Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F12/02—Monomers containing only one unsaturated aliphatic radical
  • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
  • C08F12/30—Sulfur
• • 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

Definitions

• the invention relates to insoluble, highly crosslinked, weakly swellable styrene-4-sulfonate-containing popcorn polymers, processes for their preparation and their use as adsorbents, ion exchangers, carrier materials, filter aids, color transfer inhibitors for detergents or additives in cosmetic, dermatological or pharmaceutical formulations disintegrants.
• the styrene-4-sulfonate-containing popcorn polymers are to be used for the filtration of liquids, in particular beer, and as tablet disintegrants.
• Pocpcorn-Polymerisate stands for foamy, crusty polymer grains with a structure like a cauliflower. Because of their mostly strong crosslinking, popcorn polymers are generally insoluble and hardly swellable.
• Popcorn polymers are used, for example, to adsorb tannins from beverages and as ion exchangers.
• Popcorn polymers containing carboxyl groups can e.g. can be obtained by saponification of polymers containing acrylic ester and acrylamide units.
• filter aids is understood to mean a series of products that are used in loose, powdery, granulated or fibrous form as precoat material in filtration.
• Filter aids can be applied to the filter medium as a filter auxiliary layer (precoat filter) before the start of filtration or, in order to achieve a loose cake build-up, continuously add to the mixture / solution to be filtered.
• precoat filter a filter auxiliary layer
• the main filter additives used are: • Diatoms, natural products that result from the calcination of diatomite.
• the main components are amorphous Si0 2 modifications, accompanied by aluminum, iron oxides and other elements as well as their silicate compounds.
• Pearlite these are annealed, ground, selected expanded clay of volcanic origin (rhyolite). Their structure is platelet-shaped and can be described chemically as a sodium, potassium and / or aluminum silicate.
• Bentonites are clay minerals with a high swelling and adsorption capacity.
• Cellulose organic, renewable raw materials (cellulose, wood fiber, etc.).
• fibrous products offer advantages for the consumer. Due to the fibrous structure, higher flow values are achieved. They are also soft, non-abrasive materials.
• Synthetic materials such as polymer cross-linked particles.
• the additives should have increased porosity.
• the porous environment should not deform under the influence of pressure.
• an additive should be chemically inert as well as recoverable, the cakes made from additives often comprising a heavily contaminated mass. This is particularly the case in the brewery.
• kieselguhr precoat filters and layer filters are mainly used for the filtration of beer.
• precoat filtration a kieselguhr pre-layer is washed onto a support surface (filter system) before the start of filtration. After this precoat has been suspended, a mixture of fine and coarse diatomaceous earth is added to the beer to be filtered (unfiltrate).
• a kieselguhr consumption of 150 to 200 g / hl of beer must be expected when producing beer.
• kieselguhr has proven particularly useful because of its large pore volume, low bulk density, higher absorbency and large specific surface area.
• diatomaceous earth has been under discussion for some time because of its carcinogenic effects. It is already classified as a carcinogen in the USA. Furthermore, the disposal of the filter cake from the above Basic difficulties. Protective measures that trigger expensive investments may be required to handle diatomaceous earth.
• WO 98/40149 describes the use of small particles made of plant fibers as filter aids. These filter aids include wood particles, wood fibers and wood chipping residues. These filter aids have been treated with a dilute acid and / or alkali.
• EP 351363 relates to the use of highly crosslinked polyvinylpyrrolidone (PVP) with a particle size of 1 ⁇ m to 300 ⁇ m as a stabilizing agent and at the same time filter aid of a liquid medium, in particular of beer, wine or fruit juice.
• PVP polyvinylpyrrolidone
• WO 96/35497 describes new regenerable filter aids for the filtration of a liquid medium, in particular beer, characterized in that they comprise granules of synthetic or natural, incompressible polymers. These polymer granules consist of polyamide, polyvinyl chloride, polypropylene, polystyrenes, polycaprolactams, etc. together.
• EP 483 099 describes the method of beer filtration, using filter aids which are characterized in that they use spherical particles with a particle size distribution between 5 and 50 ⁇ m. These filter aids should not be compressible, resistant to scraping, regenerable and less sensitive to temperature. However, there is a need for alternative filter aids, especially for beer filtration applications. Wood particles and fibers are not chemically inert. Synthetic polymers such as highly cross-linked polyvinylpyrrolidone are very effective binders for binding polyphenols, for example, but this effect is not desirable in beer filtration because a reduction in the polyphenols also affects the taste.
• the polymer should serve as a regenerable filter aid for the separation of fine and compressible particles. Above all for the separation of brewer's yeasts, which lead to the clogging of the pores of filter media or filter cakes.
• R L R 2 can be the same or different and are chlorine, bromine, iodine or CrC 4 alkyl and
• R 3 S0 3 " - or S0 3 H means
• the percentages by weight of the individual components a) to d) refer to the total amount of the popcorn polymer and add up to 100%.
• Monomers a) are understood to mean the alkaline earth metal or alkali metal salts of styrene-4-sulfonates, both neutralized and non-neutralized, and isomers of styrene-4-sulfonic acid, e.g. Styrene-3-sulfonic acid or sodium styrene-3-sulfonate, as well as their alkaline earth or alkali salts.
• Preferred monomer a) is styrene-4-sulfonic acid, particularly preferably sodium styrene-4-sulfonate.
• the monomers a) are used in amounts of 20 to 100% by weight, preferably 50 to 100% by weight, particularly preferably in amounts of 70 to 100% by weight, based on the total amount of the polymer used.
• Hydrophilic components b) generally mean N-vinyl lactams or N-vinyl amines, for example the following polymerizable comonomers: N-vinyl lactams and N-vinyl amines, in particular N-vinyl pyrrolidone, N-vinyl piperidone, N-vinyl caprolactam, N-vinyl imidazole , N-vinyl-2-methylimidazole, N-vinyl-4-methylimidazole and N-vinylformamide.
• Preferred hydrophilic components are N-vinylpyrrolidone, N-vinylimidazole and N-vinylcaprolactam, particularly preferably N-vinylpyrrolidone.
• the monomers b) are used in amounts of 0 to 40% by weight, preferably 0.5 to 30% by weight, particularly preferably in amounts of 1 to 25% by weight, based on the total amount of the polymer used.
• Monomers c) are generally compounds which contain at least two ethylenically unsaturated non-conjugated double bonds in the molecule and thus act as difunctional crosslinkers in the polymerization.
• Preferred representatives of the monomers c) are, for example, alkylenebisacrylamides such as methylenebisacrylamide and N, N'-acryloylethylenediamine, N, N'-divinyl ethylene urea, N, N'-divinylpropyleneurea, ethylidene-bis-3- (N-vinylpyrrolidone), N, N'-divinyl-imidazolyl (2,2 ') butane and 1,1'-bis- (3,3') vinylbenzimidazolite-2-one) 1,4-butane.
• alkylenebisacrylamides such as methylenebisacrylamide and N, N'-acryloylethylenediamine, N, N'-divinyl ethylene urea, N, N'
• crosslinkers are, for example, alkylene glycol di (meth) acrylates such as ethylene glycol diacrylate, ethylene lenglykoldimethacrylat, Tetraethylengiykoldiacrylat glycol diacrylate, tetraethylene glycol dimethacrylate, diethylene glycol dimethacrylate, diethylene aromatic divinyl compounds such as divinylbenzene and divinyltoluene, and vinyl acrylate, allyl acrylate, allyl methacrylate, divinyldioxane, pentaerythritol triallyl ether, triallyl and mixtures of the crosslinkers.
• alkylene glycol di (meth) acrylates such as ethylene glycol diacrylate, ethylene lenglykoldimethacrylat, Tetraethylengiykoldiacrylat glycol diacrylate, tetraethylene glycol dimethacrylate, diethylene glycol dimethacrylate, diethylene aromatic diviny
• crosslinkers are ethylene glycol diacrylate, ethylene glycol dimethacrylate, N, N'-divinylethylene urea (DVEH) and divinylbenzene (DVB).
• the crosslinkers are used in amounts of 0 to 10% by weight, preferably 0.1 to 8% by weight, particularly preferably in amounts of 0.2 to 5% by weight, based on the total amount of the polymer.
• Monomers d) are generally compounds which are capable of free-radical polymerization. Representatives of these monomers d) are, for example, alkenes or dialkenes such as ethene, propene, butene, isobutene, methylbutene, methylpentene, isoprene, butadiene, hexadiene, dicyclopentadiene, norbornene, styrene and their derivatives. Further monomers are halogen-containing vinyl monomers, such as, for example, vinyl chloride, vinyl fluoride, chloroprene, vinylidene chloride.
• Monomer derivatives of unsaturated acids such as acrylic esters, methacrylic esters such as acrylamides and acrylonitrile are also meant.
• these esters are, in particular, methyl acrylate, methyl methacrylate, ethyl acrylate, methyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl methacrylate, isopropyl methacrylate, urea acrylate and methacrylate and methacrylate, acrylate methacrylate Methacrylic acid derived from the isomeric butanols, as well as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxymethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate.
• suitable monomers are, for example, unsaturated alcohols and amines and derivatives such as, for example, vinyl alcohol, vinyl acetate, vinyl propionate, vinyl stearate, vinyl benzoate, vinyl maleate, vinyl butyral, allyl phthalate, allyl melamine.
• Popcorn polymers containing are preferred
• N-vinyllactam or N-vinylamine selected from the group N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinylimidazole, and methylated N-vinylimidazole or N-vinylformamide ;
• the polymerization is carried out according to known methods, e.g. as precipitation polymerization, solution polymerization or by bulk polymerization.
• Another object of the invention is therefore a process for the production of insoluble, only slightly swellable popcorn polymers, characterized in that
• R L R 2 may be the same or different and are chlorine, bromine, iodine or dC 4 alkyl and R 3 S0 3 " - or SO 3 H.
• a procedure is preferred in which, as described in EP-A-0177812, the popcorn polymerization is started by mixing 99.6% to 98.8% by weight of N-vinylpyrrolidone and 0 , 4 to 1, 2 wt .-% of a compound having at least two ethylenically unsaturated double bonds as a crosslinker heated to a temperature of 100 to 150 ° C in the absence of oxygen and polymerization initiators.
• This polymerization is initiated in particular by the presence of small amounts of sodium hydroxide solution or potassium hydroxide solution.
• a polymerizable Popcom polymer is formed which, when the remaining monomer mixture, i.e.
• the popcorn polymerization of these monomers starts without an induction period.
• the polymerization can also be carried out without a solvent.
• the monomer mixture from a), b) and c) is rendered inert by introducing nitrogen and then heated to a temperature in the range from 20 to 200 ° C., preferably 100 to 200 ° C., particularly preferably 150 to 180 ° C. , It is advantageous to continue to pass a weak stream of nitrogen through the monomer mixture even during the polymerization.
• the exclusion of oxygen is achieved by polymerizing the batch under negative pressure.
• the mixture polymerizes within 1 to 20 hours.
• the first polymer particles form, the amount of which slowly increases until after about 10 hours of polymerization the reaction mixture consists of a powder.
• the Popcom polymer is obtained therefrom in yields of over 90% in the form of a powder with an average particle size of approximately 1 ⁇ m to 1 mm, preferably 1 ⁇ m to 250 ⁇ m.
• Precipitation polymerization in water is preferred for the preparation of the polymers.
• concentration of the monomers is expediently chosen so that the reaction mixture can be stirred well over the entire duration of the reaction. If the concentration of the monomers in water is too high, for example 95%, the polymer grains often become sticky, so that stirring becomes more difficult than in the absence of solvents.
• monomer concentrations, based on the aqueous mixture of about 5 to 30, preferably 10 to 20,% by weight are chosen. If more powerful stirrers are available, the monomer concentration of the aqueous solution can also be increased to 50% by weight, if appropriate also above this.
• the exclusion of oxygen can best be achieved by heating the mixture to be polymerized to boiling and, if appropriate, additionally working in an inert gas atmosphere, for example by passing nitrogen through the reaction mixture.
• the polymerization temperature can be varied within a wide range, e.g. from about 20 to 200 ° C, preferably 50 to 150 ° C.
• a reducing agent such as sodium sulfite, sodium pyrosulfite, sodium dithionite (blankite), ascorbic acid or mixtures of the reducing agents, in order to completely remove dissolved oxygen ,
• the comonomer b), part of the crosslinking agent, water and, if appropriate, a buffer and a reducing agent are heated in a weak stream of nitrogen until the first polymer particles show up. Then a mixture, previously inertized by blowing in nitrogen, of, in particular, sodium styrene-4-sulfonate, optionally crosslinking agent and optionally water as diluent is added within 0.2 to 10 hours.
• the sodium styrene-4-sulfonate and the crosslinker can also be dissolved in a water-miscible solvent.
• the popcorn polymers are usually obtained in a yield of about 90 to> 99% of the theoretical yield. They can be isolated from the aqueous suspension by filtering or centrifuging, followed by washing with water and drying in conventional dryers such as forced-air or vacuum dryers, paddle dryers or current dryers become. The popcorn polymers are practically insoluble in water and all solvents and swell only slightly.
• Popcorn polymers of sodium styrene-4-sulfonate can be polymerized in aqueous solution in the absence of oxygen.
• the addition of small amounts of a multifunctional monomer (0.1% to 5%) accelerate the reaction and increase the yield to about 95%.
• the name solution polymers stands for a polymer which was produced by a homogeneous polymerization in a monomer-miscible solvent.
• the type of precipitation polymerization is known to the expert.
• the polymers according to the invention thus obtainable result in insoluble, highly crosslinked polymer particles which can be used as adsorbents, ion exchangers, carrier materials, filter aids, color transfer inhibitors for detergents or additives in cosmetic, dermatological or pharmaceutical formulations.
• the polymers according to the invention are preferably used as tablet disintegrants or for the filtration of liquids, in particular beer.
• the invention further relates to tablet disintegrants containing the polymers according to the invention.
• Another object of the invention is a method for filtering a liquid with a filter aid containing
• R u R 2 can be the same or different and are chlorine, bromine, iodine or dC 4 alkyl and
• R 3 S0 3 " - or S0 3 H means
• the percentages by weight of the individual components a) to d) refer to the total amount of the popcorn polymer and add up to 100%.
• the precoat filtration technique is preferably used as the filtration technique.
• the invention also relates to a filter aid
• RL R 2 can be the same or different and mean chlorine, bromine, iodine or -CC alkyl and
• filtration is understood to mean the flow through a porous filter medium through a suspension (turbidity) consisting of a discontinuous phase (dispersed substances) and a continuous phase (dispersing medium). Solid particles are deposited on the filter medium and the filtered liquid (filtrate) leaves the filter medium clear. An applied pressure difference acts as an external force to overcome the flow resistance.
• precoat filters are used in various designs for beverage filtration (Kunze, Wolfgang, Technologie Brauer and Gurlzer, 7th edition, 1994, p. 372).
• filter aids the solids contained in the liquid to be filtered and also the deliberately added solids (filter aids) are retained by a filter medium, whereby a filter cake builds up.
• filter medium and the filter medium must be flowed through.
• Such filtration is also known as precoat filtration.
• the liquids to be filtered according to the invention are fruit juices or fermentation beverages, such as wine or beer.
• the method according to the invention is particularly preferably used for the filtration of beer.
• the filter aids provided according to the invention are notable for good wettability with water and a constant flow rate with a good filtering effect.
• a quantity of vinylpyrrolidone corresponding to the particular composition to be adjusted is placed in water, sodium hydroxide solution (5%), crosslinking agent and blanket (Na 2 S 2 0) and gassed with nitrogen.
• the nitrogen flow throughout the test is 12 l / h.
• the tempera tur is set to 70 ° C.
• Feed 1 150.0 g of styrene-4-sulfonic acid sodium salt hydrate, 825.0 g of demineralized water
• Feed 1 250.0 g of styrene-4-sulfonic acid sodium salt hydrate, 1100.0 g of demineralized water
• Feed 2 7.5 g of DVB, 75.0 g of ethanol
• the tannoid content of beer is determined using polyvinylpyrrolidone. Protein-like compounds accumulate tannoids over H-bridges. This creates a cloudiness due to complexation. The turbidity is measured in the tannometer depending on the amount of PVP added. The result provides the tannoid content in mg PVP / I beer.

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• 2002
  • 2002-12-05 DE DE10257095A patent/DE10257095A1/de not_active Withdrawn
• 2003
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