WO1997017180A1 - Halohydantoin forms and method by melt extrusion - Google Patents
Halohydantoin forms and method by melt extrusion Download PDFInfo
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- WO1997017180A1 WO1997017180A1 PCT/US1996/018403 US9618403W WO9717180A1 WO 1997017180 A1 WO1997017180 A1 WO 1997017180A1 US 9618403 W US9618403 W US 9618403W WO 9717180 A1 WO9717180 A1 WO 9717180A1
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- WIPO (PCT)
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- mole
- product
- melt
- halogenated hydantoin
- halogenated
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/72—Two oxygen atoms, e.g. hydantoin
- C07D233/80—Two oxygen atoms, e.g. hydantoin with hetero atoms or acyl radicals directly attached to ring nitrogen atoms
- C07D233/82—Halogen atoms
Definitions
- halogenated hydantoins in the form of high integrity granules, pellets and shaped forms, such as tablets, briquettes, and the like. These halohydantoin forms are useful in a variety of applications, such as bleaching, dishwashing, toilet bowl disinfection, and water treatment applications such as swimming pools, cooling water systems, and spas.
- High integrity refers to solid products having a predetermined shape, which are hard, shape-retentive, and dust-free. Dust-free products are desirable because halogen donor compounds are irritating in nature. Furthermore, high dusting intensifies the halogen odor associated with these compounds, which is also irritating.
- Halogenated derivatives of dimethylhydantoin are used in a variety of applications, such as swimming pool sanitizers (bromochloro-dimethylhydantoin) and bleaching (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.
- binders to produce a commercial form of halodimeth- ylhydantoin increases costs, and can require additional processing steps, e.g., a blending operation. Moreover, the binders do not alleviate the dust problem to the degree of the present invention. Many of the forms made by compaction are dusty and friable, and lack true integrity.
- Briquettes which are useful for water treatment, can be made by compaction.
- applications such as toilet cleaning require the halohydantoin to be in tablet form and the problems of producing larger forms by compaction techniques are increased in this form.
- halogenated hydantoins for pool disinfection need to be in a different form because of the high dissolution rate of the compacted briquettes.
- the forms necessary for pool disinfection also cannot be made by compaction.
- melt techmques i.e. , casting a molten material into a form, solidifying the material, and discharging the product by conventional means
- melt techmques i.e. , casting a molten material into a form, solidifying the material, and discharging the product by conventional means
- Melt techniques provide particular advantage in the making of forms in that virtually any form of any size can be made, requiring only a mold of the specific size and shape, and that only limited by the creativity of the designer. "Designer" forms that might incorporate a logo or specific shape are possible. In some instances, the mold itself may serve as a dispenser for the compound, e.g. , institutional dishwashing applications.
- halogenated methylethylhydantoin is an excellent candidate for melt techniques because of its low melt range and the great differential between its melt temperature and decomposition temperature. It has been found that, when halogenated methylethylhydantoin is mixed with halogenated dimethylhydantoin, the mixture can be shaped via melt techniques.
- the low melting methylethylhydantoin derivatives serve to disperse unmelted components to give the overall mix flow properties. See U.S. Patent No. 4,560,766 issued to Girard et al.
- the melt technique set forth in Girard et al. and used in the art for halohydantoins consists of a melt pot with a feed to a molding system.
- This system has several disadvantages. For one, it is very difficult to uniformly heat melt pots of halohydantoin, due to poor heat transfer in powders of this nature. In order to melt the material enough so that flow is established, the material near the heat source will necessarily be heated to a higher temperature than the material in the middle of the pot.
- these halohydantoins have a rather large temperature differential between their melt temperature and their decomposition temperature, some breakdown and loss of material does occur in the melt pot techmque when the material is left at the required high temperatures for too long.
- the breakdown of the material is undesirable for a number of reasons. For one, the fumes which will result from the breakdown are toxic. Further, the breakdown of the material can lead to a less pure and less effective compound. Further, the halohydantoin material being heated in the melt pot will have a long heat history. When making a mold using this technique, more halohydantoin than is needed 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 the halohydantoin. However, after several times, the halohydantoin will break down and be unsatisfactory for use.
- melt extrusion techniques melt only the discrete, exact amount of material needed for the mold. Also, the material is subjected to elevated temperatures for only short periods of time due to large surface area contact with the material in an extruder. Moreover, a large change in temperature is not required to achieve the desired melt. Further, because melt extrusion techniques can cause materials to flow that are not readily flowing, only partial melting of the material is necessary. This reduces heat input.
- melt extrusion techniques are not normally used with these systems.
- no one has applied melt extrusion techniques to produce forms of halohydantoins.
- the resulting halohydantoin forms made by the melt extrusion process are dust-free, of high integrity, and stronger than forms made by conventional commercial methods.
- An additional advantage of extrusion techniques is that additives can be formulated into the halohydantoin at the extruder itself because of the ability of the extruder to mix materials, particularly with twin screw equipment.
- the present invention relates to the production of a solid halogenated hydantoin product by extruding a melt or a partial melt of the halohydantoin, cooling the extrudate to solidify the halohydantoin, and recovering the solid product.
- This process can be used to produce a variety of halohydantoin forms.
- One embodiment of the invention relates to the production of halohydantoin forms by extruding a melt or partial melt of the halohydantoin into a mold of a predetermined size and shape, cooling the mold to solidify the halohydantoin, and recovering the solidified form from the mold in traditional techniques.
- the mold may serve as a dispenser for the chemical in its final application. Any form that can be produced in a mold or a die can be produced by this method, including tablets, pucks, pastilles, briquettes, pellets, granules, and so-called "designer" forms such as Christmas ornaments.
- Another embodiment of the invention relates to a method of making granules of halohydantoin by extruding a melt or partial melt of the halohydantoin into sheets, cooling the sheets to solidify the halohydantoin, and grinding the sheets to obtain granules.
- a further embodiment of the invention is a method for making pellets of halohydantoin by extruding a melt or partial melt of the halohydantoin through a die or screens to form strands, which are subsequently cut by conventional techniques into pellets, and cooling the resulting pellets.
- a further embodiment of the invention is a method for producing an
- the extruder used in this method is a twin screw extruder. 5
- the invention also relates to the solid halohydantoin product produced by the methods described above, including forms, granules, pellets, and feedstocks.
- this extrusion technique can be applied to compositions containing the halohydantoins along with additives.
- Another embodiment of the present invention are the extruded solid halogenated hydantoin products comprised of halohydantoins alone or with an additive.
- halohydantoin compounds contemplated for use in this invention are described in U.S. Patent No. 4,560,766, which is hereby incorporated by reference. These halohydantoin compounds have methylethylhydantoin (MEH) as a sole constituent or are an admixture of MEH and a halogenated dimethylhydantoin (DMH).
- MEH methylethylhydantoin
- DMH halogenated dimethylhydantoin
- halogenated methylethylhydantoin for use in this invention has the following structure:
- X, and X 2 may be the same or different and are chlorine and bromine.
- halogenated dimethylhydantoins for use in this invention have the following structure:
- X, and X may be the same or different and are chlorine and bromine.
- Halogenated MEH compounds as compared to their 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 halogenated MEH compounds. These MEH compounds melt from about
- mixtures of the dihalo DMH and MEH have the melt characteristics of the MEH derivatives such that fluid systems, consisting of unmelted dispersed solids in a molten medium, can be formed at low temperatures. Temperatures significantly below the thermal decomposition point of the mix are utilized.
- Table 1 shows a range of products with melt and decomposition data. The products are listed in terms of their makeup relative to DMH, MEH and bromine (moles).
- Dantobrom ® is - 0_ DMH + ⁇ 2 MEH + Q NaBr and is thus referred to as product "8-2-5". Since each molecule of the hydantoin final product contains 2 moles of halogen, the moles of chlorine in each final product is 2.0 minus the moles of
- the composition is then halogenated using conventional techniques. Two (2) moles of chlorine are added to every composition. If a bromochlorohydantoin or dibromohydantoin is desired, bromine, in the form of NaBr, is added in the desired molar amount. In a simple oxidation/reduction reaction, the chlorine oxidizes the bromine in the NaBr to Br + , which then halogenates the DMH and MEH. Since each product has two moles of halogen, the remainder is halogenated by chlorine. For example, in making Dantoin ® 5-5-5, 0.5 mole of NaBr and 2.0 moles of chlorine are used to halogenate the MEH and DMH.
- the chlorine (0.5 mole) oxidizes the 0.5 mole of NaBr to Br + , which halogenates the DMH/MEH, and the remaining chlorine (1.5 moles) halogenates the MEH/DMH.
- the final product contains 1.5 moles 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.
- the temperatures the halohydantoin compounds begin to melt are the lowest temperatures in the melt ranges shown.
- the data in Table 1 show that, with the exception of the dibromo derivatives, products containing greater than or equal to 20% MEH in the hydantoin makeup have differences between start of melt temperatures and decomposition temperatures greater than or equal to 65°C and typically 70-100°C.
- Halohydantoins with differences greater than 60°C, preferably greater than 70 °C, between their start of melt and decomposition temperature can be used in the method of the present invention.
- Halohydantoins with no more than 95 mole % of DMH and at least 5 mole % MEH can be used in this invention, with 0 to 90 mole % DMH and 10 to 100 mole % MEH being preferred.
- the most preferred halohydantoins used in this invention contain 0 to 80 mole % DMH and 20 to 100 mole % MEH.
- Halohydantoins made of 50 mole % DMH and 50 mole % MEH are preferred for melt extrusion of molded forms and granules.
- Halohydantoins made of 80 mole % of DMH and 20 mole % of MEH are preferred for making pellets.
- Halohydantoins made of no more than 95 mole % of DMH and at least 5 mole % MEH are preferred for making agglomerate.
- Halogenated MEH compounds can be prepared as described in U.S. Patent No. 4,560,766 or, alternatively, are available commercially from Lonza Inc., Fair Lawn, NJ, such as Dantobrom ® BTB (MEH with 3: 1 active bromine to chlorine).
- the mixtures of halo MEH and halo DMH used in this invention can be made by mixing DMH and MEH in a predetermined quantity prior to halogenation. Mixtures can also be prepared in situ from the corresponding ketones, e.g., acetone and methylethylketone, using the Bucherer-Berg Synthesis, and then halogenating the product. Methods for obtaining these mixtures of halo MEH and DMH are set forth in U.S.
- compositions used in the invention also include a mixture of halohydantoins with additives.
- additives which can be used in the present invention include solubility modifiers, compaction aids, fillers, surfactants, dyes, fragrances, dispersants, lubricants, mold releases, detergent builders, corrosion inhibitors, chelants, stabilizers, biocides, bromide sources, and oxidizing halogen compositions.
- the additives provide an additional function or serve as a processing aid in the preparation of the form. The only requirement is that the material be compatible with the halohydantoin composition. Products made of halohydantoins with no more than 95 mole
- % of DMH at least 5 mole % MEH, and certain additives in the amounts given below are a further embodiment of the present invention. Any of the additives listed above could be used in these products, with solubility modifiers, compaction aids, fillers, fragrance, mold releases, and oxidizing halogen compositions being the most preferred.
- Solubility modifiers which may be added to the halohydantoin described herein include, for example, sodium bicarbonate, aluminum hydroxide, magnesium oxide, barium hydroxide, and sodium carbonate. See United States Patent No. 4,537,697. Solubility modifiers can be used in the compositions in an amount ranging from 0.5 to 50% by weight.
- compaction aids include inorganic salts comprised of lithium, sodium, potassium, magnesium and calcium cations associated with carbonate, bicarbonate, borate, silicate, phosphate, percarbonate and perphosphate. See United States Patent No. 4,677,130. Compaction aids can be used in the compositions in an amount ranging from 0.5 to 50% by weight.
- Fillers added to the halohydantoins 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 the compositions to reduce product costs and can be added in an amount ranging from 1 to 50% by weight.
- surfactants examples include Aerosol OTB (sodium dioctyl sulfosuccinate), disodium lauryl sulfosuccinate, sodium lauryl sulfoacetate, and sodium cocoy -isethionate, as well as other sulfonates.
- Surfactants are used in the compositions to enhance cleaning performance and can be added in an amount ranging from 0.5 to 40 % by weight.
- Dyes and pigments can be added to the compositions in an amount of 0.1 to 10% by weight.
- dyes and pigments are copper phthalocyanine tetrasulfonic acid tetra sodium salt, all derivatized and underivatized phthalocyanines such as Pigment Green 7, Pigment Blue 15, and Pigment Blue 86, as well as inorganic pigments, such as lazurite.
- Fragrances can also be used as additives and can be added in an amount ranging from 0.1 to 10% by weight.
- Dispersants may be added to inhibit scale deposition 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 ® , 2-phosphono-l,2,4-butanetricarboxylic acid tetra-Na salt (PBTC).
- Bayhibit S ® 2-phosphono-l,2,4-butanetricarboxylic acid tetra-Na salt
- Lubricant/mold releases which may be added to the hydantoin include Acrawax ® C, magnesium, calcium, and sodium stearate. These lubricant/ mold releases are added to the compositions in an amount ranging from 0.1 to 20% by weight.
- Detergent builders are added to the compositions in order to enhance cleaning performance.
- An example of a detergent builder is sodium tripolyphosphate. They are added in an amount ranging from 1 to 50% by weight.
- Chelants are used in the compositions to sequester metal ions and enhance hard water performance and are added in an amount ranging from 1 to 50% by weight.
- chelants include sodium gluconate, ethylene diamine tetraacetic acid (EDTA), citric acid, and sodium nitrilotriacetate (NTA).
- N-hydrogen stabilizers are added to the compositions in order to enhance tablet stability and increase additive compatibility and are added in an amount ranging from 0.5 to 20% by weight.
- N-hydrogen stabilizers include dimethylhydantoin, 5, 5 -dimethylhydantoin (DMH), 5, 5 -methylethylhydantoin (MEH), cyanuric acid, sulfamic acid, sulfonamide, sulfamates, glycoluril, and succinimide.
- inorganic biocides which may be added to the compositions include molybdates, copper sulfate, selenates, tungstates, and chromates. See United States Patent No. 4,995,987. These biocides are added in an amount ranging from 0.1 to 10% by weight.
- Bromide sources may be added to provide biocidal bromide (Br + ) in the presence of active chlorine. Bromide sources may 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 may be added to optimize product performance by optimizing Br/Cl and DMH/MEH ratios.
- An example of an oxidizing 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 halohydantoin compounds and obtaining halohydantoin forms without the problems of the prior known processes.
- the halohydantoin powder of choice is introduced into the extruder.
- the extruder is zone-heated and controlled to achieve the specified temperature for the particular halohydantoin.
- a single extruder can provide wide flexibility in producing forms.
- the molten slurry extrudate can be directly flowed into molds for tablets, briquettes, or other shapes, including "designer" shapes.
- the slurry can be extruded to sheets for subsequent granulation or through dies for pelletization.
- Any extruder used in a commercial setting can be used for this invention. It has been found that a screw extruder, either single or twin, is particularly useful in practice of the method of the present invention.
- a system for cooling and solidification of the product is required.
- Belt 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 for recovering the form from the mold.
- techniques known in the art for granulation, cutting extrudate, and cooling can be used in this method for obtaining pellets and granules.
- 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 chlorine halohydantoin (melt range - 53-95 °C DSC) (Dantoin ® 5-5-0 powder, Lonza) was fed through the hopper of an extruder (CW. Brabender, Electronic Plasti-Corder Torque Rheometer, Type EPL-V302, with Brabender single screw extruder, 3-zone, Type 2523 with a stainless steel screw 25:1L/D, 2: 1 compression ratio and rod die with no insert (thermal collar attached), screw speed - 60 RPM).
- CW. Brabender Electronic Plasti-Corder Torque Rheometer
- Type EPL-V302 with Brabender single screw extruder, 3-zone, Type 2523 with a stainless steel screw 25:1L/D, 2: 1 compression ratio and rod die with no insert (thermal collar attached), screw speed - 60 RPM).
- Zones 1, 2, 3 70°C
- Die 65°C (readout); and melt temperature: 64-65°C.
- the approximate residence time of the halohydantoin in the extruder was 30 to 40 seconds.
- the output was approximately 62 grams/minute.
- the exudate had the consistency of light, well-mixed pancake batter and was collected in the following molds: a) 70 mm smooth aluminum weight dishes (approximately 100 grams); b) small ice cube trays, % " x 34" (approximately 16 grams); c) small aluminum cups 1%" X 7 / ⁇ ", (approximately 45 grams); and d) various plastic molds of animals, trees and Christmas decorations ("designer" forms).
- the material was also "spilled" into trays for eventual break-up and screening to form granules.
- the molded products were recovered by conventional laboratory techmques. For example, 100 gram tablets were simply popped out of the 70 mm aluminum dishes by exerting finger pressure on the outside bottom center of the dish. The recovered tablet maintained full integrity (hard, uniform surface) and was completely dustless. Measurement of the force required to fracture the tablet was performed by contacting a vertical blade across the face of a suspended tablet (Instron ® Instrumentation). The force required to fracture the tablet was 125 lb. as opposed to an average of 83 lb. 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 10,000 pounds.
- the 100 gram tablets obtained maintained full integrity and were dustless. Breaking of the tablets required 135 lb. force.
- a halohydantoin comprising 100% methylethylhydantoin with 3:1 active bromine to chlorine (melt range 57°-91°C, DSC) (Dantobrom ® BTB powder, Lonza) was processed as described in Example 1, except the extruder had the following settings: Zones 1, 2, 3: 70°, 75°, 70°C, respectively; Die 80°C; melt temperature: - 81 C C.
- the output had the consistency of thick pancake batter and was discharged onto a tray for grinding and conversion to granule products.
- the resolidified mass had good integrity and ground readily with minimal dust.
- Example 4 Dantobrom ® BTB used in Example 3 was processed as described in
- Example 1 except the extruder had the following settings and die: Zones 1, 2, 3: 70°C; Die: 65°C; melt temperature: 65°C; and a 3/16" plug die. A strand of extrudate was produced which had good integrity at the die face, and which could be cut at the die face directly into pellets. The pellets hardened rapidly into handleable form.
- Example 2 A dry blend of 70% Dantoin ® 5-5-0, 20% dimethylhydantoin (stabilizer), and 10% copper phthalocyaninetetrasulfonic acid, tetra sodium salt dye was processed and extruded as described in Example 1 , with die and melt temperature at approximately 70°C. A flowing melt was produced which was readily cast into 30 and 100 gram molds. The cooled tablets were blue, hard, non-dusting forms.
- Dantochlor ® an 8-2-0 composition
- Zones 1, 2, and 3 were 70°, 65°, and 60°C, respectively; die: 55 °C; melt temperature: 61 °C.
- a strand-like extrudate was obtained which on cooling had an agglomerated/granular appearance. It was readily broken into a granular powder with good flow properties and minimal fines.
- the mixtures were heated to a range of 85° to 95 °C in an oil bath. Upon melting, the mixture was poured into a small hexagonal plastic mold and allowed to cool. In each case, there was no visual discoloration and the forms were solid and dust-free.
- Dantochlor ® an 8-2-0 composition
- the screw elements consisted of conveying, kneading, and pumping designs. The following settings were made on the extruder: Zone 1: 40° C; Zones 2, 3, 4: 50°C; die: 50°C (readont); and die face plate: 60°C.
- Dantochlor ® was fed at a rate of 50 lbs/hr. The exudate had a uniform strand-like consistency with an excellent integrity. The die hole was 3.5 mm. Addition and operation of a knife blade pelletizer at the die face resulted in the formation of pellets in handleable, packageable 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 Dantochlor ® , an 8-2-5 composition, was fed into the extruder as described in Example 8; Zones 1, 2, 3, and 4 were 35°, 45°, 50°, and 55°C, respectively; die: 65 °C; die face plate: 75 °C. Pellets with excellent integrity were obtained.
- Dantochlor ® BTB used in Example 3 was processed as described in Example 8, except the extruder had the following settings, die and die face plate temperatures: Zone 1: 55°C; Zones 2-4: 60°C; die: 65°C; die face plate: 60°C.
- the extrudate produced gave a readily formed product.
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Abstract
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Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP96940490A EP0859692A4 (en) | 1995-11-07 | 1996-11-07 | Halohydantoin forms and method by melt extrusion |
AU77359/96A AU7735996A (en) | 1995-11-07 | 1996-11-07 | Halohydantoin forms and method by melt extrusion |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US55447695A | 1995-11-07 | 1995-11-07 | |
US08/554,476 | 1995-11-07 | ||
US08/645,798 US5750061A (en) | 1995-11-07 | 1996-05-16 | Halohydantoin forms produced by melt extrusion and method for making |
US08/645,798 | 1996-05-16 |
Publications (1)
Publication Number | Publication Date |
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WO1997017180A1 true WO1997017180A1 (en) | 1997-05-15 |
Family
ID=27070597
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/US1996/018403 WO1997017180A1 (en) | 1995-11-07 | 1996-11-07 | Halohydantoin forms and method by melt extrusion |
Country Status (4)
Country | Link |
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EP (1) | EP0859692A4 (en) |
AU (1) | AU7735996A (en) |
CA (1) | CA2236992A1 (en) |
WO (1) | WO1997017180A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5972864A (en) * | 1997-02-14 | 1999-10-26 | Lonza Inc. | Bleaching and cleaning compositions containing fragrances |
US7279582B2 (en) | 1995-12-13 | 2007-10-09 | Abbott Laboratories | Retroviral protease inhibiting compounds |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3803285A (en) * | 1971-01-20 | 1974-04-09 | Cpc International Inc | Extrusion of detergent compositions |
US4418030A (en) * | 1980-12-24 | 1983-11-29 | Bayer Aktiengesellschaft | Process for the production of granulates of organic substances present in the form of a melt |
US4560766A (en) * | 1983-02-02 | 1985-12-24 | Glyco Chemicals, Inc. | Shaped halogenated hydantoins |
EP0206725A2 (en) * | 1985-06-14 | 1986-12-30 | Jeyes Group Limited | Lavatory cleansing compositions |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3485328D1 (en) * | 1984-09-13 | 1992-01-16 | Lonza Ag | METHOD FOR PRODUCING HALOGENED HYDANTOINE. |
US5753602A (en) * | 1995-12-18 | 1998-05-19 | The Block Drug Company | Chlorine cleanser tabletting process and product |
-
1996
- 1996-11-07 WO PCT/US1996/018403 patent/WO1997017180A1/en not_active Application Discontinuation
- 1996-11-07 CA CA 2236992 patent/CA2236992A1/en not_active Abandoned
- 1996-11-07 AU AU77359/96A patent/AU7735996A/en not_active Abandoned
- 1996-11-07 EP EP96940490A patent/EP0859692A4/en not_active Withdrawn
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3803285A (en) * | 1971-01-20 | 1974-04-09 | Cpc International Inc | Extrusion of detergent compositions |
US4418030A (en) * | 1980-12-24 | 1983-11-29 | Bayer Aktiengesellschaft | Process for the production of granulates of organic substances present in the form of a melt |
US4560766A (en) * | 1983-02-02 | 1985-12-24 | Glyco Chemicals, Inc. | Shaped halogenated hydantoins |
EP0206725A2 (en) * | 1985-06-14 | 1986-12-30 | Jeyes Group Limited | Lavatory cleansing compositions |
Non-Patent Citations (1)
Title |
---|
See also references of EP0859692A4 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7279582B2 (en) | 1995-12-13 | 2007-10-09 | Abbott Laboratories | Retroviral protease inhibiting compounds |
US5972864A (en) * | 1997-02-14 | 1999-10-26 | Lonza Inc. | Bleaching and cleaning compositions containing fragrances |
Also Published As
Publication number | Publication date |
---|---|
EP0859692A1 (en) | 1998-08-26 |
AU7735996A (en) | 1997-05-29 |
CA2236992A1 (en) | 1997-05-15 |
EP0859692A4 (en) | 1999-02-03 |
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