-diethylthiophosphate and O- (n-propyl-2-methyl-6-pyrimidine)

  dinyl-4) (e) O-dimethyl thiophosphate and O- (3-methyl-4-methylthiophenyl) (f) O-dimethyl dithiophosphate and S- [bis (ethoxycarbonyl) 1,2 ethyl] (g) 0.0-Dimethyl phosphate and 0- (dibromo-1,2-dichloro-2,2) ethyl

  (h) bis (thiophosphate) of 0,0,0 ', 0'-tetramethyl and 0,0' - (thiodiphenyl)

  NYLENE-diyl-4,4 '); this substance is often referred to as

name of "Abate".

  The disks thus produced were each placed in sand whose water content was close to 16.7% and, after 9 days, 35 days and 60 days, the quantities of active ingredient diffused were

measured.

246 1456

- 32 -

  In no case and at any time was it possible to

  find an active ingredient emission exceeding 0,05% of the quan-

implemented.

  Experiment 19: A composition according to the invention was prepared

  using the method described in Experiment 2 and operating at 1250C for 15 minutes with the following constituents: Butocarboxime 35.3% Polyvinyl chloride: 35.0% Dioctyl phthalate: 19.8% PVA polymer (a ') "') 9.9%

  Polyvinyl acetate hydrolyzed to 88% polyvinyl alcohol

  with a viscosity of 18 centipoise in solution at

4% in water at 20C.

  This composition was formed into 4 mm thick plates that were cut to obtain cubic granules of

4 mm edge.

  The granules were buried near the rose bushes of the variety Red Favorite located in a clay-siliceous soil of the

  department of Vienne in France.

  Three doses were used: 30.45 and 67 grams per rose.

  A watering of 6 liters of water per rose was made three times per

  week. After 15 days, the leaves of the rose bushes were

  crushed and extracted for their insecticidal content. The following contents have thus been established:

- 33 -

  dose 30 grams: 35 ppm dose 45 grams: 60 ppm dose 67 grams: 75 ppm It was further established that these levels were sufficient

  to prevent the proliferation of aphids on plants.

  Experiment 20: The six compositions from 20A to 20F were prepared

  according to the invention using the method described in the ex-

  feeding 2 and operating at 125 C for 15 minutes with the following constituents (values in percentages):

Table XXXIV

  (i) Starch modified with carboxymethylation and pregelatinization.

  These compositions were formed into 4 mm thick plates.

  which have been cut to obtain cubic granules

4 mm edge.

  The granules of each composition were spread over the

  face of the earth pots 11 cm in diameter each containing a

  plant of the species Hibiscus rosasinensis; after application, granules

  were slightly covered with soil and a

A 20B 20C 20D 20E 20F

  Technical Butocarboxime 35.3 23.5 14.7 35.3 23.5 14.7 Polyvinylchloride 38.8 45.9 51.2 35.0 35.0 35.0 Dioctyl phthalate 25.9 30.6 34.1 19.8 27.7 33.5 Maize starch - - - 9.9 13.8 16.8 solubilized (i)

246 1,456

- 34 -

  watering with one liter of water per pot; the amount of each composition was calculated to correspond to 50 mg of butocarboxime per pot: A and. 20D B and. 20E C and 20F 167 mg 250 mg 400 mg The plants were infested with aphids of the species Myzus persicae and the insecticidal efficacy was measured periodically

  for 35 days. Five plants were used for each composition.

  The results after and expressed in the quantity noted at the averages noted for: Table XXXV

  recorded are summarized in the table below.

  percentages of dead insects compared to first day; the given values are the

  each position on all five plan-

  ) 20A 20B 20C 20D 20E 20E day 3 55 59 49 57 86 69 day 7 71 76 69 79 95 89 12th day 76 75 62 82 91 90 day 16 93 84 79 90 96 94th day 90 79 77 89 95 90 24th day 93 80 85 85 93 95 28th day 87 79 74 77 82 74 th day 79 74 72 69 79 67

2 4 6 14 5 6

- 35 -

Claims (19)

claims   1. A systemic insecticidal composition consisting of a rigid or flexible homogeneous solid mass comprising A - an insecticidal material, B - a polyvinyl chloride having a higher molecular weight at 10,000,   C - a regulating agent chosen from hydrophobic diluents, D optionally, a complementary regulating agent chosen from hydrophilic diluents and pulverulent fillers,   said compositions being characterized in that the insect material   ticide A is constituted by an oxime carbamate of formula: R1-r = N-O-CO NH CH3 (I)   wherein R is selected from monovalent groups R'X -   and R'-XC (R ") (R" ') - in which X represents a sulfur atom or a sulphonyl radical, R' represents a methyl or ethyl radical, R "and R" 'represent independently one of the another a hydrogen atom or a methyl or ethyl residue, R2 being selected from   the methyl, ethyl isopropyl and tert-butyl residues.   2. Composition according to claim 1, characterized in that it contains the insecticidal material A in a proportion of   weight of between 5 and 50 parts per 100 parts of composition.   3. Composition according to claim 2, characterized in that it contains the insecticidal material A in a proportion by weight of between 10 and 40 parts per 100 parts of composition. - 36 -   4. Composition according to any one of claims 1 to 3,   characterized in that it contains polyvinyl chloride B in a proportion by weight of 20 to 70 parts per 100 parts decomposition.   5. Composition according to claim 4, characterized in that it contains polyvinyl chloride B in a proportion   by weight of 30 to 50 parts per 100 parts of composition.   6. Composition according to any one of claims -1 to 5   characterized in that it contains the regulating agent C in a proportion by weight of 15 to 70 parts per 100 parts of composition. 7. Composition according to claim 6, characterized in that it contains the regulating agent C in a proportion by weight   from 20 to 55 parts per 100 parts of composition.   8. Composition according to any one of claims 1 to 7,   characterized in that the insecticidal material A is selected from (N-methylcarbamoyloxyimino) -2-methylthio, -2-ethane, (N-methylcarbamoyloxyimino) -2-methylthio-3-butane, (N-methylcarbamoyloxyimino) -2-methylsulfonyl-butane,   and (N-methylcarbamoyloxyimino) -2-dimethyl-3,3-methylthio-1-butane.   9. Composition according to claim 8, characterized in that the insecticidal material is (NX-methylcarbamoyloxyimino) -2 3-methylthio butane.   10. Composition according to any one of claims 1 to 9,   characterized in that the regulating agent C is selected from low molecular weight polymers, chlorinated paraffins and heavy esters. 2 46 1 45 6 - 37 -   11. Composition according to any one of claims 1 to 10 characterized in that it contains a hydrophilic diluent, as complementary regulator, selected from polymers, polyols and miscible esters, soluble or dispersible in water and among the polyoxyalkylated products.   12. Composition according to any one of claims 1 to 11,   characterized in that it is in the form of a solid mass,   homogeneous, compact, rigid or flexible of any shape.   13. Process for preparing a composition according to one of   any of claims 1 to 12, characterized in that the   powdered polyvinyl chloride B is mechanically mixed at room temperature with compounds A and C of the   obtain a dry powder or a fluid paste which is then trans-   formed into a homogeneous solid mass by molding, injection or casting   or by heating to the gelling temperature of the mixture.   14. Process for the preparation of a composition according to one   any of claims 1 to 12, characterized in that the   components A, B and C are dissolved in a volatile solvent which is then evaporated at a higher or lower temperature or reduced pressure.   15. Process for the preparation of a composition according to one   any of claims 1 to 12, characterized in that one   disperses in the form of sol, the polyvinyl chloride in the liquid mixture of the constituents A and C previously heated and in that after obtaining a homogeneous dispersion is allowed to cool The mixture.   16. Process for the preparation of a composition according to one   any of claims 1 to 12, characterized in that one   introduced components A and C into vinyl chloride or 246 1456 - 38 -   a semi-polymer of this compound and which is then carried out   a polymerization of the mixture after addition of a catalyst.   17. Process for the preparation of a composition according to one of the   Claims 1 to 12, characterized in that a mass is placed   solid polyvinyl chloride having the desired form for the final composition in the liquid component A which optionally contains the component C if it is not already   contained in polyvinyl chloride and in that   penetrate all liquids in the mass of polyvinyl chloride   for a period of time inversely proportional to the temperature.   18. The method of claim 17, characterized in that the constituents A + C are introduced into a packaging container, impermeable to said components A + C, the internal volume is adapted so that the liquid mixture is in contact with the maximum surface area of the solid mass of polyvinyl chloride, the package then being closed and then stored for a sufficient time so that it no longer contains free liquid at the end of the storage period.   19. Use of a composition according to any one of   Claims 1 to 12 as a systemic insecticidal composition   to obtain a controlled diffusion of the active agent in water or in the ground.