MXPA98003627A - Forms of halohidantoin and method by extrusion by fus - Google Patents

Abstract

A halohydantoin product and method for producing solid halogenated hydantoin forms using melt extrusion. The shape of the products include tablets, tablets, discs, dispensers, designer forms such as granules, pellets and Christmas ornaments. The halogenated hydantoin compounds used include halogenated methylethylhydantoins alone or in admixture with dimethylhydantoins. The compositions used to make the forms may include additives such as solubility modifiers, compaction aids, fillers, surfactants, colorants, fragrances, dispersants, lubricants, mold releasers, detergent developers, corrosion inhibitors, chelants, stabilizers, biocides, bromide sources, or halogen oxidant compositions. The product as well as the improved supply is obtained by melt extrusion. The supply can be used for making shapes by compaction without pol

Description

FORMS OF HALOHIDANTOIN AND METHOD BY FUSION EXTRUSION This application is a continuation request in part of the US application with serial No. 08 / 554,476, filed on November 7, 1995.

BACKGROUND OF THE INVENTION There is a distinct need for halogenated hydantoins in the form of granules, high integrity pellets and shaped forms, such as tablets, tablets, and the like. These forms of halohydantoins are useful in a variety of applications, such as bleaching, washing dishes, disinfecting toilet bowls, and water treatment applications such as swimming pools, water cooling systems and mineral water spas. "High integrity" refers to solid products that have a predetermined shape, which are hard, shape retentive and dust-free. Dust-free products are desirable because the halogen-donor compounds are irritant in nature. In addition, much dust intensifies the halogen smell associated with these compounds, which is also irritating. Halogenated dimethylhydantoin derivatives are used in a variety of applications, such as pool sanitizers (bromochloro-dimethylhydantoin) and bleach (dichlorodimethylhydantoin). These halogenated dimethylhydantoins are fine, dusty powders, which are difficult to obtain in solid forms. In the past, compaction has been suggested (see U.S. Patent No. 4,242,216 issued to Daugherty et al.); however, many of the compounds require binders in order to compact well and some compounds do not compact at all. The use of binders to produce a commercial form of halodimethylhydantoin increases costs, and may require additional processing steps, for example, a blending operation. Moreover, the binders do not alleviate the dust problem to the extent of the present invention. Many of the forms made by compaction are dusty and friable, and lack true integrity. The tablets, which are useful for water treatment, can be made by compaction. However, applications such as toilet flushing require that halohydantoin be in the form of a tablet and problems in producing larger forms by compaction techniques are increased in this way. Additionally, the halogenated hydantoins for pool disinfection need to be in a different form, due to the high dissolution rate of the compacted tablets. The necessary forms for the disinfection of swimming pools can not be done by compaction either. The production of shapes by melting techniques (ie, emptying a melted material into a form, solidifying the material, and discharging the product by conventional means), is well known in other industries, such as in the manufacture of sweets. The fusion techniques provide particular advantages for the elaboration of forms in that virtually any shape of any size can be made, requiring only a mold of specific size and shape, and that is only limited by the creativity of the designer. The forms of "designer" that could incorporate a logo or specific form are possible. In some cases, the mold itself can serve as a dispenser for the compound, for example, dishwashing applications in institutions. None of the traditional active halogen compositions (ie, those based on cyanuric acid, succinimide, dimethylhydantoin, or the inorganic ones) are good candidates for the melting techniques formed, because the melting temperatures of the compounds are higher (>100 ° C) and very close to decomposition temperatures. However, halogenated methylethylhydantoin is an excellent candidate for fusion techniques due to its low melting range and the large differential between its melting temperature and decomposition. It has been found that when the halogenated methylethylhydantoin is mixed with halogenated dimethylhydantoin, the mixture can be formed via fusion techniques. The low melting methylethylhydantoin derivatives serve to disperse components without fusing to give the overall blend flow properties. See US Patent No. 4,560,766 issued to Girard et al. The fusion technique set forth in Girard et al. and used in the art for halohydantoins consists of a melting pot with a feed to a molding system. This system has several disadvantages. For one, it is very difficult to uniformly heat melting pots of halohydantoin due to poor heat transfer in powders of this nature. In order to melt enough material so that the flow is established, the material near the heat source will necessarily be heated to a higher temperature than the material in the center of the pot. 5 Moreover, while these halohydantoins have a much higher temperature differential between their melting temperature and their decomposition temperature, some decomposition and loss of material occurs in the melting pot technique, when the material is left at high temperatures required for too long. The * 10 Decomposition of the material is undesirable for a number of reasons. For one, the fumes that will result from decomposition are toxic. In addition, the decomposition of the material can lead to a less pure and less effective compound. In addition, the halohydantoin material being heated in the melting pot will have a more heat history long. When making a mold using this technique, more halohydantoin than is necessary in the form is cooled and hardened. This means that the extra material has been repeatedly melted and cooled, in an effort not to waste halohydantoin. However, after several times, halohydantoin will decompose and will not be satisfactory for used. Finally, using the melting pot technique, the hardened residue will often be left in the melting pot after molding, which requires extensive cleaning.

BRIEF DESCRIPTION OF THE INVENTION It has been unexpectedly found that the melt extrusion method, normally used in plastic applications, can be used to make forms of haiohydantoin and avoid the problems associated with conventional fusion techniques. For example, unlike traditional fusion techniques, fusion extrusion techniques only fuse the exact, discrete amount of material needed for the mold. In addition, the material is subjected to high temperatures only for short periods of time due to the large contact surface area 10 with the material in an extruder. Moreover, a large change in temperature is not required to achieve the desired fusion. Additionally, since melt extrusion techniques can cause materials to flow that do not flow easily, only partial melting of the material is necessary. This reduces the heat input. 15 The use of this technique to mold halohydantoins is quite novel and produces unexpected advantages. As previously noted, melt extrusion techniques are not normally used with these systems. In fact, although the patent of Girard et al. was issued almost ten years ago, no one has applied fusion extrusion techniques to produce forms of halohydantoins. The resulting halohydantoin forms made by the melt extrusion process are free of dust, of high integrity, and stronger than forms made by conventional commercial methods. An additional advantage of extrusion techniques is that the additives can be formulated in the haiohydantoin in the extruder by itself due to the ability of the extruder to mix materials, particularly with the twin screw equipment. There is no need for pre-mix equipment and, in this way, the cost and processing benefits are realized. The present invention relates to the production of a solid halogenated hydantoin product by extruding a smelting or partial melting of the haiohydantoin, cooling the extrudate to solidify the haiohydantoin and recovering the solid product. This process can be used to produce a variety of forms of haiohydantoin. * 10 An embodiment of the invention relates to the production of haiohydantoin forms by extruding a smelting or partial melting of the haiohydantoin in a mold of a predetermined size and shape, cooling the mold to solidify the haiohydantoin, and recovering the solidified form of the mold in traditional techniques. Alternatively, the mold can serve as a dispenser for the chemical in its final application. Any form that can be produced in a mold or die can be produced by this method, including tablets, disks, pills, tablets, pellets, granules, and so-called "designer" forms such as Christmas ornaments. Another embodiment of the invention relates to a method for making haiohydantoin granules by extruding a smelting or partial melting of the sheet haiohydantoin, cooling the leaves to solidify the haiohydantoin, and grinding the leaves to obtain granules. A further embodiment of the invention is a method for making pellets of haiohydantoin by extruding a smelting or partial melting of the haiohydantoin through a die or screens to form filaments, which are subsequently cut by conventional pellet techniques, and cooling the resulting pellets. A further embodiment of the invention is a method for producing an "agglomerate" of the original powdery powder by subjecting the powder to sufficient heat in an extrusion process to melt only a small portion of the powder (the melt acting as a "binder"). ), extrude the mixture, and recover the agglomerate by conventional means. This product has much better handling characteristics and minimal dust compared to the original powder, and would serve as a more efficient supply for the traditional compaction processes used to make large shapes, ie, tablets for automatic toilet bowl applications. In a preferred embodiment, the extruder used in this method is a twin screw extruder. The invention also relates to the solid haiohydantoin product produced by the methods described above, including forms, granules, pellets and supplies. In a further embodiment of the invention, this extrusion technique can be applied to the compositions containing the haiohydantoins together with additives. Another embodiment of the present invention are extruded solid halogenated hydantoin products, comprised of haiohydantoins alone or with an additive.

DETAILED DESCRIPTION OF THE INVENTION The haiohydantoin compounds contemplated for use in this invention are described in U.S. Patent No. 4,560,766, which is incorporated herein by reference. These haiohydantoin compounds have methylethylhydantoin (MEH) as a single constituent or are in a mixture of MEH and a halogenated dimethylhydantoin (DMH). The halogenated methylethylhydantoin for use in this invention has the following structure: C2Hs; O 1 // H: 3C- -C - C / \ 15 N N wherein Xi and X2 may be the same or different and are chlorine and bromine. The halogenated dimethylhydantoins for use in this invention have the following structure: CH3 O 25 | // H3C- C - C / \ N N ^ C ^ 30 X! || X2 O where X ^ and X2 may be the same or different and are chlorine and bromine.

The halogenated MEH compounds, as compared to their II corresponding halogenated DMH compounds, have significantly different thermal properties. One such property is the temperature differential between the melting point and the decomposition temperature of the halogenated MEH compounds. These MEH compounds melt from about 60 ° to 70 ° C, while decomposing from about 150 ° to 170 ° C. This large temperature differential allows these compounds to melt and form without decomposition. In addition, the dihalo mixtures DMH and MEH have the melting characteristics of the MEH derivatives so that fluid systems, consisting of solids dispersed without melting in a molten medium, can be formed at low temperatures. The temperatures significantly below the point of thermal decomposition of the mix are used. Table 1 shows a range of products with fusion and decomposition data. The products are listed in terms of composition relative to DMH, MEH and bromine (moles). For example, Dantobrom® is 0 3 DMH + (2 MEH + 0 J NaBr and in this way is referred to as a product "8-2-5". Since each molecule of the final product of hydantoin contains 2 moles of halogen, the moles of chlorine in each final product is 2.0 minus the moles of NaBr added. Each of the products listed in Table 1 is first made by mixing MEH and DMH. The composition is haiogenated then using conventional techniques. Two (2) moles of chlorine are added to each composition. If a bromochlorohydantoin or dibromohydantoin is desired, bromine, in the NaBr form, is added in the desired molar amount. In a simple oxidation / reduction reaction, chlorine oxidizes bromine in NaBr to Br +, which halogen then DMH and MEH. Since each product has two moles of halogen, the rest is halogenated by chlorine. For example, when making Dantoin® 5-5-5, 0.5 mole of NaBr and 2.0 mole of chlorine are used to halogen the MEH and DMH. Chlorine (0.5 mole) oxidizes 0.5 mole of NaBr to Br +, which halogen the DMH / MEH, and the remaining chlorine (1 .5 moles) halogen the MEH / DMH. Thus, the final product contains 1.5 mole of chlorine and 0.5 mole of bromine. No NaBr is added to make the dichlorohydantoins. Two moles of NaBr are added to make the dibromohydantoins. While 2 moles of chlorine are also added to make the dibromohydantoins, all the chlorine is used to convert the 2 moles of NaBr to Br +.

TABLE 1 (A) DICHLOROHIDANTOINES (B) IDOMINOUS BROMOCLOROH F (C) DIBROMOHIDANTOINAS Fusion range data based on differential scanning calorimetry 2 Capillary fusion data The temperatures at which the haiohydantoin compounds begin to melt (measured in most cases by differential scanning calorimetry, which provides a clearer picture of the beginnings of the melting phenomenon) in Table 1, are the temperatures lower in the melting ranges shown. The data in Table 1 show that, with the exception of dibromo derivatives, products containing more or equal to 20% MEH in the The composition of hydantoin, have differences between the beginning of the melting temperatures and the decomposition temperatures greater than or equal to 65 ° C and usually 70-100 ° C. Haiohydantoins with differences greater than 60 ° C, preferably greater than 70 ° C, between their onset of melting temperature and decomposition can be used in the method of the present invention.

The haiohydantoins with not more than 95 mol% of DMH and at least - ^^^. 5 mol% of MEH can be used in this invention, with 0 to 90 mol% of DMH and 10 to 100 mol% of MEH being preferred. The most preferred haiohydantoins used in this invention contain 0 to 80 mole% of DMH and 5 to 100 mole% of MEH. The haiohydantoins made from 50 mol% DMH and 50 mol% MEH are preferred for melt extrusion of molded shapes and granules. The haiohydantoins made from 80 mol% DMH and 20 mol% MEH are preferred for making pellets. The haiohydantoins made of no more than 95 mol% DMH and at least 5 mol% MEH are preferred for making agglomerates. Halogenated MEH compounds can be prepared as described in U.S. Patent No. 4,560,766 or, alternatively, are commercially available from Lonza Inc., Fair Lawn, NJ, such as Dantobrom® BTB (MEH with 3: 1 active bromine a chlorine). The mixtures of halo MEH and halo DMH used in this invention can be made by mixing DMH and MEH in a predetermined amount prior to halogenation. The mixtures can also be prepared in situ from the corresponding ketones, for example, acetone and methyl ethyl ketone, using the Bucherer-Berg Synthesis, and then halogenating the product. The methods for obtaining these mixtures of MEH and DMH halo are disclosed in U.S. Patent No. 4,560,766. Alternatively, halo mixtures MEH and DEH are available from Lonza Inc., under trade names such as Dantoin® 5-5-0 (50/50 mole ratio of MEH to DEH, all chlorine and Dantoin® 5-5- 5 (50/50 molar ratio of MEH to DEH with 3: 1 active chlorine or bromine).

Additionally, the compositions used in the invention also Á include a mixture of haiohydantoins with additives. Examples of additives which may be used in the present invention include solubility modifiers, compaction aids, fillers, surfactants, colorants, fragrances, dispersants, lubricants, mold release, detergent developers, corrosion inhibitors, chelating agents, stabilizers, biocides, bromide sources, and halogen oxidant compositions. The additives provide an additional function or serve as a processing aid in the preparation of the form. # 10 The only requirement is that the material is compatible with the composition of haiohydantoin. Products made from haiohydantoins with no more than 95 mol% DMH, at least 5 mol% MEH, and certain additives in the amounts given below are a further embodiment of the present invention. Any of the additives listed The above could be used in these products, with fc solubility modifiers, compaction aids, fillers, fragrance, mold releasers, and oxidant halogen compositions being most preferred. Solubility modifiers which can be added to the haiohydantoin described herein include, for example, sodium bicarbonate, aluminum hydroxide, magnesium oxide, barium hydroxide and sodium carbonate. See U.S. Patent No. 4,537,697. Solubility modifiers can be used in the compositions in an amount ranging from 0.5 to 50% by weight. Examples of compaction aids include inorganic salts composed of lithium, sodium, potassium, magnesium and calcium cations associated with carbonate, bicarbonate, borate, silicate, phosphate, # Percarbonate and perfosphate. See U.S. Patent No. 4,677,130. Compaction aids can be used in the compositions in an amount ranging from 0.5 to 50% by weight. The fillers added to the haiohydantoins include, for example, inorganic salts, such as combinations of lithium, sodium, potassium, magnesium and calcium cations with sulfate and chloride anions, as well as other inorganics such as clays and zeolites. Fillers are used in compositions to reduce product costs and can is added in an amount ranging from 1 to 50% by weight. Examples of surfactants include OTB aerosol (sodium dioctyl sulfosuccinate), disodium lauryl sulfosuccinate, sodium lauryl sulfoacetate, and sodium cocoyl isethionate, as well as other sulfonates. The surfactants are used in the compositions to intensify the cleaning performance and can be added in an amount ranging from 0.5 to 40% by weight. The dyes and pigments can be added in the compositions in an amount of 0.1 to 10% by weight. Examples of dyes and pigments are tetrasodium acid salt flatlocyanotetransulfonic copper, all phthalocyanines derived and without derivatizing, such as Pigment Green 7, Pigment Blue 15 and Pigment Blue 86, as well as inorganic pigments, such as lazurite. The fragrances can also be used as additives and can be added in an amount ranging from 0.1 to 10% by weight.

The dispersants can be added to inhibit the scale sediment in treated waters in an amount ranging from 0.1 to 20% by weight. Examples of dispersants include all polyacrylate-based polymers including secondary and tertiary polymers and some phosphonate dispersants, such as Bayhibit S®, tetrasodium salt of 2-phosphono-1, 2,4-butanetricarboxylic acid (PBTC). Mold releasers / lubricants, which can be added to the hydantoin include Acrawax® C, sodium stearate, calcium and magnesium. These mold / lubricant releases are added to the compositions in an amount ranging from 0.1 to % by weight. Detergent developers are added to the compositions in order to intensify the cleaning performance. An example of a detergent developer is sodium tripolyphosphate. 15 are added in an amount ranging from 1 to 50% by weight. The chelants are used in the compositions to sequester metal ions and enhance the performance of hard water and are added in an amount ranging from 1 to 50% by weight. Examples of chelating agents include sodium gluconate, ethylenediaminetetraacetic acid (EDTA), citric acid, and sodium nitrilotiracetate (NTA). The N-hydrogen stabilizers are added to the compositions in order to enhance the stability of the tablet and increase the compatibility of the additive and are added in an amount ranging from 0.5 to 20% by weight. Examples of stabilizers of N-hydrogen include dimethylhydantoin, 5,5-dimethylhydantoin (DM H), 5,5-methylethylhydantoin (MEH), cyanuric acid, sulfamic acid, sulfonamide, sulfamates, glycoluril and succinimide. Examples of inorganic biocides, which may be added to the compositions include molybdates, copper sulfate, selenates, tungstates, and chromates. See U.S. Patent No. 4,995,987. These biocides are added in an amount ranging from 0.1 to 10% by weight. Bromide sources can be added to provide f biocidal bromide (Br +) in the presence of active chlorine. The sources of The bromide can be added in an amount ranging from 1 to 30% by weight. Examples of bromide sources include sodium bromide and potassium bromide. Oxidizing halogen compositions can be added to optimize the performance of the product by optimizing the proportions of Br / CI and DMH / MEH. An example of an oxidant halogen composition is bromochlorodimethylhydantoin. They are added to the compositions in an amount ranging from 1 to 95% by weight. It has been unexpectedly found that melt extrusion processing is an ideal technique for exploiting the melting properties of the haiohydantoin compounds and obtaining haiohydantoin forms without the problems of the processes known before. The haiohydantoin powder of choice is introduced into the extruder. The extruder is heated by zones and controlled to reach the specified temperature for the particular haiohydantoin. When using this technical, only small amounts of materials are subjected to heating and only for limited periods. Other advantages of using f extruders are the high yield and the consistency of the production. The ability to mix additives in the extruder, thereby eliminating pre-mixing equipment, is an additional advantage. 5 A single extruder can provide ample flexibility in the production of shapes. The molten paste extrudate can be flowed directly into molds for tablets, tablets or other forms, including "designer" forms. Alternatively, the paste can ^ - be extruded into sheets for subsequent granulation or through dice ~~ 10 for pellet formation. An extruder used in a commercial establishment can be used for this invention. It has been found that a screw extruder, either single or double, is particularly useful in practicing the method of the present invention. A cooling and solidification system of the product is required. Band systems, used for flaking operations, can be used. Other systems known in the art can be used in this method. Any method known in the art can be used to recover the shape from the mold. Moreover, the techniques shown in the technique for granulation, extrusion cutting and cooling can be used in this method to obtain pellets and granules. The following examples are illustrative of the present invention; however, it will be understood that the invention is not limited to the specific details set forth in the examples. Examples 1-7 use a single screw extruder and Examples 8-10 use a semi-commercial twin screw extruder in the methods described therein.

Example 1 A 50/50 mixture of methylethylhydantoin and dimethylhydantoin, all chlorinated haiohydantoins (fusion range ~ 53-95 ° C DSC) (Dantoin® 5-5-0 powder, Lonza) was fed through the feed tank of an extruder (CW Brabender, Electronic Plasti-Corder Torque Rheometer, Type EPL-V302, with single screw extruder Branbender, 3-zones, type 2523 with a 25: 1 L / D stainless steel screw, 2: 1 compression ratio and bar die without insert (thermal collar attached), screw speed - 60 RPM). The following arrangements were made in the extruder: Zones 1, 2, 3: 70 ° C; Given: 65 ° C (reading); and melting temperature: 64-65 ° C. The approximate residence time of the haiohydantoin in the extruder was 30 to 40 seconds. The yield was approximately 62 grams / minute. The extrudate had the consistency of well-mixed, light pie dough and was collected in the following molds: a) 70 mm soft aluminum weight plates (approximately 100 grams); b) Small trays for ice cubes, 1 .905 cm x 1 .905 cm (approximately 16 grams); c) Small aluminum cups 4.127 cm x 1.27 cm (approximately 45 grams); and d) Various plastic molds of animals, trees and Christmas decorations (forms of "designer"). The material was also "spilled" into trays for eventual separation and sifted to form granules. After cooling to room temperature, the molded products were recovered by conventional laboratory techniques. For example, 100-gram tablets were simply removed from the 70-mm aluminum plates by pressing with the finger j = > in the center of the outer bottom of the plate. The recovered tablet kept complete integrity (uniform surface, hard) and was completely free of dust. The measurement of the force required to fracture the tablet was made by contacting a vertical blade through the face of a suspended tablet (Instron® Instrumentation). The force required to fracture the tablet was 556 N as opposed to an average of 369.184 N for commercially produced tablets of similar weight and shape. The commercial tablets used for comparison are currently made by any number of standard compaction techniques and equipment, such as rotary tablet presses, in which a powder or granule is injected into a mold and subjected to compression forces of approximately 44488 N.

Example 2 ^ w ^ A 50/50 mixture of methyl ethyl hydantoin and dimethylhydantoin, 3: 1 chlorinated to brominated haiohydantoin (melting range ~ 54.1 10 ° C, DSC) (Dantoin® 5-5-5 powder, Lonza) was processed as it was described in Example 1. The 100 gram tablets obtained maintained complete integrity and were free of dust. The breaking of the tablets required strength of 600.48 N.

^. ^ Example 3 - 10 A haiohydantoin comprising 100% methylethylhydantoin with 3: 1 active bromine to chlorine (melting range 57 ° -91 ° C, DSC) (Dantobrom® BTB powder, Lonza) was processed as described in Example 1, except that the extruder had the following provisions: Zones 1 , 2, 3: 70 °, 75 °, 70 ° C, respectively; Given 80 ° C; 15 melting temperature: ~ 81 ° C. The yield had the consistency of thick cake dough and was unloaded on a tray for grinding and conversion of granule products. The resolidified mass had good integrity and was easily ground with minimal powder. Example 4 The Dantobrom® BTB used in Example 3 was processed as described in Example 1, except that the extruder had the following provisions and given: Zones 1, 2.3: 70 ° C; Given: 65 ° C; Temperature of melting: 65 ° C; and a plug die of 0.4762 cm. An extruded filament was produced, which had good integrity on the face of the die, and which * could cut on the face directly in pellets. The pellets hardened quickly in a manageable manner.

Example 5 A dry blend of 70% Dantoin® 5-5-0, 20% dimethylhydantoin (stabilizer), and 10% copper phthalocyanotetrasulfonic acid, tetrasodium salt dye, was processed and extruded as described in Example 1, with melting temperature and given to approximately 70 ° C. A flowing smelter was produced, which was easily emptied into 30 and 100 gram molds. The cooled tablets were powder-free, hard and blue forms.

Example 6 15 Dantochlor®, a composition 8-2-0, was fed to the extruder as described in Example 1. Zones 1, 2, and 3 were 70 °, 65 °, and 60 ° C, respectively; given: 55 ° C; Melting temperature: 61 ° C. An extrudate similar to a filament was obtained, which upon cooling had an agglomerated / granular appearance. Easily broke into a powder granulate with good flow properties and minimal fines.

Example 7 Various additives were tested for their compatibility with haiohydantoins for use in melt extrusion. The mixtures are prepared comprising 90% by weight of a haiohydantoin and 10% by weight of the additive. The haiohydantoins used were either Dantoin® 5-5-0 or Dantoin® 5-5-5. The specific additives are listed in Table 2, column 3 and the category of the additive is listed in Table 2, column 2.

TABLE 2 TABLE 2 The mixtures were heated to a range of 85 ° to 95 ° C in an oil bath. Upon melting, the mixture was emptied into a small hexagonal plastic mold and allowed to cool. In each case, there was no visual discoloration and the shapes were solid and free of dust.

Example 8 Dantobrom®, a composition 8-2-0, was fed through the feed tank of a Werner / Pfleiderer ZSK-30, co-rotating twin screw extruder, established with four heating zones, one die and one plate die face The screw elements consisted of transport, kneading and pumping designs. The following arrangements were made in the extruder: Zone 1: 40 ° C; Zones 2,3,4: 50 ° C; given: 50 ° C (reading); and die face plate: 60 ° C. Dantochlor® was fed at a speed of 22.68 kg / h. The extrudate had a consistency similar to a uniform filament with excellent integrity. The die hole was 3.5 mm. The addition and operation of a knife blade pelletizer on the face of the die resulted in the formation of pellets in manageable, packable forms. The size of the pellets could be modified by adjusting the speed of the pelletizer. The pellets cooled rapidly on the conveyor belt. Example 9 Dantobrom®, a composition 8-2-5, was fed into the extruder as described in Example 8; Zones 1, 2.3 and 4 were 35 °, 45 °, 50 ° and 55 ° C, respectively; given: 65 ° C; face plate die: 75 ° C. They obtained 10 pellets with excellent integrity.

Example 10 Dantochlor® BTB used in Example 3 was processed as described in Example 8, except that the extruder had the following arrangements, die temperatures and die face silver: Zone 1: 55 ° C; Zones 2-4: 60 ° C; given: 65 ° C; Die face plate: 60 ° C. The extruded product gave an easily formed product.

Claims (20)

1. CLAIMS # 1. A method for the production of a solid halogenated hydantoin product containing from 5 to 20 mol% of methyethylhydantoin and from 80 to 95% mol of dimethylhydantoin, comprising: (a) extruding said halogenated hydantoin under conditions sufficient to partially melt only said halogenated hydantoins for a residence time not exceeding 40 seconds; f (b) cooling said extrudate to solidify said halogenated hydantoin; and (c) recovering a product substantially free of dust. The method of claim 1, wherein said methylethylhydantoin and dimethylhydantoin are halogenated with either chlorine alone or chlorine and bromine. The method of claim 1, wherein said composition contains at least 10 mol% of methylethylhydantoin and not more than 90 mol% of dimethylhydantoin. The method of claim 1, wherein said solid halogenated product also contains at least one of the following additives: a solubility modifier, a compaction aid, a filler, a 20 surfactant, a dye, a fragrance, a dispersant, a lubricant, a mold release, a detergent developer, a corrosion inhibitor, a chelator, a stabilizer, a biocide, a bromide source, and an oxidant halogen composition . The method of claim 1, wherein said solid product is a tablet, tablet, granule, pellet or dispenser. 6. The method of claim 1, wherein said halogenated hydantoin is extruded through a screw extruder. The method of claim 6, wherein said screw extruder is a single screw extruder or a twin screw extruder. 8. The method of claim 1, wherein said casting or partial melting of said halogenated hydantoin is extruded into a mold of predetermined size and shape, cooled and recovered from said mold. The method of claim 1, wherein said melting or partial melting of said halogenated hydantoin is extruded into sheets, and said 10 sheets are cooled and milled to obtain granules of halogenated hydantoin. The method of claim 1, wherein said melting or partial melting of said halogenated hydantoin is extruded through a die, cut into pellets, and cooled. 15 1 1. A solid halogenated hydantoin product containing at least 5 mol% of methylethylhydantoin and not more than 95 mol% of dimethylhydantoin made by: (a) extruding said halogenated hydantoin under conditions sufficient to partially melt only said halogenated hydantoins 20 during a residence time of not more than 40 seconds; (b) cooling said extrudate to solidify said halogenated hydantoin; and (c) recovering a solid product substantially free of dust. 12. The product of claim 1, wherein said casting or Partial casting of said halogenated hydantoin is extruded into a mold of predetermined size and shape, cooled and recovered from said mold as a solid product. The product of claim 1, wherein said casting or partial melting of said halogenated hydantoin is extruded into sheets, and Said leaves are cooled and ground into granules. The product of claim 9, wherein said casting or partial melting of said halogenated hydantoin is extruded through a die, cut into pellets and cooled. 15. The product of claim 9, wherein said product also contains at least one of the following additives: a solubility modifier, a compaction aid, a filler, a surfactant, a colorant, a fragrance, a dispersant, a lubricant, a mold release, a detergent developer, a corrosion inhibitor, a chelant, a stabilizer, a biocide, a bromide source, an oxidant halogen composition. 16. A method for making a supply of halogenated hydantoin for compaction containing at least 5 mol% of methylethylhydantoin and not more than 95 mol% of dimethylhydantoin, comprising extruding a powdery powder of said halogenated hydantoin under sufficient conditions 20 to only partially melt said halogenated hydantoins for a residence time of no more than 40 seconds to obtain an agglomerate. The method of claim 16, wherein said methylethylhydantoin and dimethylhydantoin are halogenated with chlorine alone or chlorine and bromine. 18. The method of claim 16, wherein said composition contains at least 10 mol% of methylethylhydantoin and not more than 90 mol% of dimethylhydantoin. The method of claim 16, wherein said supply of halogenated hydantoin also contains at least one of the following additives: a solubility modifier, a compaction aid, a filler, a surfactant, a dye, a fragrance, a dispersant, a lubricant, a mold release, a detergent developer, a corrosion inhibitor, a chelant, a stabilizer, a biocide, a bromide source, and an oxidant halogen composition. 20. The product of claim 13, wherein the partial melting of the solid halogenated hydantoin product contains a powdery powder and the recovered solid product is an agglomerate.