CA2258994A1 - Polyamide compositions for removal of polyphenols from liquids - Google Patents
Polyamide compositions for removal of polyphenols from liquids Download PDFInfo
- Publication number
- CA2258994A1 CA2258994A1 CA002258994A CA2258994A CA2258994A1 CA 2258994 A1 CA2258994 A1 CA 2258994A1 CA 002258994 A CA002258994 A CA 002258994A CA 2258994 A CA2258994 A CA 2258994A CA 2258994 A1 CA2258994 A1 CA 2258994A1
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- CA
- Canada
- Prior art keywords
- amide
- piperazine
- polymer
- dicarboxylic
- liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L2/00—Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation
- A23L2/70—Clarifying or fining of non-alcoholic beverages; Removing unwanted matter
- A23L2/80—Clarifying or fining of non-alcoholic beverages; Removing unwanted matter by adsorption
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12H—PASTEURISATION, STERILISATION, PRESERVATION, PURIFICATION, CLARIFICATION OR AGEING OF ALCOHOLIC BEVERAGES; METHODS FOR ALTERING THE ALCOHOL CONTENT OF FERMENTED SOLUTIONS OR ALCOHOLIC BEVERAGES
- C12H1/00—Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages
- C12H1/02—Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages combined with removal of precipitate or added materials, e.g. adsorption material
- C12H1/04—Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages combined with removal of precipitate or added materials, e.g. adsorption material with the aid of ion-exchange material or inert clarification material, e.g. adsorption material
- C12H1/0416—Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages combined with removal of precipitate or added materials, e.g. adsorption material with the aid of ion-exchange material or inert clarification material, e.g. adsorption material with the aid of organic added material
- C12H1/0424—Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages combined with removal of precipitate or added materials, e.g. adsorption material with the aid of ion-exchange material or inert clarification material, e.g. adsorption material with the aid of organic added material with the aid of a polymer
Abstract
Amide-containing polymers characterized by the presence of piperazine amide and/or substituted piperazine amide in the polymer chain are used as adsorbents to remove polyphenolic compounds from liquids. The compositions are especially useful in combination with protein removal agents such as silica gel or tannin. The amide-containing polymer compositions (alone or in combination with protein removal agents) are especially useful in the stabilization and/or chillproofing of plant derived liquids or beverages such as beer, wine, fruit juice and vegetable juice.
Description
CA 022~8994 1998-12-23 Polyamide Compositions for Removal of Polyphenols from Liquids Backqround of the Invention It is well known that many liquids such as beverages derived from 5 grains/fruits/vegetables may contain certain polyphenols and proteins which create problems when beverages are mass produced. Specifically. these compounds may cause degradation of flavor and/or appearance for such beverages where they are stored for prolonged periods of time, subjected to variations in temperature, etc. The problem of removing adverse components is made more difficult by the fact that the ; 10 adverse components are chemically similar to components which are desired in the beverage .
The removal of these adverse components from beverages prior to packaging for sale has been addressed by treating the beverages with various materials designed to adsorb one or more of the adverse components from the 15 beverage. Due to the diverse nature of these adverse components, most treatments have involved contacting of the beverage with a combination of adsorbents, either simultaneously or sequentially. For removal of polyphenolics, certain polyamideshave been used such as nylons and polyvinylpolypyrrolidone (PVPP). By far~ PVPP
has been the most widely used adsorbent for removal of polyphenolics and is 20 considered to be significantly more effective than nylons. For removal of adverse . proteins, the adsorbents such as silica gels and tannins have been used.
While PVPP is an effective polyphenol adsorbent, PVPP is an expensive material in the context of treating liquids on a commercial scale. This is especially true for the commercial production of beer and fruit juices. Due to its expense, most 25 users of PVPP regenerate it after use by treatment with basic and acidic solutions.
The regenerability of PVPP is limited. Also, the use of regenerated PVPP may result in the introduction of unwanted acid or base into the liquid to be treated. PVPP has further disadvantages in that it is affected by the presence of yeast. Thus, PVPP can be added to the processing of a beverage only after the yeast has been substantially 30 removed. Thus, there is a need for alternative polyphenol adsorbents which provide the adsorption performance of PVPP without its disadvantages.
AMENDED StlEET
i CA 022~8994 1998-12-23 Summarv of the Invention ~ he invention provides alternative polyphenol adsorbents for use in treating polyphenol-containing liquids. These alternative adsorbents are amide-containingpolymers characterized by the presence of piperazine amide units in the polymer chain.
In one aspect, the invention encomp~-~ses a method of treating a liquid containing polyphenolic compounds to remove some or all of the polyphenolic compounds from said liquid, the method comprising:
(a) contacting the liquid with a polymer wherein at least a portion of the polymer chain comprises piperazine amide units whereby at least a portion of the polyphenolic compounds is adsorbed by the amide-containing polymer, and (b) separating said amide-containing polymer with the adsorbed polyphenolic compounds from the liquid.
In another aspect, the invention encompasses a method of treating a liquid containing polyphenolic compounds and proteins to remove some or all of the polyphenolic compounds and proteins from said liquid, the method comprising:
(a) contacting the liquid with a polymer wherein at least a portion of the polymer chain comprises piperazine arnide units whereby at least a portion of the polyphenolic compounds is adsorbed by the amide-containing polymer, (b) separating the amide-containing polymer with the adsorbed polyphenolic compounds from the liquid, (i) contacting the liquid with a protein adsorbent whereby at least a portion of the proteins are adsorbed by the protein adsorbent, and (ii) separatin~ said adsorbed protein from said liquid. Steps (a) and (i) may be performed simultaneously or sequentially. Preferably, a protein-adsorbingsilica is used in step (i).
The amide-containing polymer preferably contains piperazine C2-C,2 carboxylamides. The amide-containing polymer may contain additional chain constituents such as aliphatic or alicyclic diamines (as diamides).
. , . ,, . . ,, .... ~ ~ . . .. . . .. .
CA 022~8994 1998-12-23 Wo 98/004S3 PC r/uss71os822 Detailed Description of the Invention The invention encompasses the discovery that amide-containing polymers which contain piperazine amide are especially useful for removing undesired polyphenolic compounds from liquids, especially beverages (e.g., beer, wine or juice) derived from plant matter (e.g., grains, fruits or vegetables). These polymers are useful in the stabilization and/or chillproofing of such beverages. For such purposes, the piperazine amide-containing polymers may be used alone or in combination with a conventional beverage treatrr~ent agent, especially a protein removal agent such as silica gel.
The polyphenol-adsorbing polymers of the invention are characterized by the presence in the polymer chain of a piperazine amide component:
~ ~ C --C
Il 11 / \
C--Q--C--N N--C - C /
where Q can be any constituent corresponding to the body of the polycarboxylic compound used to form the amide. The piperazine trepresented in brackets above) of the piperazine amide component is preferably ordinary piperazine, however, N-substituted piperazines such as 1-(2-aminoethyl) piperazine (AEP) or other substituted piperazines such as C1 -C6 dialkyl piperazine may also be used to provide the piperazine amide component. In using such alternative piperazines, it is preferred that the formation of water-soluble polyamides is avoided. Thus, ordinary piperazine is preferably not completely replaced with AEP.
The acyl portion of the piperazine amide component is preferably derived from a dicarboxylic compound such as a dicarboxylic acid or dicarboxylic acid ester - or other dicarboxylic compound. Preferred dicarboxylic compounds are aliphatic C2-C12 dicarboxylic compounds and compounds based on fatty acid dimers. Preferred aliphatic dicarboxylic compounds are:
R~CO~[CH2]n~CO~R~
CA 022~8994 1998-12-23 where R and Rl can be OH. OR", or a halogen; n=0-10, and R" is any ester group wherein the compound would react with the piperazine to release R and R'. Of these compounds. adipoyl and succinyl compounds are most preferred. Other polycarboxylic compounds may be substituted for the dicarboxylic compound.
Examples of suitable di- and polycarboxylic compounds are disclosed in US Patent4,182,844 and British Patent 1,496,508, the disclosures of which are incorporated herein by reference. If desired, mixtures of different polycarboxylic compounds may be employed.
The polyphenol-adsorbing polymers of the invention may further contain other - 10 components to modify and improve the performance of the resulting polymer. For example, a portion of the piperazine component may be replaced with another polyamine component such as aliphatic polyamines (e.g., triethylenetetramine~
hexamethylenediamine~ 2,2-dimethyl-1,3-propanediaminel N-methyl-1,3-propanediamine) and alicyclic polyamines (e.g., 1, 4-diaminocyclohexane). Other suitable polyamines are disclosed in US Patent 4,182,844 and German Patent 43 28254, the disclosures of which are incorporated herein by reference. Where such other polyamine is present, the mole ratio of piperazine to all other polyamines (total) is preferably about 5-95:95-5. More preferably, the total of other polyamines ispresent at about 5-25 mole percent of the combination of piperazine and such other polyamines.
The proportions of the piperazine, polycarboxylic acid, and alternative ~- polyamine may be varied to some extent. On an equivalents basis, the amide-containing polymers of the invention preferably contain approximately equal amounts of (a) piperazine + alternative polyamine and (b) polycarboxylic acid.
The amide-containing polymers of the invention preferably not water soluble.
The polymer particles preferably have a particle size of about 0.1-300 ~Lm, morepreferably about 0.5-200 ~Lm, and a surface area of about 0.1-50 m2/g.
If desired, the amide-containing polymers of the invention may be supported on support particles or a support substrate. For example, the amide-containing polymers of the invention may be supported on inorganic oxide particles such as siliceous oxides, especially amorphous silicas. In such instances, the supported A~\/IEN~E~ S~IEET
CA 022~8994 1998-12-23 composition preferably comprises at least about 10 wt.% (more preferably about 20-50 wt.%) of the amide-containing polymer based on the total weight of the amide-containing polymer and the support.
The amide-containing polyphenol adsorbents of the invention may be used alone or in combination with other adsorbents known to be useful for treating beverages. If desired, conventional polyphenol adsorbents such as nylon or PVPP
may be used in combination with the amide-containing polyphenol adsorbents of the invention. Preferably, the amide-containing polyphenol adsorbents of the invention are used in combination with a protein adsorbent such as tannin or silica gel. Most preferably, the amide-containing polyphenol adsorbent is used in combination with a silica gel such as Daraclar~ 7500 (sold by W. R. Grace & Co.). Conventional tannins such as Brewtan~ (Omnichem N.V.) may be used to adsorb proteins. Silica gels (xerogels or hydrogels) are preferred especially because of their relative ease of use compared to tannins. Where tannin is used, it is preferred that the tannin and the polyphenol adsorbent of the invention are not present simultaneously in the beverage to be treated.
The amide-containing polyphenol adsorbents of the invention may be used to treat various liquids where polyphenol removal is desired, however, the amide-containing polyphenol adsorbents of the invention are especially useful for the removal of polyphenols from plant-derived beverages such as juices and fermentedbeverages (e.g., beer, wine, etc.). In plant derived beverages, the amide-containing polyphenol adsorbents, when used alone or in combination with a protein adsorbent, provide excellent stabilization and/or chillproofing. The amide-containing polyphenol adsorbents of the invention may be used to treat be~lerages in a similar manner as PVPP and nylon are currently used in the art, however, the adsorbents of the invention are especially advantageous in that they may be added directly to yeast-containing beverages (i.e. prior to yeast removal). See for example the techniques described in U.S. Patents 3,264,372; 4,073,954 and 4,008,339, the disclosures ofwhich are incorporated herein by reference. The amide-containing polyphenol adsorbents of the invention are preferably used in an amount effective to achieve the desired degree of polyphenol removal. Typical dosages may be on the order of 1-150 g/h-L.
. .
CA 022~8994 1998-12-23 When a combination of the amide-containing polyphenol adsorbents of the invention and a protein adsorbent are used, the relative proportions of these may be varied to achieve the desired performance for the specific liquid or beverage used.
The relative proportions may vary significantly even for treatment of beverages of the 5 same general class (e.g. beers). Where the protein adsorbent is a siliceous material, the weight ratio of the siliceous adsorbent to the polyphenol adsorbent is preferably about 0.01-100:1, more preferably about 5-10:1. Where the polyphenol adsorbent is used in a supported form, the above ratios should be determined excluding the weight of the support (as part of the polyphenol adsorbent or as part of the siliceous ~, 10 adsorbent where the support is siliceous). The combination of polyphenol and protein adsorbents may be used sequentially (with removal of the one adsorbent before addition of the other) or simultaneously (except for tannin as noted above) wherein both adsorbents are added at the same time or where one is added while the other is present in the liquid to be treated. The polyphenol adsorbent and protein 15 adsorbent may be used in any order.
The amide-containing polyphenol adsorbents of the invention may be synthesized by any known technique such as those described in US Patent 4,182.844, British Patent 1,~96,508 and German Patent 43 28 254. In one method (interfacial polymerization), the piperazine component and a base such as sodium20 hydroxide or sodium carbonate are dissolved in water. A solution of dicarboxyl ~ chloride (e.g. succinyl chloride) in methylene chloride is then added rapidly (in less '- than one minute) to the piperazine solution using strong agitation (e.g. a blender).
Agitation is then maintained for an additional 5-20 minutes. The resulting slurry is then dried at about 40-50~C and washed (to remove chloride by-products of the 25 polymerization) with deionized water until a neutral pH is reached. Where alternative polyamines are used in combination with the piperazine component, the alternative polyamine is preferably dissolved in the piperazine solution.
Where the amide-containing polymer is to be made in a supported form, the above mentioned components are preferably first combined and the resulting 30 solution is impregnated onto the desired support. The impregnated support is then heated (preferably to about to 100-250~C) for sufficient time preferably about 1 -3 hours) to facilitate the formation of the amide-containing polymer. The resulting AMENDED S~EET
CA 022~8994 1998-12-23 WO 98/004~3 PCT/US9'7109822 supported amide-containing polymer is then preferably washed with water to remove any remaining reactants or reaction products. The material is then preferably dried in air before use.
The invention is further illustrated by the following examples. The invention isnot limited to the specific details of the examples.
Example 1 Preparation of Polv(Riperazine succinamide) (nP4") and Poly(piperazine adipamide) (~P6~) 5.0 g piperazine and 12.31 g sodium carbonate were dissolved in 100 ml deionized water. The solution was then poured into a blender. 9.0 g succinyl chloride was dissolved in 20 ml CH2CI2. 10 ml CHzCI2 was added to the piperazinesolution in the blender and the blender was turned on. The succinyl chloride solution was then added to the blender in less than one minute. The blender agitation wascontinued for 10 more minutes. The resulting slurry was then dried at 45~C and repeatedly washed with deionized water until the pH of the resulting wash water was neutral. The washed polymer was then dried again at 45~C to produce the desired P4 material.
The P6 material was prepared in a similar manner except that 10.62 9 adipoyl chloride was substituted for the succinyl chloride.
Example 2 Polyphenol adsorption To determine the polyphenol adsorption capacities of P4 and P6, each material was used to treat beer A after maturation. PVPP was used as a comparison. The results are shown in Table 1 where the amount of polyphenols wasmeasured using ASBC method: Beer-35.
W O 98/00453 ~CTrUS97109822 Table 1 MaterialDose (~IhL) Reduction in Polvphenols (PPm) Example 3 Chillproofinq The chillproofing perforrnance of the P4 and P6 materials of exampie 1 was tested using neat samples of the materials as well as combinations thereof with a silica gel protein adsorbent (Daraclar~ 7500). Samples of the silica gel were also tested alone for comparison. The samples were contacted with a chip beer A at the dosages described in Table 2. All samples were filtered through a diatomaceous earth coated filter, carbonated, bottled and pasteurized. The samples were then held at 38i C for 6 days and then for two days at 2~C. The level of chill haze was measured in nephelometer turbidity units (NTU).
Table 2 Material Dose (q/hL) Haze (NTU) Silica Gel 60 6 Silica Gel 40 10 P6 + Silica Gel 10 + 30 8 P4 + Silica Gel 10 + 30 2 P4 + Silica Gel 20 + 20 Example 4 Preparation of triethvlenetertramine-modified Polv(piperazine succinamide) 2.68 g piperazine and 0.24 9 triethylenetetramine (TET) were dissolved in 100 ml deionized water. 17.0 ml of 4N sodium hydroxide solution was added to thepiperazine solution. ~he resulting solution was poured into a blender. 5.0 g succinyl , . , .. ., ~ ... .. , ....... , .~ ~ ... ... ..
CA 022~8994 1998-12-23 W O 98~53 PCTAUS97~M~22 chloride was dissolved in 20 ml CH2C12. tO ml CH2C12 was added to the piperazinesolution in the blender and the blender was turned on. The succinyl chloride solution was then added to the blender in less than one minute. The blender agitation wascontinued for 10 more minutes. The resulting slurry was then dried at 45~C and repeatediy washed with deionized water until the pH of the resulting wash water was neutral. The washed polymer was then dried again at 45~C to produce the desired TET-modified P4 material.
The chillproofing performance of the TET-P4 material with a silica gel (Daraclar~ 7500) was compared to a sample of the silica gel alone using a beer B.
The results are indicated in Table 3.
Table 3 Material Dose (q/hL) Haze (NTU) Silica Gel 60 8 Siiica Gel + TET-P436 + 4 Example 5 Preparation of 1,4-diaminocvclohexane-modified poly(piperazine adipamide) 1.88 g piperazine and 1.25 g 1,4-diaminocyclohexane (DAC) were dissolved in 100 ml deionized water. 1 1.4 ml of 4N sodium hydroxide solution was added to the piperazine solution. The resulting solution was poured into a blender. 4.0 g adipoyl chloride was dissolved in 20 ml CHzC12. 10 ml CH2CI2 was added to the piperazinesolution in the blender and the blender was turned on. The succinyl chloride solution was then added to the blender in less than one minute. The blender agitation wascontinued for 10 more minutes. The resulting slurry was then dried at 45~C and repeatedly washed with deionized water until the pH of the resulting wash water was neutral. The washed polymer was then dried again at 45~C to produce the desired DAC-modified P6 material.
The chillproofing performance of the DAC-modified P6 material with a silica gel (Daraclar~ 7500) was compared to a sample of the silica gel alone using a beer C. The results are indicated in Table 4.
Wo 981004S3 PcrluS97lo9822 A further chillproofing test was performed comparing the combination of DAC-P6 and silica gel with combinations of PVPP (Polyclar~ from GAF Corp.) usingbeer D. The results are indicated in Table 5.
Table 4 Material Dose (qlhL) Haze (NTU) Silica Gel 80 6 Silica Gel ~ DAC-P636 + 4 2 Table 5 Material Dose (q/hL) Haze (NTU~
Silica Gel + DAC-P636 + 4 4 Silica Gel + PVPP36 + 8 10 Silica Gel + PVPP36 + 12 8 Example 6 Preparation of supported triethvlenetertramine-modified poly(piperazine succinamide) 2.772 9 piperazine, 0.2476 9 triethylenetetramine (TET), and 4.00 g succinic acid were combined with 11.7 ml water to form a solution. 7.71 9 silica gel (9% TV) particles were then irnpregnated with the solution. The resulting material was then heated in a stream of nitrogen gas at 220~C for about two hours. The material was then washed with water and air dried to achieve the supported triethylenetertramine-modified poly(piperazine succinamide) containing about 50 wt.%
triethylenetertramine-modified poly(piperazine succinamide).
The chillproofing performance of the supported TET-P4 was similar to that of the material of Example 4 above.
The removal of these adverse components from beverages prior to packaging for sale has been addressed by treating the beverages with various materials designed to adsorb one or more of the adverse components from the 15 beverage. Due to the diverse nature of these adverse components, most treatments have involved contacting of the beverage with a combination of adsorbents, either simultaneously or sequentially. For removal of polyphenolics, certain polyamideshave been used such as nylons and polyvinylpolypyrrolidone (PVPP). By far~ PVPP
has been the most widely used adsorbent for removal of polyphenolics and is 20 considered to be significantly more effective than nylons. For removal of adverse . proteins, the adsorbents such as silica gels and tannins have been used.
While PVPP is an effective polyphenol adsorbent, PVPP is an expensive material in the context of treating liquids on a commercial scale. This is especially true for the commercial production of beer and fruit juices. Due to its expense, most 25 users of PVPP regenerate it after use by treatment with basic and acidic solutions.
The regenerability of PVPP is limited. Also, the use of regenerated PVPP may result in the introduction of unwanted acid or base into the liquid to be treated. PVPP has further disadvantages in that it is affected by the presence of yeast. Thus, PVPP can be added to the processing of a beverage only after the yeast has been substantially 30 removed. Thus, there is a need for alternative polyphenol adsorbents which provide the adsorption performance of PVPP without its disadvantages.
AMENDED StlEET
i CA 022~8994 1998-12-23 Summarv of the Invention ~ he invention provides alternative polyphenol adsorbents for use in treating polyphenol-containing liquids. These alternative adsorbents are amide-containingpolymers characterized by the presence of piperazine amide units in the polymer chain.
In one aspect, the invention encomp~-~ses a method of treating a liquid containing polyphenolic compounds to remove some or all of the polyphenolic compounds from said liquid, the method comprising:
(a) contacting the liquid with a polymer wherein at least a portion of the polymer chain comprises piperazine amide units whereby at least a portion of the polyphenolic compounds is adsorbed by the amide-containing polymer, and (b) separating said amide-containing polymer with the adsorbed polyphenolic compounds from the liquid.
In another aspect, the invention encompasses a method of treating a liquid containing polyphenolic compounds and proteins to remove some or all of the polyphenolic compounds and proteins from said liquid, the method comprising:
(a) contacting the liquid with a polymer wherein at least a portion of the polymer chain comprises piperazine arnide units whereby at least a portion of the polyphenolic compounds is adsorbed by the amide-containing polymer, (b) separating the amide-containing polymer with the adsorbed polyphenolic compounds from the liquid, (i) contacting the liquid with a protein adsorbent whereby at least a portion of the proteins are adsorbed by the protein adsorbent, and (ii) separatin~ said adsorbed protein from said liquid. Steps (a) and (i) may be performed simultaneously or sequentially. Preferably, a protein-adsorbingsilica is used in step (i).
The amide-containing polymer preferably contains piperazine C2-C,2 carboxylamides. The amide-containing polymer may contain additional chain constituents such as aliphatic or alicyclic diamines (as diamides).
. , . ,, . . ,, .... ~ ~ . . .. . . .. .
CA 022~8994 1998-12-23 Wo 98/004S3 PC r/uss71os822 Detailed Description of the Invention The invention encompasses the discovery that amide-containing polymers which contain piperazine amide are especially useful for removing undesired polyphenolic compounds from liquids, especially beverages (e.g., beer, wine or juice) derived from plant matter (e.g., grains, fruits or vegetables). These polymers are useful in the stabilization and/or chillproofing of such beverages. For such purposes, the piperazine amide-containing polymers may be used alone or in combination with a conventional beverage treatrr~ent agent, especially a protein removal agent such as silica gel.
The polyphenol-adsorbing polymers of the invention are characterized by the presence in the polymer chain of a piperazine amide component:
~ ~ C --C
Il 11 / \
C--Q--C--N N--C - C /
where Q can be any constituent corresponding to the body of the polycarboxylic compound used to form the amide. The piperazine trepresented in brackets above) of the piperazine amide component is preferably ordinary piperazine, however, N-substituted piperazines such as 1-(2-aminoethyl) piperazine (AEP) or other substituted piperazines such as C1 -C6 dialkyl piperazine may also be used to provide the piperazine amide component. In using such alternative piperazines, it is preferred that the formation of water-soluble polyamides is avoided. Thus, ordinary piperazine is preferably not completely replaced with AEP.
The acyl portion of the piperazine amide component is preferably derived from a dicarboxylic compound such as a dicarboxylic acid or dicarboxylic acid ester - or other dicarboxylic compound. Preferred dicarboxylic compounds are aliphatic C2-C12 dicarboxylic compounds and compounds based on fatty acid dimers. Preferred aliphatic dicarboxylic compounds are:
R~CO~[CH2]n~CO~R~
CA 022~8994 1998-12-23 where R and Rl can be OH. OR", or a halogen; n=0-10, and R" is any ester group wherein the compound would react with the piperazine to release R and R'. Of these compounds. adipoyl and succinyl compounds are most preferred. Other polycarboxylic compounds may be substituted for the dicarboxylic compound.
Examples of suitable di- and polycarboxylic compounds are disclosed in US Patent4,182,844 and British Patent 1,496,508, the disclosures of which are incorporated herein by reference. If desired, mixtures of different polycarboxylic compounds may be employed.
The polyphenol-adsorbing polymers of the invention may further contain other - 10 components to modify and improve the performance of the resulting polymer. For example, a portion of the piperazine component may be replaced with another polyamine component such as aliphatic polyamines (e.g., triethylenetetramine~
hexamethylenediamine~ 2,2-dimethyl-1,3-propanediaminel N-methyl-1,3-propanediamine) and alicyclic polyamines (e.g., 1, 4-diaminocyclohexane). Other suitable polyamines are disclosed in US Patent 4,182,844 and German Patent 43 28254, the disclosures of which are incorporated herein by reference. Where such other polyamine is present, the mole ratio of piperazine to all other polyamines (total) is preferably about 5-95:95-5. More preferably, the total of other polyamines ispresent at about 5-25 mole percent of the combination of piperazine and such other polyamines.
The proportions of the piperazine, polycarboxylic acid, and alternative ~- polyamine may be varied to some extent. On an equivalents basis, the amide-containing polymers of the invention preferably contain approximately equal amounts of (a) piperazine + alternative polyamine and (b) polycarboxylic acid.
The amide-containing polymers of the invention preferably not water soluble.
The polymer particles preferably have a particle size of about 0.1-300 ~Lm, morepreferably about 0.5-200 ~Lm, and a surface area of about 0.1-50 m2/g.
If desired, the amide-containing polymers of the invention may be supported on support particles or a support substrate. For example, the amide-containing polymers of the invention may be supported on inorganic oxide particles such as siliceous oxides, especially amorphous silicas. In such instances, the supported A~\/IEN~E~ S~IEET
CA 022~8994 1998-12-23 composition preferably comprises at least about 10 wt.% (more preferably about 20-50 wt.%) of the amide-containing polymer based on the total weight of the amide-containing polymer and the support.
The amide-containing polyphenol adsorbents of the invention may be used alone or in combination with other adsorbents known to be useful for treating beverages. If desired, conventional polyphenol adsorbents such as nylon or PVPP
may be used in combination with the amide-containing polyphenol adsorbents of the invention. Preferably, the amide-containing polyphenol adsorbents of the invention are used in combination with a protein adsorbent such as tannin or silica gel. Most preferably, the amide-containing polyphenol adsorbent is used in combination with a silica gel such as Daraclar~ 7500 (sold by W. R. Grace & Co.). Conventional tannins such as Brewtan~ (Omnichem N.V.) may be used to adsorb proteins. Silica gels (xerogels or hydrogels) are preferred especially because of their relative ease of use compared to tannins. Where tannin is used, it is preferred that the tannin and the polyphenol adsorbent of the invention are not present simultaneously in the beverage to be treated.
The amide-containing polyphenol adsorbents of the invention may be used to treat various liquids where polyphenol removal is desired, however, the amide-containing polyphenol adsorbents of the invention are especially useful for the removal of polyphenols from plant-derived beverages such as juices and fermentedbeverages (e.g., beer, wine, etc.). In plant derived beverages, the amide-containing polyphenol adsorbents, when used alone or in combination with a protein adsorbent, provide excellent stabilization and/or chillproofing. The amide-containing polyphenol adsorbents of the invention may be used to treat be~lerages in a similar manner as PVPP and nylon are currently used in the art, however, the adsorbents of the invention are especially advantageous in that they may be added directly to yeast-containing beverages (i.e. prior to yeast removal). See for example the techniques described in U.S. Patents 3,264,372; 4,073,954 and 4,008,339, the disclosures ofwhich are incorporated herein by reference. The amide-containing polyphenol adsorbents of the invention are preferably used in an amount effective to achieve the desired degree of polyphenol removal. Typical dosages may be on the order of 1-150 g/h-L.
. .
CA 022~8994 1998-12-23 When a combination of the amide-containing polyphenol adsorbents of the invention and a protein adsorbent are used, the relative proportions of these may be varied to achieve the desired performance for the specific liquid or beverage used.
The relative proportions may vary significantly even for treatment of beverages of the 5 same general class (e.g. beers). Where the protein adsorbent is a siliceous material, the weight ratio of the siliceous adsorbent to the polyphenol adsorbent is preferably about 0.01-100:1, more preferably about 5-10:1. Where the polyphenol adsorbent is used in a supported form, the above ratios should be determined excluding the weight of the support (as part of the polyphenol adsorbent or as part of the siliceous ~, 10 adsorbent where the support is siliceous). The combination of polyphenol and protein adsorbents may be used sequentially (with removal of the one adsorbent before addition of the other) or simultaneously (except for tannin as noted above) wherein both adsorbents are added at the same time or where one is added while the other is present in the liquid to be treated. The polyphenol adsorbent and protein 15 adsorbent may be used in any order.
The amide-containing polyphenol adsorbents of the invention may be synthesized by any known technique such as those described in US Patent 4,182.844, British Patent 1,~96,508 and German Patent 43 28 254. In one method (interfacial polymerization), the piperazine component and a base such as sodium20 hydroxide or sodium carbonate are dissolved in water. A solution of dicarboxyl ~ chloride (e.g. succinyl chloride) in methylene chloride is then added rapidly (in less '- than one minute) to the piperazine solution using strong agitation (e.g. a blender).
Agitation is then maintained for an additional 5-20 minutes. The resulting slurry is then dried at about 40-50~C and washed (to remove chloride by-products of the 25 polymerization) with deionized water until a neutral pH is reached. Where alternative polyamines are used in combination with the piperazine component, the alternative polyamine is preferably dissolved in the piperazine solution.
Where the amide-containing polymer is to be made in a supported form, the above mentioned components are preferably first combined and the resulting 30 solution is impregnated onto the desired support. The impregnated support is then heated (preferably to about to 100-250~C) for sufficient time preferably about 1 -3 hours) to facilitate the formation of the amide-containing polymer. The resulting AMENDED S~EET
CA 022~8994 1998-12-23 WO 98/004~3 PCT/US9'7109822 supported amide-containing polymer is then preferably washed with water to remove any remaining reactants or reaction products. The material is then preferably dried in air before use.
The invention is further illustrated by the following examples. The invention isnot limited to the specific details of the examples.
Example 1 Preparation of Polv(Riperazine succinamide) (nP4") and Poly(piperazine adipamide) (~P6~) 5.0 g piperazine and 12.31 g sodium carbonate were dissolved in 100 ml deionized water. The solution was then poured into a blender. 9.0 g succinyl chloride was dissolved in 20 ml CH2CI2. 10 ml CHzCI2 was added to the piperazinesolution in the blender and the blender was turned on. The succinyl chloride solution was then added to the blender in less than one minute. The blender agitation wascontinued for 10 more minutes. The resulting slurry was then dried at 45~C and repeatedly washed with deionized water until the pH of the resulting wash water was neutral. The washed polymer was then dried again at 45~C to produce the desired P4 material.
The P6 material was prepared in a similar manner except that 10.62 9 adipoyl chloride was substituted for the succinyl chloride.
Example 2 Polyphenol adsorption To determine the polyphenol adsorption capacities of P4 and P6, each material was used to treat beer A after maturation. PVPP was used as a comparison. The results are shown in Table 1 where the amount of polyphenols wasmeasured using ASBC method: Beer-35.
W O 98/00453 ~CTrUS97109822 Table 1 MaterialDose (~IhL) Reduction in Polvphenols (PPm) Example 3 Chillproofinq The chillproofing perforrnance of the P4 and P6 materials of exampie 1 was tested using neat samples of the materials as well as combinations thereof with a silica gel protein adsorbent (Daraclar~ 7500). Samples of the silica gel were also tested alone for comparison. The samples were contacted with a chip beer A at the dosages described in Table 2. All samples were filtered through a diatomaceous earth coated filter, carbonated, bottled and pasteurized. The samples were then held at 38i C for 6 days and then for two days at 2~C. The level of chill haze was measured in nephelometer turbidity units (NTU).
Table 2 Material Dose (q/hL) Haze (NTU) Silica Gel 60 6 Silica Gel 40 10 P6 + Silica Gel 10 + 30 8 P4 + Silica Gel 10 + 30 2 P4 + Silica Gel 20 + 20 Example 4 Preparation of triethvlenetertramine-modified Polv(piperazine succinamide) 2.68 g piperazine and 0.24 9 triethylenetetramine (TET) were dissolved in 100 ml deionized water. 17.0 ml of 4N sodium hydroxide solution was added to thepiperazine solution. ~he resulting solution was poured into a blender. 5.0 g succinyl , . , .. ., ~ ... .. , ....... , .~ ~ ... ... ..
CA 022~8994 1998-12-23 W O 98~53 PCTAUS97~M~22 chloride was dissolved in 20 ml CH2C12. tO ml CH2C12 was added to the piperazinesolution in the blender and the blender was turned on. The succinyl chloride solution was then added to the blender in less than one minute. The blender agitation wascontinued for 10 more minutes. The resulting slurry was then dried at 45~C and repeatediy washed with deionized water until the pH of the resulting wash water was neutral. The washed polymer was then dried again at 45~C to produce the desired TET-modified P4 material.
The chillproofing performance of the TET-P4 material with a silica gel (Daraclar~ 7500) was compared to a sample of the silica gel alone using a beer B.
The results are indicated in Table 3.
Table 3 Material Dose (q/hL) Haze (NTU) Silica Gel 60 8 Siiica Gel + TET-P436 + 4 Example 5 Preparation of 1,4-diaminocvclohexane-modified poly(piperazine adipamide) 1.88 g piperazine and 1.25 g 1,4-diaminocyclohexane (DAC) were dissolved in 100 ml deionized water. 1 1.4 ml of 4N sodium hydroxide solution was added to the piperazine solution. The resulting solution was poured into a blender. 4.0 g adipoyl chloride was dissolved in 20 ml CHzC12. 10 ml CH2CI2 was added to the piperazinesolution in the blender and the blender was turned on. The succinyl chloride solution was then added to the blender in less than one minute. The blender agitation wascontinued for 10 more minutes. The resulting slurry was then dried at 45~C and repeatedly washed with deionized water until the pH of the resulting wash water was neutral. The washed polymer was then dried again at 45~C to produce the desired DAC-modified P6 material.
The chillproofing performance of the DAC-modified P6 material with a silica gel (Daraclar~ 7500) was compared to a sample of the silica gel alone using a beer C. The results are indicated in Table 4.
Wo 981004S3 PcrluS97lo9822 A further chillproofing test was performed comparing the combination of DAC-P6 and silica gel with combinations of PVPP (Polyclar~ from GAF Corp.) usingbeer D. The results are indicated in Table 5.
Table 4 Material Dose (qlhL) Haze (NTU) Silica Gel 80 6 Silica Gel ~ DAC-P636 + 4 2 Table 5 Material Dose (q/hL) Haze (NTU~
Silica Gel + DAC-P636 + 4 4 Silica Gel + PVPP36 + 8 10 Silica Gel + PVPP36 + 12 8 Example 6 Preparation of supported triethvlenetertramine-modified poly(piperazine succinamide) 2.772 9 piperazine, 0.2476 9 triethylenetetramine (TET), and 4.00 g succinic acid were combined with 11.7 ml water to form a solution. 7.71 9 silica gel (9% TV) particles were then irnpregnated with the solution. The resulting material was then heated in a stream of nitrogen gas at 220~C for about two hours. The material was then washed with water and air dried to achieve the supported triethylenetertramine-modified poly(piperazine succinamide) containing about 50 wt.%
triethylenetertramine-modified poly(piperazine succinamide).
The chillproofing performance of the supported TET-P4 was similar to that of the material of Example 4 above.
Claims (38)
1. A composition comprising inorganic oxide and amide-containing polymer wherein at least a portion of the polymer comprises piperazine amide or substituted piperazine amide.
2. The polymer of claim 1 wherein said polymer comprises piperazine dicarboxylic amide, substituted piperazine dicarboxylic amide or a combination thereof.
3. The polymer of claim 2 wherein said piperazine dicarboxylic amide and substituted piperazine dicarboxylic amide comprises an aliphatic dicarboxylic component.
4. The polymer of claim 3 wherein said aliphatic dicarboxylic component is selected from the group consisting of C2 - C12 dicarboxylic components.
5. The polymer of claim 2 wherein said piperazine dicarboxylic amide and substituted piperazine dicarboxylic amide are selected from the group consisting of piperazine succinamide, piperazine adipamide, substituted piperazine succinamide, substituted piperazine adipamide and mixtures thereof.
6. The polymer of claim 1 wherein said polymer further comprises an additional amide component other than piperazine amide.
7. The polymer of claim 6 wherein said additional amide component is an aliphatic amide.
8. The polymer of claim 6 wherein said aliphatic amide is derived from an aliphatic amine selected from the group consisting of triethylenetetramine, hexamethylenediamine, 2,2-dimethyl-1,3-propanediamine, N-methyl-1,3-propanediamine, and mixtures thereof.
9. The polymer of claim 7 wherein said additional amide component is an alicyclic amide.
10. The polymer of claim 9 wherein said alicyclic amide is derived from 1, 4-diaminocyclohexane.
11. The polymer of claim 1 wherein said amide-containing polymer contains an amide of 1-(2-aminoethyl) piperazine.
12. The composition of claim 1 wherein said inorganic oxide is a siliceous oxide.
13. The composition of claim 12 wherein said composition comprises an admixture of (a) particles of said siliceous oxide and (b) particles of said polymer.
14. The composition of claim 12 wherein said composition comprises a particulate composite of said siliceous oxide and said polymer.
15. The composition of claim 13 wherein the siliceous oxide is impregnated with the polymer.
16. A method of treating a liquid containing polyphenolic compounds to remove some or all of said polyphenolic compounds from said liquid, said method comprising:
(a) contacting said liquid with an amide-containing polymer wherein at least a portion of the polymer comprises piperazine amide or substituted piperazine amide whereby at least a portion of said polyphenolic compounds is adsorbed by said amide-containing polymer, and (b) separating said amide-containing polymer with said adsorbed polyphenolic compounds from said liquid.
(a) contacting said liquid with an amide-containing polymer wherein at least a portion of the polymer comprises piperazine amide or substituted piperazine amide whereby at least a portion of said polyphenolic compounds is adsorbed by said amide-containing polymer, and (b) separating said amide-containing polymer with said adsorbed polyphenolic compounds from said liquid.
17. The method of claim 16 wherein said amide-containing polymer contains piperazine amide.
18. The method of claim 16 wherein said amide-containing polymer contains piperazine dicarboxylic amide, substituted piperazine dicarboxylic amide or a combination thereof.
19. The method of claim 18 wherein said piperazine dicarboxylic amide and substituted piperazine dicarboxylic amide contain an aliphatic dicarboxylic component.
20. The method of claim 19 wherein said aliphatic dicarboxylic component is selected from the group consisting of C2-C12 dicarboxylic components.
21. The method of claim 18 wherein said piperazine dicarboxylic amide and substituted piperazine dicarboxylic amide are selected from the group consisting of piperazine succinamide, piperazine adipamide, substituted piperazine succinamide, substituted piperazine adipamide and mixtures thereof.
22. The method of claim 16 wherein said amide-containing polymer further comprises an additional amide component other than piperazine amide
23. The method of claim 22 wherein said additional amide component is an aliphatic amide.
24. The method of claim 23 wherein said aliphatic amide is derived from an aliphatic amine selected from the group consisting of triethylenetetramine, hexamethylenediamine, 2,2-dimethyl-1,3-propanediamine, N-methyl-1,3-propanediamine, and mixtures thereof.
25. The method of claim 22 wherein said additional amide component is an alicyclic amide.
26. The method of claim 25 wherein said alicyclic amide is derived from 1,4-diaminocyclohexane.
27. The method of claim 16 wherein said amide-containing polymer contains an amide of 1-(2-aminoethyl) piperazine.
28. The method of claim 16 wherein said liquid is based on a plant-derived substance.
29. The method of claim 28 wherein said liquid is selected from the group consisting of fruit juices, vegetable juices, and fermented beverages.
30. The method of claim 29 wherein said liquid is beer.
31. The method of claim 16 wherein said liquid further contains proteins.
32. The method of claim 31 wherein said method further comprises (i) contacting said liquid with a protein adsorbent whereby at least a portion of said proteins are adsorbed by said protein adsorbent and (ii) separating said adsorbed protein from said liquid.
33. The method of claim 32 wherein step (a) and step (i) are conducted simultaneously.
34. The method of claim 33 wherein step (b) and step (ii) are conducted simultaneously.
35. The method of claim 32 wherein step (i) comprises contacting said liquid with a siliceous adsorbent to adsorb at least a portion of said proteins.
36. The method of claim 35 wherein said siliceous adsorbent is a silica gel.
37. The method of claim 33 wherein step (a) and step (i) are performed by contacting said liquid with an admixture of said amide-containing polymer and a protein-adsorbing siliceous adsorbent.
38. The method of claim 37 wherein said liquid is selected from the group consisting of fruit juices, vegetable juices, and fermented beverages.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/672,860 US5628910A (en) | 1996-06-28 | 1996-06-28 | Polyamide compositions for removal of polyphenols from liquids |
| US08/833,613 | 1997-04-08 | ||
| US08/672,860 | 1997-04-08 | ||
| US08/833,613 US5856429A (en) | 1996-06-28 | 1997-04-08 | Polyamide compositions for removal of polyphenols from liquids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2258994A1 true CA2258994A1 (en) | 1998-01-08 |
Family
ID=27100833
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002258994A Abandoned CA2258994A1 (en) | 1996-06-28 | 1997-06-10 | Polyamide compositions for removal of polyphenols from liquids |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US5856429A (en) |
| EP (1) | EP0907671A1 (en) |
| JP (1) | JP2000514111A (en) |
| KR (1) | KR20000022316A (en) |
| CN (1) | CN1228794A (en) |
| AU (1) | AU3379197A (en) |
| BR (1) | BR9710037A (en) |
| CA (1) | CA2258994A1 (en) |
| NZ (1) | NZ333377A (en) |
| WO (1) | WO1998000453A1 (en) |
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| DE10018533C2 (en) * | 2000-04-13 | 2002-10-31 | Herbstreith & Fox Kg Pektin Fa | Process for the recovery of valuable materials from by-products of fruit and vegetable processing |
| DE10051266A1 (en) * | 2000-10-16 | 2002-04-25 | Basf Ag | Filter aid used for filtering fruit and fermented drinks comprising polystyrene and silicate, carbonate, oxide, silica gel, diatomaceous earth and/or polymers |
| FR2820738B1 (en) | 2001-02-15 | 2003-05-16 | Agronomique Inst Nat Rech | PROCESS FOR THE EXTRACTION, FRACTIONATION AND PURIFICATION OF POLYPHENOLIC COMPOUNDS FROM SORTING GAPS OF FRESH PLANTS USING A HIGH-YIELD ADSORPTION AND ELUTING RESIN |
| DE10215147A1 (en) * | 2002-04-05 | 2003-10-16 | Basf Ag | Use of polymerization containing thermoplastic polymers as filter aids and / or stabilizers |
| EP1545734A4 (en) * | 2002-10-01 | 2009-11-11 | Dow Corning | Method of separating components in a sample using silane-treated silica filter media |
| US7264728B2 (en) | 2002-10-01 | 2007-09-04 | Dow Corning Corporation | Method of separating components in a sample using silane-treated silica filter media |
| WO2005113738A1 (en) * | 2004-05-18 | 2005-12-01 | Inbev S.A. | Method of preparing a liquid, containing proteins for subsequent separation, by using one or more protein-complexing agents |
| FR2898891B1 (en) * | 2006-03-22 | 2008-05-30 | Centre Nat Rech Scient | PROCESS FOR EXTRACTING CARBONYL COMPOUNDS FROM A LIQUID-SOLID EXTRACTION BEVERAGE WITH FUNCTIONALIZED INERT SUPPORT |
| JP4935173B2 (en) * | 2006-04-26 | 2012-05-23 | 東洋紡績株式会社 | Process for preparing polyamine compositions from plants |
| FR2907792A1 (en) * | 2006-10-25 | 2008-05-02 | Inst Oenologique De Champagne | Process useful for elimination of undesirable compound e.g. fenchol, olefinic hydrocarbons and borneol, altering the taste of (non)fermented drinks containing ethanol, comprises using active material comprising dispersed granular support |
| JP5569485B2 (en) * | 2011-08-09 | 2014-08-13 | 東洋紡株式会社 | Process for preparing polyamine compositions from plants |
| US8883239B2 (en) * | 2013-02-26 | 2014-11-11 | Universidad De Talca | Clarification and selective binding of phenolic compounds from liquid foodstuff or beverages using smart polymers |
| CN103570938B (en) * | 2013-10-07 | 2016-01-13 | 西北大学 | A kind of polymeric amide and its preparation method and application |
| CN105669970B (en) * | 2016-01-04 | 2018-11-02 | 四川大学 | Polyamide-based expandable flame retardant carbon forming agent and its preparation method and application of the main chain containing piperazine structure |
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-
1997
- 1997-04-08 US US08/833,613 patent/US5856429A/en not_active Expired - Fee Related
- 1997-06-10 JP JP10504132A patent/JP2000514111A/en not_active Ceased
- 1997-06-10 CN CN97197491A patent/CN1228794A/en active Pending
- 1997-06-10 CA CA002258994A patent/CA2258994A1/en not_active Abandoned
- 1997-06-10 AU AU33791/97A patent/AU3379197A/en not_active Abandoned
- 1997-06-10 EP EP97929821A patent/EP0907671A1/en not_active Withdrawn
- 1997-06-10 WO PCT/US1997/009822 patent/WO1998000453A1/en not_active Application Discontinuation
- 1997-06-10 NZ NZ333377A patent/NZ333377A/en unknown
- 1997-06-10 KR KR1019980710739A patent/KR20000022316A/en not_active Application Discontinuation
- 1997-06-10 BR BR9710037A patent/BR9710037A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| NZ333377A (en) | 2000-08-25 |
| BR9710037A (en) | 1999-08-10 |
| EP0907671A1 (en) | 1999-04-14 |
| US5856429A (en) | 1999-01-05 |
| CN1228794A (en) | 1999-09-15 |
| WO1998000453A1 (en) | 1998-01-08 |
| KR20000022316A (en) | 2000-04-25 |
| JP2000514111A (en) | 2000-10-24 |
| AU3379197A (en) | 1998-01-21 |
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