DE2236735A1 - BIOCIDE AGENTS - Google Patents

Description

"Bioeide means"

The invention relates to new biocidal agents, comprising vinyl phosphoric esters, hydroxylated polymers, with these Esters are compatible, and optionally thermoplastic Resins. The invention also relates to a method of controlling entropic pests in one place Use of the new funds.

It is known that vinyl phosphoric esters are biologically active. It is also known to be used to combat certain Pests are effective and act by touching, ingesting or inhaling the fictitious ester. These connections can be formulated in a plasticizing resin such as plasticized polyvinyl chloride. This phosphorus

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Ester carcinogens slowly release the active ester into the atmosphere and are also effective at Pest Control (U.S. Patent 3,318,769). Resin preparations, which slowly release a biocidal agent into the atmosphere are referred to below with terms referred to as "slow release preparation", 'Slow release agents', or simply 'agents'.

During slow-release preparations of the active ingredient due to their ease of use, application and consumer convenience have proven effective with the use of a phosphoric ester in a plasticized resin such as polyvinyl chloride there are still certain disadvantages associated with it. So is e.g. the amounts of active ingredient such as dimethyl 2,2-dichlorovinyl phosphate (DDVP), which is practically combined with such a plasticized polyvinyl chloride resin can be relatively low. That means that the agent has a slow release of active ingredient the basis of this preparation must be relatively large so that it activated the required amount Phosphorus ester contains »Associated with the size of the agent and the content of active ingredient in the plasticized resin is the surface area that the surrounding atmosphere is required for the diffusion of the activated phosphoric ester. To a sufficient Sustaining strong release of the biocidal substance over a period of time is a relatively large surface area required in relation to the size of the agent. However, this leads to an increased initial release of the biocidal substance when it is necessary. A-

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Another disadvantage of the known agents is that the plasticized resin cannot retain the active ingredient in sufficiently high concentrations. At concentrations required for effectiveness, a certain amount of the active phosphoric ester binds with atmospheric moisture, resulting in uncomfortable wetness or bleeding of the surface of the agent. Difficulties also arise in the processing of the combination of plasticized polyvinyl chloride resin and activated phosphoric ester, Z ₀ Bo is required for extrusion of the known agents, a fairly high temperature, which led to a loss of part of the activated phosphoric ester a limitation with regard to the size and shape of the means from the known masses.

It has now been shown that means comprising a with a phosphoric ester compatible hydroxylated polymer and a phosphorus-containing ester, in which a smaller amount of this ester with the hydroxylated polymer reacted to form a \ * - crosslinked polymer do not have these disadvantages of the known preparations.

The invention therefore relates to a biocidal agent comprising a mixture of a phosphoric ester of the formula:

(I) ~ ⁴ 209886/1322

in which R and R ^{1 are} each independently alkyl, alkenyl or alkynyl groups with up to 12 carbon atoms, cycloalkyl groups with 3 to 8 carbon atoms, aryl, alkaryl, aralkyl or aralkenyl groups with 6 to 15 carbon atoms, which are replaced by halogen _} lower alkoxy, nitro, hydroxy, amino, alkylamino or dialkylamino groups can be substituted, η 0 or 1, X an oxygen or sulfur atom, Y a hydrogen or alogen atom and Z a halogen atom or a group:

0 0 R "

Il H •

-C-NHR "or -COCH (

in which R "has a hydrogen atom or an alkyl group up to 6 carbon atoms and R '"a hydrogen atom, is phenyl or halopbenyl, and A is Denote hydrogen atom, an alkyl group with up to 6 carbon atoms, a phenyl or halophenyl group, with a hydroxylated polymer compatible with the ester and having a molecular weight of 30,000 to 1,000,000, with a minor portion of the ester forming a crosslinked polymer with the polymer responded.

It is not clear whether the phosphorus is in this network

is covalently bonded to the hydroxylated polymer or in the form of a solid complex. The in such a

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However, the amount of phosphate contained in the network is in of the order of about 0.5 to 5% by weight, below normal conditions, but it can increase with curing time and temperature. The crosslinking contributes largely to the gel strength of the means while the bulk of the phosphate ester is not attacked. These gel-like agents contain larger amounts of phosphorus compounds per unit area than the known agents have a more solid cross-linking processed to low-cost agents that have a low surface area per unit of active ingredient, have good storage stability and resistance to bleeding. In addition, this can Means can be easily processed at relatively low temperatures and poured into any desired shape or shaped.

The new preparations have a better diffusion coefficient and can contain relatively large amounts of phosphoric esters, they are with a smaller one Surface area effective, resistant to bleeding and can be made to be less initially of the biocidal agent. They can also be more easily brought into different sizes and shapes v / ground than the known preparations.

The hydroxylated polymers used for the invention Agents that are suitable are those with phosphoric esters are compatible »Under the term" compatible "or" compatibility "is meant the ability of two or more Understanding substances that they form with each other

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a homogeneous mass can be mixed, which has suitable plastic properties or that such substances can be intimately mixed with one another (see Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd edition, vol. 15 »p. 750). The invention is not intended to a specific group or groups of hydroxylated polymers, but it appears that three criteria are decisive for the polymer.

1. The polymer must match the phosphoric ester used be compatible »

2. The polymer must contain hydroxyl groups.

3. The polymer must have a molecular weight in the range of be about $ 0,000 to 1,000,000.

The invention is not limited to any particular group or groups of polymers, but it is believed that all polymers are useful provided they meet the meet the criteria given above. For example, the following groups of hydroxylated polymers are suitable: Polyvinyl acetate, such as polyvinyl formal, polyvinyl acetal, Polyvinyl butyral and polyvinyl valeral, the hydroxyl groups contain; Polyvinyl esters such as polyvinyl acetate and polyvinyl butyrate containing hydroxyl groups; Mixtures of polyvinyl acetal and polyvinyl esters with hydroxyl groups; Terpolymers of vinyl chloride with vinyl esters, which contain hydroxyl groups; Copolymers of partially

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wise hydrolyzed vinyl chloride and polyvinyl acetate ξ hydroxylated cellulose ethers _} such as hydroxypropyl cellulose, ethylene-vinyl acetate copolymers with hydroxyl groups; hydroxylated polybutadiene5 hydroxylated block copolymers such as SBS rubber; hydroxylated polyethylene and polypropylene and / copolymers, as well as hydroxylated copolymers of vinyl acetate and acrylic esters, such as polyethyl methacrylate and polyethylene methacrylate.

Preferred hydroxylated polymers because of their Easily accessible are the hydroxylated polyvinyl acetals and polyvinyl esters, such as polyvinyl butyral and hydroxylated polyvinyl acetates and mixtures thereof. These compounds can be represented by the formula:

CH ₂ CH

OH

CH ₂ -CH O

C = O Τ «

wherein Y is a Wasserstoffatora _s sine alkyl, haloalkyl or hydroxyalkyl group having 1 to 8 carbon atoms, · an alkenyl group having 2 to 8 carbon atoms, a halogen atom or a hydroxyl group, Y ¹ represents an alkyl group having 1 to 8 carbon atoms and a, b and c are numbers representing the relative percentage weight

- 8th

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proportion of acetal, hydroxyl and ester groups in the Specify polymer. These groups are statistically distributed over the molecule. To create a network between the To achieve polymer and the phosphoric esters, it is necessary that the polymer has a certain number of hydroxyl groups contains. As will be discussed in more detail, the number of hydroxyl groups varies from polymer to polymer. polymer and cannot be precisely defined. Therefore, in the above formula, b is preferably at least and especially from about 3 to 35 »however, it can too up to 97 and more, provided that the specified conditions regarding compatibility and Molecular weight are met, a and c are integers from 0 to 99 and preferably from 3 to 97 · The sum of a + b + c is 100, preferably a is about 80, b is about 18-20 and c is 0-2.

The number or percentage of hydroxyl groups in the polymer can vary and depends on the species the polymer used and the compatibility of this polymer with the phosphoric ester. It is also possible, to choose a polymer that does not yet contain hydroxyl groups, but groups that easily convert into hydroxyl groups can be transferred. In such a case, the hydroxyl groups can be in situ before or during gel formation are formed. In general, the number of

Hydroxyl groups in the polymer, calculated as —-fCHpCHOH-}

Groups should be as low as 1.0% by weight, based on the Total polymer, with the upper limit for the hydroxyl group content exclusively through the requirement of

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tolerance is determined. - ■

Phosphorus compounds used with preference according to the invention are those of the formula I, where R and E ^{1 are} alkyl groups, η 1, Z is a halogen atom and A is a hydrogen atom.

Typical such compounds are dimethyl - !, 2-dichloro ~ vinyl phosphate (DDVP) and diethyl ~ 2-chlorovinyl phosphate.

The crosslinking reaction is acid catalyzed. The acid can be either an organic or inorganic acid
be. Examples of typical acids are hydrochloric acid, nitric acid, sulfuric acid, sulfonic acid, phosphoric acid, phosphorous acid and others. The acid is preferably a phosphoric acid, which is a hydrolysis product of the
Reaction used is phosphoric ester- If the phosphoric ester is not produced and in an anhydrous environment
is stored, there is usually enough moisture in the atmosphere that the phosphoric ester partially hydrolyzes and forms a catalytic amount of the corresponding phosphoric acid. If no catalytic amount of. If acid is present, the reaction does not proceed and no crosslinking takes place. It is believed that the crosslinking reaction proceeds according to the following scheme.

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OH

.0

R "

xc / ¹

- X - C-C

Ά. ^ j H +

t 0

RO-P = X OR '

RO-P = X

X-C = C

or

Ht-

0 t

RO-P = X

R ¹ OP = X

ι or X-P -

0 ι

X - C = C, A

UPSi.

11 -

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Gel formation can be achieved by adding as little as 0.5% by weight of the hydroxylated polymer on the weight of the total remedy.

The maximum amount of hydroxylated polymer that can be used in gel formation depends on the special polymer and the phosphoric ester used.

There must be sufficient liquid phosphoric ester to produce a uniform mixture. In other words, there must be sufficient liquid phosphoric ester around each hydroxylated polymer particle that the polymer surface is completely wetted. If, au much polymer is used, the mixture contains wet and dry spots and does not form a uniform gel structure "In general, appear to about 35 wt .-% Λ hydroxylated to polymer of the favorable range au his"

The gels are made by physically mixing the hydroxylated polymers with the activated phosphoric ester prepared in the presence of a catalytic amount of an acid. After mixing, the mixture is liquid and can be cast into any desired geometric shape or extruded and hardened. The temperature, mixture ext and curing time depend of the specific polymer and the phosphoric ester used away. Higher temperatures lead to a faster erosion Gel formation and hardening than low temperatures “Higher Proportions of hydroxylated polymer, based on the activated Phosphorestcr, also lead to a faster gel formation. Therefore, if with proportionate

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Al

moderately larger amounts of hydroxylated polymer worked it will be beneficial to carry out the mixing at lower temperatures in order to make the mixture sufficient to keep liquid for a long time to allow careful mixing and pouring into the desired shape.

Gels can also be made or regenerated, by making a pre-formed crosslinked polymer or gel from which the phosphoric ester partially or completely removed with a new amount of the liquid phosphoric ester t ranks.

The gels have different viscosity and are flexible or elastic. Since only a smaller toil of the phosphoric ester connected to the hydroxyl-localized polymer the greater part of the boarding remains unchanged. When the vapor pressure of the phosphorus eater is high enough is, the ester diffuses from the gel-like crosslinked polymer into the surrounding atmosphere. Esters with lesser Vapor pressure diffuse to the surface of the gel and, if the ester is removed from there, e.g. by rubbing, new ester diffuses to the outside. The esters can also be leached from the gel, e.g. by leaching the gel exposed to a suitable liquid.

Since many phosphoric esters have biocidal activities and since the rate of release of the ester from the Gel-like cross-linked polymer takes place over a predictable long period of time, these gels are excellent slow release biocidal agents

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Wii \ kstoffs.

The total rate of release of the phosphoric ester from the gel-like network structure at any given time depends on the temperature of the gel and the environment, the concentration of the phosphoric ester in the gel, the size the free surface of the gel and the speed of migration of the phosphoric ester from inside the Gels to the surface, this latter stage being the rate-limiting step. At a certain temperature and size of the agent, the rate of release depends on the Ability of the phosphoric ester to diffuse from inside the gel to the surface. This rate of change depends on a proportionality coefficient, the so-called diffusion coefficient.

One of the disadvantages of the known insecticidal preparation with slow release of the active ingredient is that the diffusion coefficient is low and limited. Therefore, in order to maintain a steady rate of release of an insecticide from the

Means that are to be used for a longer period of time to control pests, certain strictly limited geometric shapes are observed. The usual geoB; etrischo shape is that of a strip of plasticized PVC, which contains certain amounts of a ß-halophosphate, such as Contains DDVP as a biocidal substance. The strip is · rectangular; and must because of the low diffusion coefficient one, verhal-tnisiaäßis large surface and one thin

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λ *

Have a suitable cross-section

To achieve the rate of diffusion of an effective amount of the biocidal agent from the agent to the surface. Due to the low diffusion coefficient it corresponds to the emission of the pesticide into the surrounding atmosphere for such a preparation is essentially an exponential one Curve with a relatively high emission speed at the beginning, which drops to a relatively constant speed. With these well-known Preparations is only a very limited flexibility in the rate of release from such Funding possible due to the limitation, the required fixed geometric shape and the Diffusion coefficient is necessary.

If the initial release of the biocidal substance from the known PVC agents is just above the minimum Effective range, the diffusion coefficient is so low that the diffusion of the biocidal agent from the agent becomes inappropriately low long before the biocidal substance has escaped from the resin matrix. if - on the other hand, the well-known PVC agents in rooms or to be used effectively over a long period of time in another environment is initially a high rate of release of the pesticidal substance into the atmosphere required, followed by a gradually slowing permanent release. All these Preparations allow an even more safe application of pesticides. However, the speed of the

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Release to a Loss of Pesticide The high initial rate is unnecessary to the insects to combat and the volatile pesticide can be physically removed from the treated area and chemically through decomposition lost through moisture. Therefore, the PYC preparations always set something at the beginning and a short time afterwards Free more pesticide than the minimum required to be effective. That doesn't just lead to one unnecessary loss of the pesticide, but also significantly reduces the life of the preparation. Because of the limitations in manufacturing it is difficult and in some. In cases impossible to use a PVC insecticide agent with a much thicker profile with a smaller surface area to manufacture the initial one Decrease release rate and, yourself if it were possible, the biocidal agent would be proportionate due to the low diffusion coefficient short time with an inappropriately low. Speed to be released from the medium »

A great advantage of the agents according to the invention is the ability to reduce the rate of release of the to regulate biocidal substance from the gel-like means much better, compared to the known means » For comparison, gel-like agents can be produced that initially have fewer biocidal agents per unit of time release than the known agents, but which are effective for as long or even longer than the known » This is achieved through the properties of the gel-like masses

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and especially by, the higher diffusion coefficient, which is achieved through the gels. Due to the higher diffusion coefficient, the biocidal substance diffuses easier from inside the gel to the surface. It is therefore possible to make the gels in different geometric Manufacture molds with much thicker profiles than the known means. This fact along with the ability of the gels to contain more biocidal substance per unit weight than the known agents and more easily Being processable enables compositions to be made that are more compact in shape and therefore smaller Surface than the known means for a similar application. Hence it is through a scheme the content of biocidor substance, the size of the agent, the surface area and the diffusion coefficient possible to produce gel-like agents which have the desired initial release rate, and which the biocidal substance over a long time

Rait a biocid effective rate to release. These variations are not possible with the known preparations.

Except for the concentration of hydroxylated polymer and phosphoric ester can be the diffusion coefficient for a specific gel mixture by adding a Plasticizer of the known type can be varied. This leads to a better way of regulating the selection a special gel with the desired release rate for the biocide into the atmosphere and allowed

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also greater flexibility "in the choice of Size and shape of the remedy. The addition of the plasticizer also serves other purposes. The presence of the plasticizer reduces the rate of gelation and makes those mixtures that tend to gel quickly, more easily processable. The plasticizer is used also as a diluent for the phosphate esters and thus reduces the toxicity of the gel preparation.

Generally speaking, the addition of the plasticizer leads to an increase in the diffusion coefficient. A higher one Diffusioncoe.efficient makes it possible to reduce the surface area of an agent, thereby reducing the geometric shape becomes more compact.

The plasticizers that can be used are those that are customarily used for plasticizing or for plasticizing thermoplastic Resins such as polyvinyl chloride (PVC) can be used. These plasticizers are generally of two different types, i.e., phosphate esters and esters of polybasic carboxylic acids. The phosphate esters are preferably proportionate not very volatile and do not have any easily cleavable groups. These connections can be displayed by the formula:

ß ° 0 0

P - OH ⁰

E ⁰ O

in which the groups ß ° can be the same or different and

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each represent a hydrocarbon group ", such as an alkyl, aryl, aralkyl or alkaryl group with preferably at least 4 carbon atoms. These esters are essentially non-volatile but have excellent softening properties for the resulting Middle. Because of their similar composition, they are gel-like with the activated phosphoric esters Medium well tolerated. Typical phosphate esters are the triaryl phosphates, such as tricresyl phosphate, triphenyl phosphate, Tri (p-tert-butylphenyl) phosphate, tri (biphenyl) phosphate, o-biphenylyl diphonyl phosphate and cresyl diphenyl phosphate; the tri-alkyl phosphates, such as tri-ii-butyl phosphate, Tri-2-ethylhexyl phosphate, tri-n-octyl phosphate and trilauryl phosphate and such mixed phosphates, such as 2-ethylhexyl diphenyl phosphate and the like. Typical Examples of esters of polybasic carboxylic acids are Phthalate esters, such as dioctyl phthalate, mphenyl phthalate, Dicyclohexyl phthalate, diethyl phthalate and the dihexyl phthalates; the sebacates such as dibutyl sebacate, Dipentyl ™ sebacate, n-butylbenzyl sebacate and dibensyl sebacate; the Adipates such as dioctyl adipate, dicapryadipate, diisobutyl adipate and dinonyl adipate and the citrates such as tributyl citrate. Because of their ready accessibility, they are generally dioctyl adipate, dioctyl phthalate and Tricresyl phosphate are used.

According to the invention, other constituents such as dyes, fillers, fragrances or other bio-oils can also be added be added to the gel mixture.

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Another important advantage of the gels according to the invention is the fact that these agents are very resistant to "bleeding" or "exudation", which terms are synonymous. These terms refer to the formation of droplets of liquid on the surface of a biocidal agent at a slow rate of release. Phosphoric esters, especially DDVP _5, are hygroscopic and when they hit the surface of an agent. diffuse, they can react with water from the environment, with droplets of hydrolysis products being formed on the surface of the agent. This problem does not essentially exist with the preparations according to the invention.

A distinct advantage of the gels is _Φ that the size in proportion to the speed at the exit of the ester from the crosslinked gel, decreases _o This makes it possible, _s based on the occurred shrinkage measure the still present in the gel Estermenge au "; For example, an insecticidal phosphoric ester such as DDVP _{5 can} interact with a hydroxylated polymer to form a gel ₃ that is manufactured in spherical form and then placed over a cylindrical opening Has a diameter of ₉ which is larger than that of the opening. The change in the position of the ball on the opening gives an indication of the degree of release of the phosphoric ester from the ball. The relative dimensions are chosen so that at the point at which an ineffective amount dos insecticids

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So

is released, the ball falls through the opening. Various other possibilities result from this for a display of the quantity dispensed. One of the disadvantages of the currently commercially available resins containing a Slowly releasing insecticide consists in it it is not possible to determine when the effective amount of the insecticide has been delivered. 80 lead the Inventive means to solve this problem.

The gels of the invention are effective for killing inyertebrate pests, including various microorganisms, roundworms, mites, spiders, ticks and insects by exposing them to the compositions of the invention. E.g. the funds can be in the form of .Medallions are made, the peton around the neck are hung, releasing phosphoric ester for a period of time, which normally occurs on such animals Ectoparasites to be found, such as fleas and ticks, are combated. In addition, the invention Means are used in the form of granules or beads, which are applied to the soil by adding the slow, even release of the phosphoric ester from the means to combat various soil pests, such as Kenyan desolate, groundworms, root veins (rootworws) etc. leads. The gels according to the invention can also be used as fumigants in storage tanks, grain containers, etc. be used. The main use of the gels, however, is to have any desired geometric shape in a ger.chloo3e.aon Reum, e.g. a Zimmer, brings, v; cdi: rch through the constant {■ bodily Alv

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from phosphoric ester into the atmosphere all pests present in the room, e.g. houseflies and mosquitoes, ■ be fought.

The agents according to the invention can also be thermoplastic Contain resin, which is optionally plasticized or plasticized. Although the networking to the gel strength while it contributes the bulk of the phosphoric ester does not attack, the gel is strongly solidified by the presence of the thermoplastic resins.

Among thermoplastic resins are those thermoplastic To understand polymers which have a molecular weight of preferably over 1,000 and which are at room temperature are firm. Typical such siblings are polyolefins, such as polyethylene, polypropylene and their copolymers; Acrylate surfaces, such as polymethyl acrylate, polyethyl acrylate, polymethyl methacrylate, Polyethylene ethacrylate and their copolymers; Vinyl resins such as polyvinyl acetate and polystyrene; Polyvinyl halides, such as polyvinyl chloride and its copolymers; Polyvinylidene compounds such as polyvinylidene chloride; synthetic or natural elastomers, such as Hevea brasiliensis, cis-1,4-polyisoprene, polybutadiene, SBR rubber and copolymers of such rubbers; Cellulose plastics, such as cellulose acetate, cellulose butyrate, cellulose nitrate, etc. The choice of resin depends on the special phosphoric ester and hydroxylated polymer with which it is to be mixed or prepared and the conditions under which the end product is used will.

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The resins with which the dialkyl-ß-halogen-substituted Vinylphospliate are best tolerated and therefore "are preferred are solid polyvinyl resins, i.e. resins, in which the monomers polymerize via the vinyl double bond are. Typical such resins are polyvinyl halides such as polyvinyl chloride, which is the term also includes other polymers containing polyvinyl chloride such as polyvinyl chloride-polyvinyl acetate copolymers; the Polyacrylate and polymethacrylate esters, such as polymethyl acrylate and poly (methyl methacrylate) and their copolymers and the polyvinylbenzenes such as polystyrene and polymerized vinyl toluene. Among other things, they have the most favorable physical properties with the best compatibility with dialkylß-halogen-EU-substituted Connect vinyl phosphates and compatible with most of the hydroxylated polymers The most preferred resins are the polyvinyl chlorides.

The plasticizers used to plasticize the resin are those mentioned above, preferably dioctyl adipate or dioctyl phthalate.

The preparations, which also include the thermoplastic Resins are dry elastic gels, which generally contain from about 10 to 80% by weight of phosphoric ester, 0.5 to 30% by weight hydroxylated polymer, 5 to 60% by weight of a thermoplastic resin and Ό to 50% by weight of one Plasticizer for the thermoplastic resin included. Preferred quantity ranges are 20 to 50% by weight of phosphoric ester, 1 to 15% by weight hydroxylated polymer, 20 to 55% by weight

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thermoplastic resin and 15 to 35 Gexir .-% plasticizer for the resin.

The gel production of the agents containing the thermoplastic resin consists in first mixing the thermoplastic resin "the phosphoric ester and the plasticizer for the resin with a catalytic amount of an acid in a mixer and then quickly adding the hydroxylated polymer with further mixing." To avoid the formation of voids, a slight vacuum is applied while mixing. The mixture is then quickly poured into a mold of any shape and the gel image is formed within a few minutes made a dry mixture hei ^ and cured in the extrusion _o the gel-forming time varies $ e according to the relative proportion of the components in the mixture, the gel time is all the more long, is the more contain thermoplastic resin, "in addition, higher temperatures lead to faster hardening and Gel & ting al s lower temperatures _o One of the advantages of using a thermoplastic resin into the erfindungsgeinäßen means "is that ₅ may thereby achieve better Variationsbreite'in the Gerbildungsgeschwindigkeit t * = ground,

The gel must be thermally hardened * - in order to achieve maximum toughness «. The hardening time and temperature naturally depend on the particular ingredients used to make this preparation * Z ₀ B ₀

_ 24 ~

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will a gel that is about 2? % By weight DDVP, 36% by weight dioctyl adipate as plasticizer, 27% by weight polyvinyl chloride and 10% by weight hydroxylated polyvinyl butyral, and weighs approximately 50 to 75 g ', advantageously within approximately 30 minutes at a temperature of about 150 G ⁰ cured. Therefore, the formulations are normally cured thermally after the ingredients have been mixed. The application of heat serves to melt the thermoplastic polymer and allow it to fuse evenly with the other components of the formulation. Through this stage the agent is converted from the foam of a flowable paste to a sewing elastic plastic. The thermal curing of the agents can be carried out either by the application of heat, such as in an electric furnace, or by irradiation, for example with microwaves.

Microwaves are very short radio waves ranging in length from 0.1 to 1,000 cm. As part of the electromagnetic Spectrum / ground by »Scnderöliren for radio frequency, such as magnet tubes, klystrons or amplitons. In contrast to thermal heating that propagates inward from the surface of the sample, microwaves penetrate through the matter, v.'obie they lead to heating of the entire volume. Such heating is quick and uniform within the whole crowd. As a rule of thumb it can be said that an amount of energy of 100 V / att.sec / g for hardening is required. The use of microwaves does not change the physical properties of the gel-making process, before

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resembled preparations hardened in the oven, as later is still being shown.

The gels can also be prepared or regenerated by adding a previously formed mixture of a crosslinked polymer and a thermoplastic resin or gel, from which the phosphoric ester partially or completely has emerged, DiIt a wider amount of the liquid phosphoric ester soaks.

The "gels" have different degrees of toughness and are "bendable or elastic. Because only a smaller one Part of the phosphoric ester with the hydroxylated polymer isfc bound to form a phase of the crosslinked gel, most of the ester in the resin is unchanged. The thermoplastic resin containing the second polymer has a strong affinity for the phosphoric ester and the ester can be dispersed through and through.

An advantage of the means that in addition the thermoplastic Resin contain, is that they additionally have an increased gel strength - due to the thermoplastic resin own. The thermoplastic resin also serves to give a wider variation in the diffusion coefficient. With a very low concentration of thermoplastic resin, the diffusion coefficient is essentially unchanged and is the main advantage consists in an increased strength, which results from the addition of the second polymer to the system.

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However, if the proportion of thermoplastic polymer is in As the gel preparation increases, the diffusion coefficient decreases away. By finding the optimal ratio between thermoplastic resin, plasticizer, hydroxylated polymer and Choosing phosphoric ester allows one to set the desired pricing rate the biocidal substance from the Ge]. reach.

The diffusion coefficient of the gels from a phospho-ester and a hydroxylated polymer can therefore be varied by adding a thermoplastic resin and it can be varied further by a plasticizer of the known type for plasticizing . Plasticization of thermoplastic resin. This enables better control in the selection of a particular gel that has the desired rate of release of the biocidal substance into the atmosphere. In addition, it leads to greater gel strength and greater flexibility in the choice of the size and poim of the agent. As stated above, the thermoplastic resin decreases the diffusion coefficient, while the addition of the plasticizer makes the thermoplastic resin softer and increases the diffusion coefficient. In the presence of a thermoplastic shark ?? and the plasticizer slows the rate of gelation, making those mixtures which tend to gel rapidly, more easily processable. In addition, the thermoplastic resin and plasticizer serve as a diluent for the phosphorus ethers, thereby reducing the cost and toxicity of the gel formulation.

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even

The problem of bleeding is / in. such preparations, which contain the resin, essentially not present «, For example, as little as 1% hydroxylated polymer can be used sufficient to prevent the formation of surface fluid in a gown, which is mainly phosphoric ester, thermoplastic Contains resin and plasticizer, to reduce *

The invention is illustrated in more detail by the following examples. .

The following example shows a method of manufacture of polyvinyl acetals with free hydroxyl groups. A 500 cm three-neck flask, the one with stirrer, internal thermometer and reflux cooling lex was provided with 300 cnr

Ethanol, 10 g polyvinyl alcohol, 25 g Paraldeyhd and

3 cur an aqueous. 1: 1 ~ HG1 solution charged, "The reactants were stirred for 30 minutes' at 78 ⁰ G, wherein the solids dissolved completely to form a clear solution, the solution was 72 h to stand at room temperature · The product was then precipitated in water containing a small amount of KH ^ OH, and redissolved in ethanol. Reprecipitation in water gave a fine white powder which was collected and dried in a vacuum oven for 18 hours. which contained about 20% by weight of OH groups calculated as polyvinyl alcohol The structure was confirmed by element analysis and IE spectrum.

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Example 2

Following the procedure of Example 1, using propionaldehyde instead of paraldehyde, polyvinylpropional was prepared containing approximately 20 % by weight of OH groups, calculated as polyvinyl alcohol. The structure was determined by elemental analysis and the IR spectrum confirmed.

B ^ e _- i s ρ JL e 1 ^ _

The Eeifjpiel 2 is repeated, with others Kengen used in polyvinyl alcohol and propionic aldehyde in order to produce a product that would be 50 years old % By weight OH groups, calculated as polyvinyl alcohol. The structure was confirmed by elemental analysis.

B e is ρ i e_l 4

The procedure of Example 1 was repeated using 40 g valoraldohyd used up. The response time was 7 1/2 h at 55 to 7 £> ° C. The polymer was purified by precipitation in water from a dioxane solution. the Elenenbaranalyne and the Infi'arot Spoktrixiu showed that the product contained about 20% by weight of OH groups, calculated on the basis of polyvinyl alcohol.

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1A-41641

Example 5

This example demonstrates the formation of "non-bleeding" solid phosphoric ester-containing gels in comparison to "bleeding" phosphoric ester resins. In all of the following approaches, DDVP was used as the phosphoric ester · The resin was a polyvinyl chloride homopolymer (GEON 135) with an inherent viscosity of 1.12 (ASTM method D 124-3-66) o The plasticizer was either dioctyl phthalate (DOP) or dioctyl adipate (DOA) * The hydroxylated polymer was a polyvinyl butyral (PVB) with an outer molecular weight in the range of 38,000 to 4-5,000 and a hydroxyl group content of 18 to 20%, expressed as% by weight of polyvinyl alcohol and an acetate content of 0 to 1%, expressed as% by weight polyvinyl acetate. The first series of tests was carried out without polyvinyl butyral. The DDVP / PVC ~ resin and plasticizer were mixed in a test tube and placed in a 125 G oil bath. The mixture was heated until clear and then cooled in the test tube. In the second series of tests, the polyvinyl chloride was replaced by polyvinyl butyral, which was added during mixing, and the procedure was as stated above. The mixture solidified in the test tube was removed therefrom by breaking the glass. Each mixture was then barked in an open room and bleeding of DDVP was observed at regular intervals, H-JH obtained the following results:

30 -

209886/1322

BATH ORIGINAL

TABEL

Gemi NS DDVP 1 2 3 4th Weight -% PVC 60 60 60 60 Weight -% Plasticizers 30th 40 - _ Weight -% PVB 1O ¹⁾ - 10 ² > - Weight -% Days - - 30th 40 after 2 Days no off
blossoms the end
blossoms no off
blossoms no off
blossoms after 9 Bleeding
th Il It Il

after 19 days "" "" after 8 months - - ""

¹ ^ dioctyl phthalate
^J dioctyl adipate

This example shows the superiority of the gels hydroxylated polyvinyl butyral versus the polyvinyl chloride resins regarding the 'i'x' sticking out.

The following examples show that the interaction between a hydroxylated polymer and an active Phosphorus compound leads to the formation of an insoluble network, due to the binding of the phosphorus with the hydroxyliorten polymer. Et; However, it cannot be sure has been said whether a kovalnet bond or a strong one KompJex is formed.

- 31 209886/1322

BATH ORIGINAL

1A-41641

Example 6

There was prepared a gel by 4 parts by weight of DDVP together with 1 part by weight of polyvinyl butyral containing about 80 wt .-% polyvinyl butyral en unit, 18 to 20 Gexv ^r .- / a polyvinyl alcohol units and 0 to 2 wt * ~% Polyvinyl acetate units dissolved together «, this polymer

5 had an average molecular weight of 1.8 to 2.7 χ 10 « This mixture was left to stand for 30 min at tree temperature, a firm, rubbery gel formed, ν The gel was successively dissolved in tetrahydrofuran (THF) and precipitated with water and the liquid decanted. A part of the precipitate was removed after each such treatment, washed a few times with water, and examined for the phosphorus content. These treatments were repeated until a constant phosphorus content was found in the re-strike, suggesting that all of the contained at that point Phosphorus, was bound. The one after every such treatment remaining phosphorus is given in the following table.

TAB 35 L LE II

% Bound phosphorus r

1 .5.0.

2 ■ 0.56

3 x 0.13

4 0.088

5 0.074

6 0.086

- 32 20 98 86/1322

BATH

The original gel had a phosphorus content of about 11.2% by weight. This example shows that while most of the phosphorus in the gel is not bound is, a small amount of phosphorus with your hydroxylated Polymer interacts to form a crosslinked product containing bound phosphorus.

The phosphorus contained in the polyvinyl butyral DDVP gels was also carried out by theMiogravimetric analysis and by thermal analysis using flame ionization certainly.

B .... CL-J: s ρ ie 1 2.

A number of gels have been prepared using various hydroxylated polymers. These Gels were made by mixing 1 g of polymer with 4 g DDVP mixed at room temperature and then 1 h cured at 80 °. The various gels were then exhaustively with Tetraliydro furan until a constant Phosphorgelialt extracted, giving the following results received:

TABLE III:

209886/1322

BATH ORIGINAL

1A-41641

TABLE E III

polymer % OH ,
Salary ^and viscosity
(cP) 2) % bound
phosphorus Polyvinyl acetal 20th 170 0.44 Polyvinyl propional 20th 110 0.41 Poly vinyl butyral 20th 116 0.3 PolyvinyΙνα1eral 20th 39 0.3 Po Iy vinyl va.l oral 80 0.16 Acetylated poly
vinyl alcohol ο1 20th 0.47 Polyvinylac e did no 500 ooo ⁵ ^ no gel - '
education

Polyvinyl alcohol

Calculated as% by weight of polyvinyl alcohol

5% χββ solution in 60:40 ToIuοl / Ethanol at 25 ° C with a Brookfield viscometer

^J mean molecular weight

"'4% i ^ e v / aqueous solution at 20 C, Hoeppler method (falling

Bullet)

J \:> d-; u'e

Polymers di u not au.r Eeihe of poly-

- 34 -

209886/1322

BATH ORIGINAL

vinyl acetal polyvinyl esters containing active phosphoric esters Forming gels, include, are the following:

T A B E L L E IV

Polymer% O1 / mol wt. %. gebundo.r -. fir

Content - phosphorus

Hydroxypropyl 17,900,000 0.2

cellulose

Carbopol 940 ^ * 17 3-5 χ 1O ⁶ 0.2

An acidic carboxyvinyl polymer that contains approximately 2% PolyalIyIsaccharose is polymerized "

At G Ό ie 1

In each case 1 g of the various polymers listed in Table V was mixed with 4 g of DDYP, as in the previous examples, and left in the room partially at the door or, in some cases, at higher temperatures in order to try to achieve networking. None of the polyniere gave a stable gel with bound phosphorus.

- 35 -

209886/1322

BATH ORIGINAL

TABLE Y

Cellulose Acetate Cellulose Acetate Butyrate Ethyl Cellulose Styrene-Allyl-Alcohol-Copolymer Ep ichl ο Rh ydrin-Bi spheno lA ~ Har ζ Ethyl-vinylacetat-Copolyiaer Nylon

Polyvinyl acetate polyvinylpyrrolidone-vinyl acetate ~ Cox) olyiaer Polymethyl ethacrylate Polyvinylpyrrolicton polyacrylic acid shellac

Vinyl pyrrolidone ethyl acrylate copolymers Polyethylene glycol

Ed is however .möglich ₃ that the polymers mentioned above, if they are modified so that they the above criteria of _{compatibility?} Molecular weight and hydroxyl group content also correspond to form stable gels with activated phosphoric esters.

Be ispiel 10

Following the procedure of the previous example, 1g of polyvinyl

- 36 - 209886/1322

BATH ORIGINAL.

butyral having a hydroxyl group content of approximately 18 to 20% by weight, based on polyvinyl alcohol and an average molecular weight of approximately 220,000, is mixed with 4 g of the phosphoric esters given in Table VI. These mixtures were cured under two different conditions, designated A and B in Table VI. Under the conditions designated with A, curing was carried out for approximately 0.5 to 4 hours at room temperature; under the conditions designated with B, the mixture was cured for 2 hours at 70 ° C. and then for more than 2 hours at room temperature. In the table, "-" means no formation; "+" partial gel formation and "++" formation of a tough gel.

TABLE VI:

- 57 -

2U9886 / 1322

BATH ORIGINAL

1A-4-1

TABLE VI

Phosphoric ester

Gel formation

CH _x O.

0 it

Cl

CH _V O _X S

- OCH = C

CH, Ov 0

CH-

, Cl

- OCH-C

Continued TABLE VI:

2 0 9 8 8 6/1322

Phosphoric ester

PO-CH = C.

C ₂ H ₅ O

TABLE VI:

Cl

Cl

GEL EDUCATION

0 ^ H

^C 2 ^H 5 ° ^ Cl

CH ₅ O '

0 / H

P-O-C-C

Cl. j ^ Cl

Cl

POCC I

₀
2

H Cl

CH _x Ov S
\

P-OC-C Cl

C.

Continued TABLE VI:

- 39 -

209886/1322

TABLE VI

PhosDhorestei * CH, O \ S

^ POC = CC ₂ H ₅ O k

Cl

y-of \ - sch.

CH,

CH, CH,

P-O

CH-

CHO.O

/ P-OCH-C-Cl / ι ι CIUO · Br Br

.P-OCIL

CH ^ O '

Cont'd, to TABLE VI: - 40

2 0 9886/1322

MD

TABLE VI

Phosphoric ester gel formation

A. B.

cIi ₁ -O
6>

This table shows that those esters which have a vinyl group form a gel more easily than those that do not contain a vinyl group.

At s ρ i e 1 1_1 ^

A device A was produced by mixing 4 g of DDVP and 1 g of polyvinyl butyral with a hydroxyl group content of approximately 20 %. Mixture B was prepared by mixing 4 grams of trimethyl phosphate and 1 gram of the same polyvinyl butyral. The two mixtures were aged for 10 minutes at room temperature and then tested. Mixture A was tough and rubbery and had a shape somewhat similar to that of a rubber ball. Geraisch B was still soft and appeared to be just a solution of the polymer in the trimethyl phosphate. Both mixtures were then cured in an oven at 55 to 6O ⁰ G 20th They were then removed from the oven, cooled and re-examined. Mixture A contained 4.7 g of an amber chewy

- 41 -

209886/1322

BATH ORIGINAL

641

rubbery gel that was resistant to abrasion. The mixture B contained 4.4 g of a soft colorless syrup that did not gel.

Each sample was then exhausted at 75 cm ^ TKP at 50 ° C extracted. Mixture A gave an insoluble residue in the solvent, while Mixture B in THF was completely resolved after only a few minutes. Mixture B was reprecipitated by adding water to the THP dissolved in THF and reprecipitated in water. The precipitate was dissolved in acetone and reprecipitated in water and dried. The mixture A was extracted for a few days with fresh THF and the remaining polymer with Washed methylene chloride and dried together with the precipitate of mixture B in vacuo. After drying 'was the mixture A obtained in the form of a hard, tough resin, while the mixture B as a colorless soft polymer Template. The analysis showed that mixture A contained 1.63% phosphorus, which corresponds to a crosslinking of 11.6% DDVP means, while mixture B contained only 0.02% phosphorus, which corresponds to only 0.09% of the trimethyl phosphate. This clearly shows the difference between the so-called "activated" Phosphoric esters and the so-called "not activated" Phosphoric esters.

B ice ρ i e 1 12

Another experiment was carried out using a 4: 1 weight ratio of phosphoric ester to hydroxylated polymer. The hydroxylated polymer was

- 42 -

209886/13 2 2

Polyvinyl butyral containing approximately 20% by weight hydroxyl groups. The products were mixed at room temperature and cured at 80 ° C for 1 hour. The following were obtained Results: ·

TABEIJjE VII:

- 43 209886/1322

1A-41641

TABLE VII

Phosphoric ester

Ö ".Cl

n /

P-OCH = C

Gel formed % bound . phosphorus

there

II

P-OC = CHC-NHCH CH ₅

there

3.0

CH ₅ O \ 0

\ 0

^ POC = JCHCOCH ₅ ^ CH

CH

there

ClL ₁ Ov. 0

POC = CHCOCH ₃ / CH ₅

there

2.8 **

C ₂ H ₅ O _n 0
C ₂ H ₄ O ^

₉ Η, -0 \ Ο

P-OCH = C

H Cl

P-OCH = C

C ₄ H ₉ O-

Oa o, 51

Ports. Tabel. VII: 209886/1322

_ 44 -

Forts, too

TABLE VII

Phosphoric ester Gel formed% bound

Phosphorus *

C ₂ H ₅ O

^ P-OC = CHCl

Cl 2.2

ti no

CH

-0

0 tf

(CH _x O) ₀ P-OH

* Based on the phosphorus content of the ester

h hardened

209886/132 2

«■■ ■;

This example shows again how important it is to be "activated" Use ester zn in order to achieve crosslinking of the hydroxylated polymer and thus good gel formation.

Example 1j5

The release rates of gel preparations were determined using the release rate of known means slow release of the active ingredient on polyvinyl chloride base containing the same amount of DDVP or the same surface area possessed, compared »

Sample A was a gel consisting of 90% by weight of DDVP and 10% by weight of the polyvinyl butyral described in Example 6. ·
This gel was stored at 38 ° C for 4 days before the experiment began in order to achieve maximum gel formation.
The gel was in a cylindrical plastic container
with a diameter of 2.8 cm and a height of 1 cm. In this way, there was only a single surface from which the active ingredient could evaporate

ο
a size of 9 j 75 cni. The initial weight of the gel was 15 * 2 g. The analysis of an identical proportion of the
Gels not used for Sample A showed
a DDVP content of 81.7% by weight, which indicates the amount of unbound DDVP that can be released. This corresponds to 12.4 g DDVP.

Sample B was a PVO-based composition containing 23% by weight DDVP, 19 % dioctyl adipate plasticizer, 3% by weight PVC stabilizer, and 55% by weight PVO.

- 46 -

20988 6/1322

Man

Bas middle had a rectangular shape with the dimensions 6.45 x 12.5 x 0.5 cm. All surfaces were free what an entire area of

2
180 cm. The initial weight of the agent was 55.7 g. Analysis of an identical portion of the agent that was not used for sample B showed a DDVP content of 22.2% by weight, corresponding to 12.4 g of DDVP. Da3 is the same amount as in sample A.

Sample G had the same composition as sample E,

but was put in a plastic container that was shaped and

Size was identical to that used for Sample A.

This sample had an initial weight of 12.8 g, correspondingly

2.8 g DDVP.

All three samples were placed in a controlled atmosphere and held at 21 to 23 ° C with a room humidity of 30 to 50%. Fresh air was passed over the samples at a linear speed of 30 m / min and these were weighed at certain time intervals.

The weight loss is given in Table IX below.

TABLE IX:

209886/1322

TABLE IX B. G Weight loss (g) 2.1 0.11 Days A. 3.0 0.16 15th 2.6 3.6 0.19 30th 4.1 ■ 3.9 0.22 45 5.1 4.2 0.25 60 6.2 ■ ^, 5 0.27 75 7.2 90 7.7

% Weight * loss after 90 days 61.2 36.3 10

Approximate diffusion _x κ ■ u.

coefficient 3, ^ 5x10 "^ 4.3x10" ^f 4.3x10 "^

cm / d cm / d cm / d

This table shows that the agent according to the invention has a greater utilization of the DDVP and a higher diffusion rate of DDVP in a more compact form than the known means.

Example 14

Gels were made using various phosphoric esters and hydroxylated polymers at various concentrations manufactured. In some cases a plasticizer has also been used. The gels were all placed in aluminum weighing pans mixed with a 0 of 6.5 cm and hardened unless otherwise stated.

- 48 -

209886/1322

1A-41641

The gels were placed in a 1.8 1.8 χ 1.8 m Peet Grady room brought about a third on the east-west center line about 30 cm from the ceiling. Four cages each with 10 iliac flies were approximately x 61 cm from the Ceiling evenly spaced along the north-south center line hung up. A fan kept the air in the room constantly in circulating motion. The time in minutes that was required to achieve 50% kill * (KD 50) and to achieve a 90% kill (KD 90) of the flies, was noted. The results are given in Table X.

* (knock down)

TABLE X:

209886/1 322

TABEL

co co t » cn

Gel composition-ong

95 $ DDVP 5% PVB ¹

Gel weight Curing time moist
(g) and temp. speed

80 ° C
H.

". ., PVB polyvinyl butyral (as in example 6)

° 2) Petri dishes 0 15.24 cm

- 3) OH content 1? Wt% MW 900

26 ° C

(min)

90
(min)

44

βθ $ 2-Garbomethoxy-l-meth.'vtJvinyl
dime thy! - phosphate, α-isomer
J0 $ FTBl)
$ 10 tributyl citrate 2002) jo ° c 26 ° C 195 225 $ 25 DDVP
50 $ dibutyl sebacate
25 $ PVB ³ - <* 40 70OC 26'OC 155 147 $ 80 DDVP
20 $ hydroxypropyl cellulose5) 35 26 ° C 64 77 40 $ 2 -chlorine-i-vinyl diethyl phosphate
4o $ tricresyl phosphate 8ooc
2i h. • 26OC
$ 50 190 205 $ 80 2-chloro-vinyl diethyl phosphate 59 80 ° C - ¹⁶ ° ^C 555 585 $ 40 DDVP
4o $ tricresyl phosphate
20 $ PVBl; 58 1 h 26oc. 94 111 $ 80 DDV?
20 $ PVßl) 58 8ooc
1 h 17 ° C 140 161

K3 CO CD

Example 15

A 6.5 cm aluminum weighing dish containing approximately 40 g of a gel consisting of 80% DDVP and 20 % of the polyvinyl butyral described in Example 6 was placed in the center of a 1.8 × 1.8 × 1.8 m foot Grady tree about 30 cm from the ceiling. Cages with various insects were hung in the center of the tree about 25 cm from the ground. Mortality was determined after 2 hours and after 24 hours. The results are given in Table XI.

TABLE XI

Insect % > Mortality % Mortality (2 h) (24 hours) Housefly 100 100 Mosquito (anopheles) 100 100 Cockroach (male
lich) 0 100 Flour beetle 0 100 Rice beetle 0 100 Grain beetle 0 100 Aphid (pea aphid) 0 100 2-winged spider mites 0 100 Earwig larva (4th state) 0 0 (Corn Earworm)

- 51 -

209886/1322

Example 16

This example shows the production of solid gels containing phosphorus ester which are resistant to the development of surface moisture in comparison with known resins containing phosphorus ester. DJDVP was used as the phosphoric ester in all of the following approaches. The resin was polyvinyl chloride homopolymer (GEON Λ3Τ®) with an inherent viscosity of 1.12 (ASTM D-124-3-66)., The plasticizer was either dioctyl phthalate (DOP) or dioctyl adipate (DOA). The hydroxylated polymer was a polyvinyl butyral (PVB) with an average molecular weight in the range from 38,000 to 45,000 and a hydroxyl group content of 18 to 20%, expressed as% by weight of polyvinyl alcohol and an acetate content of 0 to 1% by weight, expressed as percent polyvinyl acetate. The first series of tests was carried out without polyvinyl butyral. The DDVP / PVG resin and plasticizer were mixed in a test tube and placed in a 125 ° C oil bath. The mixture was heated until clear and then cooled in the test tube. In the second series of tests, the plasticizer was replaced with polyvinyl butyral, which was added during mixing. Otherwise it was worked as above. The mixture solidified in the test tube was removed by breaking the glass. The formation of surface liquid was observed at certain time intervals. The following results were obtained.

2 0 9886/1322

O O I O

vD r K \

OOOI φ sr «Λ

OO O

Φ «Λ \ K-

d d ei d

• rl -H -H · Η

Φ Φ Φ Φ Pl Pl Pl Pl Pl CQ H CO co CD Φ • ζ-. Pl -P Λ φ Pl Pl P! H • Η • Η • Η Φ Φ Φ Φ Pl Pl Pl s

ο ο ο ι ^ ιΛ γ

Ο O I O

VD CVJ OJ

CvJ

O O O O vD CvJ \ - ν-

Pl 05 π! H • ro Φ Pl Pl Pl Pl • Η ■ Η H φ Φ ω Pl Pl

Pl pl pl pj

• Η · Η · Η · Η

φ φ 0) (D

Pl pl pl pl

ο CVi I. • Ρ Pl
ι CD CD I. O fH • rl
Φ ■ Η
Φ • ο · Γ3 VD ω U c4 ο • Η Pl CD W. φ a ! ί3 Pl Pl • Ρ ο ιΗ Pl Φ φ CD • Η "H Φ bD 60 Pj O el fco CD CD O Ρ · * ο PQ φ CTj ErI ^ -O ρ » EH ο Ρ < T Ρ-ι ο CO - ο ίπ T T <Η CU _rj T φ F- * Xi rj O >. el? Q) .d υ O CD φ , ο O CD CD d Φ Previous year O O η) 0. Pl Previous year H

f = l

CM

209886/1322

This example shows the superiority of the invention Products compared to the known preparations with regard to their resistance, surface liquid to build.

Example I7

The following gels were prepared from (1) DDVP, (2) a polyvinyl butyral with an average molecular weight in the range from 180,000 to 270,000, a hydroxyl group content of 17 to 5 to 21%, expressed as% by weight of polyvinyl alcohol and an acetate content of 0 to 2.5 %, expressed as,% by weight polyvinyl acetate, (3) GEOH 135 ^ "(PVC) and optionally (4) dioctyl adipate (DOA) as plasticizers.

The golds were made by blending the DDVPj PVC and DOA in a mixer at high speed for about 60 minutes under vacuum, producing a uniform mixture originated. The polyvinyl butyral then became the solution Admittedly, the approximately 45 seconds are further mixed and bowel in Test tubes were poured. The mixture in the reagent " gläsGMi was hardened for 5 min at 160 ° and then cooled, placed in airtight, sealed, laminated pouch and used for the υei tero investigation kept.

Ks became ■ stable gels of the following her ;; en files:

2 0 9 8 8 6/1 3 2 2

BATH

SH XIII % DOA TABEL % PVC 5 % DDVP % PVB 10 - 80 5 15th - 80 5 20th 15th 70 10 10 - 70 VJl 25th 10 70 5 20th 30th 60 10 VJt 25th 60 5 10 10 60 5 25th 20th 60 VJl 20th 15th 50 10 30th 30th 50 VJ! 10 10 50 10 30th 30th 50 10 20th 15th 40 10 40. 31 40 VJI 31 40 36 2 20th 20th 30th 10 40 45 30th 10 20th 30th 30th 5 40 25th 20th 10 50 20th VJi

From these data it can be seen that the components of the gel can vary within relatively wide limits.

20 9 886/132 2

BATH ORIGINAL

B e ι s ρ ι el 18

Weighed amounts of methyl 2,2-dichlorovinyl phosphate (D]) VP), dioethyl adipate plasticizer, PVC resin (GEON 135®) and a PVC stabilizer were placed in a * Waring mixer under a lighter weight. Vacuum mixed for 60 seconds to avoid air pockets. Polyvinyl butyral polymer, containing approximately 80% by weight of polyvin3 ^r lbutyral units _i 18 to 20% by weight of polyvinyl alcohol units and. 0 to 2% polyvinyl acetate units with an average molecular weight of approximately 1.8 to 2.7 × 1CK were then added and mixed under vacuum for a further 10 seconds were placed in glass molds for hardening in an electric furnace.

The samples for microwave irradiation became a specific one approximately

Time between / 50 and 75 seconds with a consumption of 1000 watts irradiated. The samples were then removed and quenched in cold water to reduce the cooling time. After cooling, the hardened gels were removed from the mold and examined for evaporation brought to even dimensions. They were cut into pieces about 3 to 5 a length with a diameter of about Cut 4 cm and weighed about 50 to 70 g. The comparative samples were in an electric for 30 minutes Oven heated to 150 ° C and hardened into pieces of comparable size and physical dimensions to those hardened with microwaves Cut gels with which to determine their effectiveness characteristics were compared.

- 56 -

209886/1322

The uncured samples were opaque viscous mixtures and were then cured to the point where a tough, translucent, rubbery gel was formed was. These mixtures did not result in the formation of surface liquid. In other words, it was not observed that the surfaces of the samples droplets of Possessed liquid on the surface, neither during storage nor during use. After the storage examinations samples were hung under a hood and the weight loss recorded as a function of time. The diffusion coefficient of the DDVP was derived from these data determined for each sample. Man. received the following results,

TABLE XIV:

209886/1322

BATH ORIGINAL

1A-41

TABEL

ZIV

Put together enough Wt% Type of hair tion DDVP 26) PVC ²⁶ ) Microwaves DOA 35 oven PVB 10 * PV0 ~ S stabilizer 3

Diffusion coefficient cm ^ / d (double Determination)

2.2 χ 10 '' 2.2 χ 10 '

-3

DDVI ⁵
PVC
DOA
PVB
* PVC-SLabil1g ator

39)

24 ':

10 5)

Microwave oven

1.7 χ 10 "

1.8 χ 10

-3

IJJJVP
PVC
IjO Λ
PVB

U- i.b.ub.Uisabor

35) 26)

26)

I ^v Iikro \; ellen furnace 2.0 χ

2.0 χ 10

r-3

-; V (Λι ·; '; α. ". Gbd.'U'-al Co.) BATH ORIGINAL

1A-4-1 641

B is ρ ie 1 1 9

This example shows the importance of the geometry and the composition for the release of the biocidal substance from the agent. The agents A and B were composed of a gel containing 35 wt .-% DDVP, 26 wt -.% PVC (GEON 135®), 26 wt .-% of dioctyl adipate (DOA), 10 wt .-% of the method described in Example 3 Polyvinyl butyral and 3 wt% PVC stabilizer. Agent C was a known preparation with slow release of the active ingredient, containing 23% by weight DDVP, 19% by weight DOA, 55% by weight PVC and 3% by weight PVC stabilizers. The evaporation rate and the vapor concentration were investigated over a longer period of time. The measurements of the vapor concentration were carried out in an empty room of 28 rir at 25 C and a relative humidity of 50 % , in which the air was circulated but not renewed. The evaporation rate was determined by the weight loss of an agent which was in a hood at 22 to 25 ° C and 0 to 50% relative humidity under a stream of air at a speed of 30 m / min.

The agent in the fume cupboard was weighed at regular intervals and the rate of evaporation determined due to the loss of bio-secretion. The agents were bfucht O-Ln certain Zeitabntänrien in the above space [J ₁ h and kept there 2Λ, so that the 1) -impfkonzentrat ion in the Lui'b to a DC £ jowichbszu;.; :: to one TNND L Liui could. Daiui samples of the air were taken and: "· '!., -' :. ^; i -. 'IL, to the convent, cv. I Lon de"D-nro;.' Es ei ·: ■ r hioc i den ·. ;; t'iii. · ,. :%: < bttj; ti i.iüioa. ir ti ürtiL'iLt ti i.: i'i-'l ν \ -ύ ·. .; t'-Ti ·: ^ L'iLii ir '·:

21) 9 Hi; ti / I 3 "','

BAD OFUQiNAL

TABLE .XV

middle

geometry

Initial weight

Cs)

Cylindrical shape 1 cm high, 3? 7 cm 0? Surface 81 cm ²

71

by days:

Average evaporation rate (mg / h) Percent (vapor concentration (/ Ug / 1)) tuale

. 1, levy

20th

40

60 80

100 120 ^

Days

A only a ' surface with a 0 of cm ^{2 and} a depth of 1 cm

12 7 ■ 4 3.3 3 2.5 2 60 (0.12) (0.11) (0.10) (0.09) (0.08) (0.07) (0.05Γ

23 9. (O ₅ 33) (0.22)

4 3 2 1.8 65 (0.10) (0.08) (0.07) (0.05)

Rectangular strips 25 x 6.5 x 0.5 CBV ₅ surface 346 cirr

29 5 3 2 2 1 ₉ 6 * - 45 * (0.48) (0.08) (O _? O3) (O, O3) (O ₅ O3) (O ₉ O3) *

O
I.

* 90 days

From these values it can be seen that the inventive Gels initially release less bio-envy than the well-known vaporizers, but for a longer period of time they release useful amounts of the biocides Release substance. ,

B is ρ ie 1

20th

The wide range of compositions and geometrical shapes that result in a correspondingly wide range for the Diffusion rate of the biocidal substance leads, is shown in this example. Me Composition and Geometric Shape Each agent was as in the following Table specified:

Medium %

DDVP

TABLE XVI

DOA polyvinyl butyral

PVC

geometry

surface

cm

36

18th

45

10

Cylinder 7.5 cm 113.4 0, 12.5 cm length

Cylinder 2.5 cm 94.5-0, 11.2 cm length

Cylinder 3.8 cm 81.9 0.5 cm length

Cylinder 715 pn 44.1 0.15 cm in length (only one free Surface)

209886/1322

- 61 -

BAD ORJQINAi

With the above mentioned smocks you got over one Period of 140 days the following evaporation rates.

Average rate of evaporation during the day

(mg / h)

1 20th 40 60 80 100 120 140 Λ 40 12th 7th 4th 3 2 1.5 1.0 B. 30th 9.5 6.5 5 4th 3 2.5 2.5 G 23 7th 4.5 3 2.5 2 1.7 1.5

D 5 2.5 1.5 1.2 1.0 1 * 0 1.0 1.0

Example 21

This example shows the improvement in the inventive. appropriate means compared to comparable preparations that does not contain the gel-forming hydroxylated polymer "with respect to the formation of surface fluids / ib ,.

Samples of agents with slow release of the active ingredient, comprising 23% by weight DDVE ³ , 19% by weight either DOA or DOP as V / e Lelutiacher and 3% by weight of a PVO stabilizer with various contents of polyvinyl chloride (GEOiI 102 ^ ) and Polyviaylbubyralpolymer (PVB) MIB polyvinylbutyral KüLall; "vc-u ungo fiUir 80 weight Su, 18 to 20 wt .-% polyvinyl alcohols i.ühej.ben and 0 to 2 Gev-.-.% polyviny]. acebcibelM.hoi t: -..- n and a molecular weight of about 1.8 b.lü

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2.7 x 1 (P were made for research purposes. All samples were stored in individual containers measuring 25 x 5 x 5 cm. The containers were not tightly closed and the DDVP vapor remained essentially in the container while allowing water vapor to enter the container. Such an environment leads to the formation of liquid droplets on the surface of the means known as "exudation" are designated. It was made under two different conditions Tests carried out, i.e. under normal conditions (temperature 21 to 2 ° C and humidity 35 to 50%), and tougher conditions (temperature 30 to 35 ° C and Humidity 80 to 100%). The following results were obtained.

TABEL

XVII

Preparation

approximate time to exudation (d)

Plasticizers

PVC

% PVB normal conditions harder loads

DOA
DOA
DOA
DOA
DOA
DOP

TJ
1)
I)

1)
2)

DOP '

DOP ^

DOP ² )

* Corpse
1)

55 54 53 50 45 55 54

53 50

0 1

10 0 1 2 5

25-35
> 55

> 70

5-50
> 95

> 95
> 95

5-25

25th

25th

45 105 5-10 50-70 * 50-70 *

75 ·

Ct; tires 16.3 χ 6.3 x 0.75 cm, eyelets 25 x 0.3 χ 0.5 cm

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The gels formed in Examples 22-25 were made by handing 50 g of the various Ingredients in the specified proportions in a 150 cm beaker mixed. The mixtures were then cured for 15 to 45 minutes at 150 ° C, unless it is otherwise stated.

Example 22

A mixture containing 50% by weight of diethyl 2- chlorovinyl phosphate, 30% by weight of hydroxypropyl cellulose with a molecular weight of approximately 9 × 10 -4 (KLUCEL H®) and 20% by weight of polypropylene powder with a melt index of 7) 5 formed a gel quickly at room temperature with the polypropylene particles present in the suspension.

The gel was then used to melt the propylene

(roller blades in a Brabender Plasticorder mixer with rollers / on Heated to 177 C. The melted sample of the gel was something darker and brittle.

Example 23

A mixture comprising 50% by weight of 2-carbomethoxy-> 1-methylvinyldimethylphosphate, α-isomer, 15 wt .-% hydroxypropyl cellulose, corresponding to Example 22 and 30 wt .-% of a polyvinyl acetate with a medium Molecular weight of about 4-5,000 (GELVA V-7 ^) a gel at room temperature. A soft clear gel was obtained after curing at 155 ° C for 15 minutes.

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BAD ORtGlNM

Example 24

A mixture of 75% by weight dimethyl 2-chlorovinyl phosphate,

RiIUT * f ⁵ ΓΊ

10% by weight of a high molecular weight / carboxyvinyl polymer of acrylic acid which was copolymerized with 2% polyallylsucrose (CARBOPOL 934®), 10% by weight cellulose acetate with an average acetyl content of 39.8% by weight and a viscosity of 22 to 38 sec (ASTM-D 1343-56) and 5% by weight of dibutyl phthalate as a plasticizer for cellulose acetate slowly formed a gel and were cured at 155 ° C. for 45 minutes.

Example 25

A mixture of 60% by weight of diethyl ~ 2 ~ chlorovinyl phosphate, 10% by weight of a high molecular weight polymer, as in Example 24, and 30% by weight of an acrylonitrile-TButadiene-styrene resin (BLENDEX®) with a specific weight of 0.98 formed a gel and was ^{cured at 155 °} C. for 45 minutes.

Example 26

This example shows the effectiveness of a typical gel-like agent. A gel with a single free Surface that weighed 75 »82 g and was 7.5 cm in diameter and 1 cm deep (17» 5 cm surface), consisting of 35% by weight DDVP, 26% by weight PVC (GEOW 135®), 26% by weight DOA, 10% of that in Example 18 described polyvinyl butyrals and 3 wt .-% PVC stabilizer were under 'initial ^ and ^ equiv / ichtbodingungeir

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-JL Q

Maintained in a 28 nr test room at 25 C and a relative humidity of 50 % . In the initial experiments, the samples and houseflies were brought into the test room at the same time and the time stated in minutes which led to a 50% (KD 50) and 90% (KD 90) kill of the housefly. The vapor concentration of the DDVP A note was also made for KD 50 and KD 90 in / Ug / 1 air (concentration) Under the equilibrium conditions, the sample was left in the test room for 7 or 24 hours and then cages with houseflies were brought into the room and the KD 50 and KD 90 is given together with the vapor concentration of the DDVP. For each experiment, four small cages containing 10 flies, each 1.8 m above the floor and two large cages, each containing 100 flies, were placed on the floor of the room are the mean from the six cages. As long as it was not in the test room, the sample was placed in a fume cupboard that was kept at 22 to 25 ° C and 50 % relative humidity and through the one Air flow was passed through at a speed of 30 m / min. The following results were obtained:

TABLE XVIII:

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Η »

TABLE XVIII

Days conditions KP 50 KB 90

min concentration min concentration tration

0 initially 58 0.06

0 equilibrium ¹ ) 22 0.16

9 initially 62 0.06

9 Equilibrium ¹ ) 22 0.16

17 initially 62 0.06

17 equilibrium ¹ ) 25 0.16

24 initially 56 0.06

24 Equilibrium ¹ ) 52 0.11

28 initially 55 0.07

28 equilibrium ¹ ^ 26 0.14

31 initially 64 0.06

31 Equilibrium ¹ ) 29 0.12

35 initially 65 0.06

36 equilibrium ² ) 28 0.13

42 initially 62 0.06

43 equilibrium ² ^ 35 0.11

49 initially 90 0.04

50 equilibrium ² ^ 39 0.09 75 equilibrium ² ) 34 0.10 93 equilibrium ² ) 44 0.08 114 equilibrium ² ) 45 0.08 127 equilibrium ² ) 73 0.05

76 0.07 50 0.17 75 0.07 30th 0.17 78 0.06 27 0.18 75 0.07 45 0.17 80 0.06 55 0.14 77 0.06 59 0.13 82 0.06 57 0.13 80 0.06 43 0.12 104 0.05 49 0.10 46 0.11 58 0.09 61 0.08 100 0.05

'7 h in the test room

^J 24 h in the test room

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1A-41

From these values it can be seen that the sample examined is suitable as a slow release agent for at least 4 months.

Example 27

The gel prepared in Example 26 with a single surface in the form of a cylinder with "a diameter of 5" 2 cm and a depth of 0.2 cm was placed in a test room with a size of 28 microns as described in Example 26 under initial conditions. The KD 50 was reached in 95 minutes and the ED 90 in 109 minutes.

PATENT CLAIMS:

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Claims (1)

PATENT CLAIMS \\ j Bioeide means comprising a mixture of a phosphoric ester of the formula: Rv (O) -X-C A (D in which R and R ¹ each independently represent alkyl, alkenyl or alkynyl groups with up to 12 carbon atoms, cycloalkyl groups with 3 to 8 carbon atoms, aryl, alkaryl, aralkyl or aralkenyl groups with 6 to 15 carbon atoms, which are replaced by halogen, lower alkoxy, nitro, hydroxy, amino, alkylamino or dialkylamino groups can be substituted, η O or 1, X an oxygen or sulfur atom, I a hydrogen or halogen atom and Z a halogen atom or a group: Il -C-NHR " Il or -COCH R " R ¹ in which R "has a hydrogen atom or an alkyl group 209886/1322 1A-41641 "up to 6 carbon atoms and E" ^{1 is} a hydrogen atom, a phenyl or halophenyl group and A is a hydrogen atom, an alkyl group with up to 6 carbon atoms, a phenyl or halophenyl group, with a hydroxyl! inherit the polymer that comes with the. Ester is compatible and has a molecular weight of 30,000 to 1,000,000, with a minor portion of the ester having reacted with the polymer to form a crosslinked polymer. 2) Means according to claim 1, characterized in that R and R ^{1 are} each an alkyl group, η 1, Z is a halogenator and A is a hydrogen atom * 3) means according to claim 1 or 2, characterized in that g e k e η η., that R and R 'are each a methyl group, Z and Y are each chlorinated, A is a hydrogen atom and X is a Mean oxygen atom. 4) means according to claim 1 to 3, characterized in that it is also a thermoplastic Resin and optionally contain a plasticizer. 5) means according to claim 4, characterized in that that the thermoplastic resin is polyvinyl chloride. 6) means according to .Anspruch 4 or 5, characterized in that the plasticizer or dioctyl adipate Is dioctyl phthalate. 7) Means according to claim 4 to 6, characterized g e k e η η - ' draw t that they contain 10 to 80 wt .- # Phosphoreeter, 0.5 to 30 weight percent hydroxylated polymer, 5 to 60 weight percent 209886 / 1.3 22 ' BATH ORIGINAL thermoplastic resin and 0 to 50 wt keep. Plasticizer 8) Means according to claim 4 to 6, characterized in that it contains 20 to 50 wt .- ^ phosphoric ester, 1 to 15 wt. ~ 6 hydroxylated polymer, 20 to 55 wt .- 50 thermoplastic resin and 15 to 35 wt., -% of a plasticizer included. Agent according to Claims 1 to 3, characterized in that g e k e η η ~ draws that they also contain a plasticizer. 10) Agent according to claim 1 to 9 »characterized in that the hydroxylated polymer is the following Structure CH ₂ C CH, 'CH
1 .0 CH ₂ -CH OH CH ₂ -C -CH C = O Y ¹ where Y is a hydrogen or halogen atom or an alkyl, haloalkyl or hydroxyalkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms and a, b and c are numbers which represent the ratio of the respective groups in the polymer in Specify weight -JS. _4th 11) Composition according to claim 10, characterized in that a is a number from 0 to 99, _f b is a number of at least 1 and c is a number from 0 to 99. 209886/1322 BATH ORIGINAL -Century- 12) means according to claim 11, characterized in that that b is a number from 3 to 35 and a and c are numbers from 0 to 97 are. ■ 13) means according to claim 12, characterized in that that a is a number from about 80, b is a number from about 18-20, and c is a number from 0-2. 14) Agent according to claim 10 to 13, characterized in that the polymer has an average molecular weight from 180,000 to 220,000. 15) Use of the agents according to Claims 1 to 14 for combating invertebrate pests. 6244. 209886/1322 BATH ORIGINAL