EP2776512A1 - Procédé de production de gels, d'hydrogels , d'hydrocolloïdes et de superabsorbants de protéines laitiaires (gels de protéines laitières) - Google Patents

Procédé de production de gels, d'hydrogels , d'hydrocolloïdes et de superabsorbants de protéines laitiaires (gels de protéines laitières)

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Publication number
EP2776512A1
EP2776512A1 EP12799513.2A EP12799513A EP2776512A1 EP 2776512 A1 EP2776512 A1 EP 2776512A1 EP 12799513 A EP12799513 A EP 12799513A EP 2776512 A1 EP2776512 A1 EP 2776512A1
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EP
European Patent Office
Prior art keywords
milk
protein
gel
treatment
hydrogels
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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Application number
EP12799513.2A
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German (de)
English (en)
Inventor
Anke Domaske
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QMILCH IP GmbH
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QMILCH IP GmbH
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Publication date
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Publication of EP2776512A1 publication Critical patent/EP2776512A1/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D189/00—Coating compositions based on proteins; Coating compositions based on derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/18—Plasticising macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07K—PEPTIDES
    • C07K14/00—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof
    • C07K14/435—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans
    • C07K14/46—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans from vertebrates
    • C07K14/47—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans from vertebrates from mammals
    • C07K14/4701—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans from vertebrates from mammals not used
    • C07K14/4732—Casein
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H1/00—Macromolecular products derived from proteins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2389/00—Characterised by the use of proteins; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils

Definitions

  • this hydrogel group also includes milk protein-containing gels, aqueous gels, hydrogels, hydrocolloids and superabsorbents.
  • a hydrogel is a water-containing but water-insoluble polymer whose molecules are chemically or physically linked to a three-dimensional network. Built-in hydrophilic polymer components swell them up in water with a considerable volume increase, but without losing their material cohesion.
  • Polymer-based hydrogels can also be crosslinked by covalent addition of bifunctional agents with the proteins, to form a three-dimensional matrix and thus form a corresponding gel.
  • HEMA 2-hydroxyethyl methacrylate
  • PEG and PEO poly (ethylene glycol) and poly (ethylene oxide), which are referred to as PEG and PEO
  • HEMA, PEG and PEO polymers are advantageous in the preparation of biomatrices because they are pH and temperature resistant.
  • BSA bovine serum albumin
  • U.S. Patent No. 5,514,379 Teaches the synthesis of biocompatible, biodegradable hydrogels using proteins or polysaccharides with crosslinking agents, such as polyvalent derivatives of polyethylene or polyalkylene glycol.
  • the crosslinking agents are selected from the group consisting of: Bishydroxysuccinimide ester of polyalkylene glycol ("PAG") diacid, bishydroxysulfosuccinimide ester of PAG diacid, PAG diacid bisimidate, PAG diacid bisimitazolide, PAG bisimide, PAG bishalide, PAG bischlorothiazide Diacid, bis (n-aminoalkyl) of PAG and bis (polyoxyalkylene bis or bisbenzoxazolide of PAG)
  • PAG Bishydroxysuccinimide ester of polyalkylene glycol
  • U.S. Patent 5,733,563 (Fortier) teaches the basic solution preparation of bioartificial hydrogels consisting of a three-dimensional cross-linked mixture of bifunctionalized polyethylene oxide with an albumin-type protein.
  • the bifunctionalized polyethylene oxide is preferably polyethylene glycol and the albumin type protein is selected from various sources such as BSA (bovine serum albumin), lactalbumin and ovalbumin.
  • BSA bovine serum albumin
  • lactalbumin lactalbumin
  • ovalbumin ovalbumin.
  • the patent includes a method of making the hydrogels, the description of the hydrogels, and various applications for the hydrogels.
  • hydrogels have led to their use in a number of ways, including as implant materials, contact lenses and wound dressings and as carriers for the controlled release of medications.
  • the buffer systems used (such as phosphate or borate buffers) allowed a controlled cross-linking reaction
  • the constant PH value inhibited the variations produced by different raw materials.
  • the crosslinking reactions inhibited which led to long reaction times and thus to an uneconomic production.
  • German Patent 0001280849 Bioartificial Gel Technologies Inc. teaches preparation and qualitative characterization of PEG-casein hydrogel formulations.
  • PEG belongs to the allergens.
  • PEG derivatives combine water and fats, and are used to cleanse or soothe the skin. Since they make the skin more permeable, active ingredients should be able to penetrate better.
  • many PEG derivatives contain carcinogenic impurities, and so in addition to the desired agents also substances such. cancerous preservatives up to allergy substances in our skin.
  • ethylene oxide is used, with water, onoethylenglyco!
  • Ethylene oxide is a very reactive substance and potentially carcinogenic. Also no industrial production is described. In addition, the premix must be kept warm for 24 hours before further processing takes place. This results in a process that is not economical. In addition, the hydrogels had weak mechanical properties.
  • British Patent 3639524 discloses a preparation of crosslinked hydrogel polymers using (1) N-vinyl-2-pyrrolidones, (2) alkyl methacrylates.
  • NMP N-vinyl-2-pyrrolidones
  • alkyl methacrylates In the synthesis of NMP, ⁇ -butyrolactone, previously comprised of formaldehyde and acetylene was generated catalytically via several intermediates, reacted with methylamine. NMP is considered toxic, hazardous to health and irritant. Again, the polymerization takes place over several hours, which excludes an economic result.
  • German patent (PCT / EP2002 / 000825) describes the preparation of synthetic hydrogels based on poly (meth) acrylic acids, poly (meth) acrylates, poly (meth) acrylamides, polyurethanes, polyvinylpyrrolidones, polyvinyl alcohol, polyvinyl acetates or their copolymers and derivatives and mixtures thereof.
  • Hydrogels may be based on natural polymers, where the natural polymer may be selected from the group of polysaccharides such as optionally modified starch and starch derivatives, dextrins, agaroses, agargar, curdlan, alginic acid and alginates, Chitosans, polypeptides such as gelatin, pectins and pectinates, carageenans and celluloses and cellulose derivatives such as carboxymethylcellulose, cellulose acetate, cellulose acetate butyrate and alkylcelluloses and mixtures thereof.
  • polysaccharides such as optionally modified starch and starch derivatives, dextrins, agaroses, agargar, curdlan, alginic acid and alginates, Chitosans, polypeptides such as gelatin, pectins and pectinates, carageenans and celluloses and cellulose derivatives such as carboxymethylcellulose, cellulose acetate, cellulose acetate butyrate and
  • US Pat. No. 10 / 801,232 (Plochocka) describes the preparation of a hydrogel by means of a polymer and an extruder, maleic anhydride being mentioned as a substantial claim.
  • Maleic anhydride is obtained by partial oxidation of n-butane or the so-called “raffinate II” with the aid of a vanadium-phosphorus-oxide (VPO) catalyst.
  • VPO vanadium-phosphorus-oxide
  • Maleic acid is produced industrially from maleic anhydride; in turn, the anhydride is synthesized by catalytic oxidation of benzene or butane. Also used as crosslinked ethoxylated amines, amino alcohols, amides and imides. Imide groups are obtained by the reaction with ammonia. Amides are also chemical compounds that formally derive from ammonia. Ethoxylamines are reactions with ethyoxide. The ethoxylation is the addition of ethylene oxide (oxirane) to compounds such as alcohols, phenols, amines or carboxylic acids.
  • oxirane ethylene oxide
  • alkyl vinyl ethers Methyl vinyl ether, isobutyl vinyl ether, polyvinyl alcohol, olefin, ethylenes, butylenes, isobutylenes, and ethoxylated / propoxylated derivatives.
  • the polymer which is crosslinked in the extrusion process is an ester or an amide or imide. Milk proteins do not fall under any of these definitions.
  • Carboxyl modified superabsorbent proteinaceous hydrogel 0001263883 (damoong), involves preparation with glutaraldehyde. It is highly toxic to aquatic organisms and causes severe eye, nose, shark and lung irritation associated with headache, drowsiness and dizziness. In addition, a fish protein is preferably used. The industrial production is also not described. The curing overnight is industrially uneconomical. Despite these known processes, it has hitherto not been possible to give polymer hydrogels, from renewable raw materials (above all protein-based), a cost-effectiveness without the addition of acrylates and fossil raw materials, which are essential for industrial utilization. The use of acrylates and fossil raw materials should be largely avoided for health reasons, if possible.
  • the invention is based on the invention to avoid the disadvantages mentioned above and hydrogels, from renewable resources (preferably protein-based) and preferably without the addition of acrylates and fossil raw materials a necessary water or. To impart moisture resistance.
  • the invention is intended in particular to reduce the processing time and the use of chemicals and to produce the hydrogels preferably and largely from renewable or biodegradable raw materials. At the same time, water and energy consumption are to be reduced and productivity increased.
  • the present invention is directed to hydrogels prepared by a continuous or discontinuous process with a composition comprising destructured milk proteins, biodegradable thermoplastic polymers and plasticizers.
  • At least one protein obtained from milk or a protein produced by bacteria is optionally plasticized together with a plasticizer at temperatures between room temperature and preferably up to 140 ° C under mechanical stress.
  • the invention is based on the finding that the milk proteins and in particular casein and its derivatives can be plasticized and polymerized in this way. It is envisaged that the plasticizing takes place at temperatures preferably up to 140 ° C. For an even more gentle treatment, the protein is intensively mixed or kneaded together with a plasticizer and subjected to mechanical stress. The required plasticizing temperature is significantly reduced by the plasticizer.
  • the milk protein is preferably casein or lactalbumin or soy protein.
  • the milk-derived protein can be produced in situ by precipitation from milk.
  • the milk in mixture with rennet, other suitable enzymes or acid introduced directly as a flocculated mixture in the process or the pressed flocculated protein can be used wet.
  • a separately previously obtained, possibly purified, pure or mixed protein, i. a protein fraction from milk are used, e.g. dried as a powder.
  • the protein fraction can also be produced by ultrafiltration or by cell cultures.
  • the milk proteins for example, with additional salts such as sodium, and potassium can be modified in further processing steps, so that a casein arises.
  • the milk protein used according to the invention can be mixed with other proteins in a proportion of preferably up to 70% by weight, based on the milk protein.
  • other albumins such as ovalbumin and vegetable proteins, in particular lupine protein, soy protein or wheat proteins, in particular gluten come into question.
  • the mixture of solvent and proteins is heated, usually under pressure conditions and shear, to accelerate the crosslinking process.
  • Chemical or enzymatic agents can also be used to destructivate and crosslink the milk proteins, oxidize or derivatize, etherify, saponify, and esterify.
  • milk proteins are destructured by dissolving the milk proteins in water. Fully destructed milk proteins result when there are no clumps that affect polymerisation.
  • a plasticizer can be used in the present invention to destructivate the milk proteins and allow the milk proteins to flow, ie to produce thermoplastic milk proteins.
  • the same plasticizer or other plasticizer can be used to increase melt processability, or two separate plasticizers can be used.
  • the plasticizers can also improve the flexibility of the final products, believed to be due to the lowering of the glass transition temperature of the composition by the plasticizer.
  • the plasticizers are substantially compatible with the polymeric components of the present invention so that the plasticizers can effectively modify the properties of the composition.
  • the term "substantially compatible" means that the plasticizer, when heated to a temperature above the softening and / or melting temperature of the composition, is capable of forming a substantially homogeneous mixture with milk proteins.
  • the plasticizer is preferably water, which is used in an amount between 20 and 80% based on the weight of the protein, preferably in an amount of about 40 to 50 wt .-% of the protein content.
  • plasticizers in particular alcohols, polyalcohols, carbohydrates in aqueous solution and in particular aqueous polysaccharide solutions can be used.
  • plasticizers and associated weight fractions are preferably hydrogen bridge-forming, organic compounds without hydroxyl group, eg urea and derivatives, animal proteins, eg gelatin, vegetable proteins such as cotton, soybeans, and sunflower proteins, esters of producing acids, which are biodegradable, eg, citric acid, adipic acid, stearic acid, oleic acid-hydrocarbon based acids, eg ethylene acrylic acid, ethylene maleic acid, butadiene acrylic acid, butadienemalic acid, propylene acrylic acid, propylene maleic acid, sugar, eg maltose, lactose, sucrose, fructose, maltodextrin, glycerine, pentaerythritol and sugar alcohols , for example, malite, mannitol, sorbitol, xylitol, - polyols, eg hexanetriol, glycols and the like, and mixtures and polymers
  • plasticizers are nonlimiting examples of hydroxyl plasticizers. Important factors are the affinity to the proteins, the amount of protein and the molecular weight. Glycerine and sugar alcohols are among the most important plasticizers. Parts by weight of plasticizers are, for example, 5% -55%, but may also be in the range of 2% -75%. Any of alcohols, polyols, esters and polyesters may be used in proportions by weight, preferably up to 30% in the polymer blend.
  • Theological properties are the Theological properties, so that a good processing is possible. Strain-strain solidification is necessary to form a stable polymer structure.
  • the melting temperature is usually in a temperature range of 30 ° C to 190 ° C. Additional temperatures should be lowered with diluents and plasticizers.
  • the biodegradability of the hydrogels i. their decomposition by living things and their enzymes is an important property of MP gels.
  • thermoplastic polymer for this invention for example, and preferably, polyvinyl alcohol and copolymers, aliphatic amide and ester copolymers composed of monomers such as e.g. Dialcohols (1, 4-butanediol, 1, 3-propanediol, 1, 6-hexanediol, etc.) or ethylene and diethylene glycol, aliphatic polyester, (aliphatic esters are formed with aliphatic amides ⁇ or by other reactions such as lactic acid with diamines and Dicarbonsauredichloriden, diols with carboxylic acids, caprolactone and caprolactam, or ester prepolymers with diisocyanates, dicarboxylic acids, especially succinic, oxalic and adipic acid and their esters, hydroxycarboxylic acids, lactones, amino alcohols (eg, ethanolamine, propanolamine), cyclic lactams, - aminocarbox
  • monomers such as
  • Polybuylensuccinat / adipate copolymer polyalkylene; Polypentamethylsuccinate; Polyhexamethylsuccinate; Polyheptamethylsuccinate; Polyoctamethylsuccinate; Polyalkylene oxalates such as polyethylene oxalate and polybutylene oxalate polyalkylene succinate Copolymers such as polyethylene succinate / adipate copolymer and; Polyalkylene oxalate copolymers such as polybutylene oxalate / succinate copolymer and polybutylene oxalate / adipate copolymer; Polybutylene oxalate / succinate / adipate terpolymers; and mixtures thereof are non-limiting examples of aliphatic polyesters of dibasic acids / diols prepared, for example, from polymerizations of acids and alcohols or ring-opening reactions and suitable for the production of a polymeric hydro
  • biodegradable polymeric hydrogels are aliphatic / aromatic copolyesters. These are derived from dicarboxylic acids (and derivatives) such as malonic, succinic, glutaric, adipic, pimelic, azelaic, sebacic, fumaric, 2,2-dimethylglutaric, suberic, 1,3-cyclopentanedicarboxylic , 1,4-Cyclohexanedicarboxylic, 1,3-cyclohexanedicarboxylic, diglycol, itaconic, maleic, 2,5-norbornanedicarboxylic, 1,4-terephthalic, 1,3-terephthalic, 2,6-naphthoic acid -, 1, 5-naphthoic acid, ester-forming derivatives and mixtures thereof and diols, eg Ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, diethylene glyco
  • Examples of such aliphatic / aromatic copolyesters include blends of poly (tetramethylene glutarate-co-terephthalate), poly (tetramethylene glutarate-co-terephthalate), poly (tetramethylene glutarate-co-terephthalate), poly (tetramethylene glutarate-co-terephthalate), poly (tetramethylene glutarate).
  • co-terephthalate-co-diglycolate poly (ethylene glutarate-co-terephthalate), polyitetramethylene adipate-co-terephthalate), an 85/15 blend of poly (tetramethylene succinate-co-terephthalate), poly (tetramethylene-co-ethylene-glutarate-co-terephthalate ), Poly (tetramethylene-co-ethylene-glutarate-co-terephthalate).
  • the processability of the protein mass can be modified by other materials to influence the physical and mechanical properties of the protein mass, but also of the final product.
  • Non-limiting examples include thermoplastic polymers, crystallization accelerators or inhibitors, odor masking agents, crosslinking agents, emulsifiers, salts, lubricants, surfactants, cyclodextrins, lubricants, other optical brighteners, antioxidants, processing aids, flame retardants, dyes, pigments, fillers, proteins and their alkali salts, waxes, Adhesive resins, extenders and mixtures thereof. These Excipients are bound to the protein matrix and influence their properties.
  • Salts can be added to the melt.
  • Non-limiting examples of salts include sodium chloride, potassium chloride, sodium sulfate, ammonium sulfate, and mixtures thereof.
  • Salts can affect the solubility of the protein in water, but also the mechanical properties. Salts can serve as binders between the protein molecules.
  • lubricants can affect the stability of the polymer. These can reduce the stickiness of the polymer and reduce the coefficient of friction.
  • Polyethylene would be a non-limiting example.
  • the physical properties of the polymer composition can be influenced by other proteins, including without limitation, vegetable proteins, such as sunflower protein or animal, such as gelatin.
  • vegetable proteins such as sunflower protein or animal, such as gelatin.
  • Water-soluble polysaccharides and water-soluble synthetic polymers, such as polyacrylic acids, can also affect the mechanical properties.
  • Monoglycerides and diglycerides and phosphatides, as well as other animal and vegetable fats can influence and promote the flow properties of the biopolymer.
  • Inorganic fillers are also among the possible additives and can be used as processing agents. Possible examples, without limiting the use, are oxides, silicates, carbonates, lime, clay, limestone and kieselguhr and inorganic salts. Stearate-based salts and rosin can be used to modify the protein mixture.
  • Amino acids the components of the proteins and peptides may be added to the polymeric hydrogel mass to enhance particular pleated sheet structures or mechanical properties.
  • glutamic acid, histidine, trytophan, etc. are mentioned as examples.
  • Carbohydrates and polysaccharides, as well as amyloses, oligosaccharides and chenodeoxycholic acids can be used as further auxiliaries and additives.
  • Salts, carboxylic acids, dicarboxylic acids and carbonates, as well as their anhydrides, salts and esters can also be used as additional crosslinkers. Hydroxyde, butyl ester, as well as aliphatic hydrocarbons are other ways to cross-link molecules and form macromolecules.
  • additives and auxiliaries such as lipophilic, hydrophobic, hydrophilic, hydroscopic additives, gloss modifiers and crosslinkers may be provided.
  • the additives and auxiliaries should overall not exceed a proportion by weight of preferably about 30% by weight, based on the protein.
  • lipophilic additives vegetable oils, alcohols, fats and can be chosen, which readily hydrophobicize the polymer composition during plasticizing.
  • waxes and greases can be used which add strength to the polymer composition. As waxes, carnauba wax, beeswax, candelilla wax and other naturally derived waxes are preferred.
  • the MP gel or bound can be further treated.
  • a hydrophilic or hydrophobic surface treatment can be added to adjust the surface energy and chemical nature of the fabric.
  • hydrophobic MP gels or the polymeric hydrogel mass can be treated with wetting agents to facilitate the absorption of aqueous liquids.
  • a bonded fabric may also be treated with a topical solution containing surfactants, pigments, lubricants, salt, enzymes, or other materials to further adjust the surface properties of the MP gel.
  • the MP hydrogels In order for the MP hydrogels to meet the increased requirements of improved properties for a particular purpose, they are prepared in previously known and described methods.
  • the polymer composition having the required viscosity is prepared by the continuous or discontinuous process known from the literature and the skilled person, preferably by mixing or extruding a premix with the addition of additives or mixing the polymer composition by metering in the raw materials and additives during mixing or extrusion ,
  • the preparation of P-gels can be prepared by known methods z. B. by extrusion process or mixer, kneader or injection molding machine.
  • the polymer composition corresponds to a polymer in which the materials are converted by heating in a plastic state and thus deformed.
  • the temperature exceeds the glass transition temperature of the protein, so that it passes from the amorphous to the rubbery plastic state.
  • this can be further processed directly, preferably to a hydrogel in the extrusion process.
  • the polymer composition may be further processed into a hydrogel immediately after exiting the die, or in at least one later processing step.
  • the polymer composition can also pass through a bath prior to curing, this procedure is not particularly preferred and usually not required.
  • the polymer composition may be subjected to a spray treatment after exiting the nozzle.
  • smoothing agents, waxes, lipophilic or crosslinking agents can be applied to the surface of the polymer composition.
  • crosslinkers those given above are preferred, ie generally different salt solutions, preferably calcium chloride solution, dialdehyde starch solution, or aqueous lactic acid.
  • the multi-constituent hydrogels of the present invention can be in many different configurations. Ingredient, like here By definition, by definition, the chemical species or material is used. Hydrogels can have a monocomponent or multicomponent configuration. Component as used herein is defined as a separate part of the MP gel that is in spatial relationship with another part of the MP gel. The MP gel obtained can in turn be applied to a matrix.
  • the advantages achieved by the invention include the fact that in the production of hydrogels of the invention, the reduction of harmful substances and environmentally harmful substances during the process and on the hydrogels itself is made possible.
  • the hydrogel is biodegradable.
  • MP gels are attributed to firming structural changes (textural structure) during plasticization.
  • the MP gels are preferably made by an extrusion process to allow the highest possible productivity. All methods of preparation of hydrogels described in the art and in the literature are possible without exception. Essential to the invention is the preparation of a homogeneously plasticized polymer, preferably a biogenic biopolymer, which is preferably biodegradable. Unfortunately, no hydrogels have been developed on this basis to date that are water resistant and sufficiently resistant. Preferably, the use of petroleum-based raw materials and / or organic solvents, especially in hydrogels for wound dressings, baby products and cosmetics, to name just a few examples, should be reduced or even ruled out.
  • hydrogels which are preferably made from renewable raw materials, with a proportion of milk proteins and with properties such as water resistance, sufficient mechanical properties, such as tensile strength, tensile strength, antibacterial and biodegradable, and the possibility exists, by changing the raw material additions correspond Purpose of use, to influence the properties of the MP gels.
  • the MP gels prepared by the process according to the invention and their Sheets can be used in a variety of applications and may be wholly or partially sheeted; preferred examples include, without limitation, drug delivery devices that could be used for systemic, intratumoral, subcutaneous, topical, transdermal, and rectal applications; Wound dressings or artificial skin; solid, humidified reaction media for diagnostic kits for use in basic research (PCR, RT-PCR, in situ hybridization, in situ labeling with antibodies or other markers such as peptides, DNA or RNA probes, drugs or hormones, etc.) etc.; Transport media for cells, tissues, organs, eggs, organisms, etc .; Tissue culture media, with or without drugs, for basic research or commercial and therapeutic applications; Electrode materials (with or without enzymes); lontophoresemembranen; protective moistened media for tissue sections (such as replacement coverslips for microscope slides); and matrices for the immobilization of enzymes or proteins for in vivo, in vitro or ex vivo use as therapeutic agents,
  • Example 1 Preparation of a milk protein polymer mass.
  • the extrusion takes place with a twin-screw extruder type 30 E of the company. Collin with a diameter of 30 mm.
  • the MP gel is produced by extrusion technology.
  • Heating takes place via 4 cylinder heating zones with the following temperature sequence 65 ° C, 74 ° C, 75 ° C, 60 ° C: Temperature 65 74 74 74 75 60 r
  • the casein powder is added via a vibrating trough.
  • a hose pump is used to add water.
  • the additives are added.
  • the polymer composition is processed to a hydrogel by an extrusion process.
  • the extrusion process and the processing of the polymer composition into a hydrogel are additionally illustrated by FIG.
  • a metering device 1 the raw materials are added to the extruder 2 and mixed the polymer composition. From there, it is fed through a nozzle 3 to a post-treatment 4.

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  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Molecular Biology (AREA)
  • Proteomics, Peptides & Aminoacids (AREA)
  • Wood Science & Technology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Materials For Medical Uses (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

L'invention concerne un hydrogel de protéines laitiaires, pour lequel au moins une protéine, issue du lait et thermiquement plastifiable, est plastifiée à l'aide d'un agent plastifiant, par exemple, de l'eau ou du glycérol à des températures comprises entre la température ambiante et, de préférence, jusqu'à 140 °C avec une sollicitation mécanique et ensuite retraitée par un procédé continu ou discontinu pour obtenir des hydrogels.
EP12799513.2A 2011-11-12 2012-11-12 Procédé de production de gels, d'hydrogels , d'hydrocolloïdes et de superabsorbants de protéines laitiaires (gels de protéines laitières) Withdrawn EP2776512A1 (fr)

Applications Claiming Priority (2)

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DE102011118399 2011-11-12
PCT/EP2012/072420 WO2013068595A1 (fr) 2011-11-12 2012-11-12 Procédé de production de gels, d'hydrogels , d'hydrocolloïdes et de superabsorbants de protéines laitiaires (gels de protéines laitières)

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EP2776512A1 true EP2776512A1 (fr) 2014-09-17

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US (1) US20140373748A1 (fr)
EP (1) EP2776512A1 (fr)
WO (1) WO2013068595A1 (fr)

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Publication number Priority date Publication date Assignee Title
DE102010054661A1 (de) * 2010-12-15 2012-06-28 Anke Domaske Verfahren zur Herstellung von Milchproteinfasern und daraus gewonnene Milchproteinfaserprodukte
CN110607272B (zh) * 2019-09-23 2022-11-01 山东甲骨文生物科技有限公司 一种哺乳动物细胞培养液的添加剂及细胞培养液
IT202000029684A1 (it) 2020-12-03 2022-06-03 Splastica S R L Plastica compostabile a base di proteine del latte e relativo processo di preparazione
WO2024254205A2 (fr) * 2023-06-05 2024-12-12 University Of Vermont And State Agricultural College Procédés de traitement de liquides laitiers à l'aide d'agents gélifiants, et procédés, agents gélifiants et produits associés

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DE102010054661A1 (de) * 2010-12-15 2012-06-28 Anke Domaske Verfahren zur Herstellung von Milchproteinfasern und daraus gewonnene Milchproteinfaserprodukte

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HERNANDEZ-IZQUIERDO V M ET AL: "Thermoplastic Processing of Proteins for Film Formation-A Review", JOURNAL OF FOOD SCIENCE, WILEY-BLACKWELL PUBLISHING, INC, US, vol. 73, no. 2, 1 January 2008 (2008-01-01), pages R30 - R39, XP003026332, ISSN: 0022-1147, [retrieved on 20080124], DOI: 10.1111/J.1750-3841.2007.00636.X *
HONG S I ET AL: "Mechanical properties and biodegradability of poly-@?-caprolactone/soy protein isolate blends compatibilized by coconut oil", POLYMER DEGRADATION AND STABILITY, BARKING, GB, vol. 94, no. 10, 1 October 2009 (2009-10-01), pages 1876 - 1881, XP026719448, ISSN: 0141-3910, [retrieved on 20090508], DOI: 10.1016/J.POLYMDEGRADSTAB.2009.04.029 *
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WO2013068595A4 (fr) 2013-07-11
WO2013068595A1 (fr) 2013-05-16
US20140373748A1 (en) 2014-12-25

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