WO2012140561A1 - Polymère pauvre en peroxyde, sensible à l'oxydation comprenant au moins un composé inorganique du phosphore - Google Patents

Polymère pauvre en peroxyde, sensible à l'oxydation comprenant au moins un composé inorganique du phosphore Download PDF

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WO2012140561A1
WO2012140561A1 PCT/IB2012/051734 IB2012051734W WO2012140561A1 WO 2012140561 A1 WO2012140561 A1 WO 2012140561A1 IB 2012051734 W IB2012051734 W IB 2012051734W WO 2012140561 A1 WO2012140561 A1 WO 2012140561A1
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polymer
polymers
phosphorus
ppm
phosphorus compound
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Bernhard Fussnegger
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BASF China Co Ltd
BASF SE
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BASF China Co Ltd
BASF SE
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Priority claimed from DE202011005055U external-priority patent/DE202011005055U1/de
Priority claimed from EP11161981A external-priority patent/EP2511331A1/fr
Application filed by BASF China Co Ltd, BASF SE filed Critical BASF China Co Ltd
Priority to DE112012001679.3T priority Critical patent/DE112012001679B4/de
Priority to CN201280017917.1A priority patent/CN103459480B/zh
Publication of WO2012140561A1 publication Critical patent/WO2012140561A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L39/00—Compositions of homopolymers or 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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
    • C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C08L39/08—Homopolymers or copolymers of vinyl-pyridine
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds

Definitions

  • Oxidation-sensitive, low-peroxide polymer comprising at least one inorganic phosphorus compound
  • the present invention relates to oxidation-sensitive, low-peroxide polymer comprising at least one inorganic phosphorus compound, a method for stabilizing such a polymer and its use.
  • oxidation-sensitive polymers such as crosslinked and uncrosslinked homo- and copolymers of N-vinylpyrrolidone are usually converted to pourable powders following their polymerization by spray-drying or drum-drying or another warm-air drying.
  • spray-drying or drum-drying or another warm-air drying As a result of the intensive air contact and the heat, traces of peroxides are formed, the content of which increases still further in the course of the subsequent packaging, storage and handling. This tendency towards peroxide formation can present problems when using polymers such as polyvinylpyrrolidone (PVP and PVPP) in pharmaceutical preparations.
  • PVP and PVPP polyvinylpyrrolidone
  • the peroxide content for these polymers is limited to a maximum of 400 ppm.
  • the kinetics of peroxide formation can indeed be slowed, but not prevented.
  • these processes are associated with a very high expenditure, meaning that the acceptance of such measures by the user is low.
  • Buhler also reports on the color change in aqueous solutions of PVP, especially after storage or heating, for example during sterilization: the resulting yellow to brown-yellow coloration results from the oxidation by means of atmospheric oxygen. According to Buhler, this can be avoided by adding suitable antioxidants to the polymer (after its polymerization).
  • antioxidants even upon their addition to the polymer and thus reduce the protection and the storage time. To compensate, relatively large amounts of antioxidant therefore have to be used.
  • polyvinylpyrrolidones are mixed with an antioxidant for stabilization during storage and are stored under an atmosphere which comprises not more than 50 000 ppm of oxygen.
  • the antioxidants used are, for example, phenolic or bisphenolic compounds, preferably thioamide or thiourea derivatives.
  • such antioxidants are physiologically not entirely without risk and are completely unsuitable for the use of the polymers in pharmaceutical preparations.
  • EP 1263813 B1 discloses a process for popcorn polymerization with adjustment of the particle size of the popcorn polymers by means of passing through a stream of inert gas and/or adding reducing agents.
  • a reducing agent can optionally be added in amounts of from 0.1 to 1 % by weight, based on the monomer mixture, for achieving full freedom from oxygen in the reaction mixture.
  • the reducing agents described are sodium sulfite, sodium pyrosulfite, sodium dithionite, ascorbic acid or mixtures of the reducing agents.
  • sodium dithionite was used in an amount of 2.2 * (10 to the power of -7) to 1 .9% by weight, based on the monomer mixture.
  • EP-B 1 083 884 describes a process for stabilizing polyvinylpyrrolidones against peroxide formation, in which aqueous solutions of the polymers are admixed with very small amounts of heavy metal salts or with peroxide-cleaving enzymes. These remain in the product. Suitable heavy metals are manganese, zinc, cobalt and in particular copper.
  • GB 836,831 discloses a process for stabilizing polyvinylpyrrolidones against discolorations, in which solutions of the polymers are treated with sulfur dioxide, sulfurous acid or alkali metal sulfites.
  • DE-A 10 2005 005 974 discloses a process in which the polyvinylpyrrolidones are treated firstly with sulfur dioxide, sulfurous acid or alkali metal salts thereof and then with a free-radical scavenger.
  • WO 2010/072640 discloses a process for the preparation of low-peroxide polymer comprising the treatment of the polymer with elemental metal in the presence of a liquid, and also a polymer obtainable by the process according to the invention with a peroxide content of less than 20 ppm based on the polymer solids content, where the peroxide content is determined two days after treatment by means of the titanyl sulfate method in accordance with European Pharmacopeia edition 7, and the polymer has not more than 5 ppm, based on the polymer solids content, of any precious metal and not more than 1000 ppm, based on the polymer solids content, of any nonprecious metal.
  • Alkali metals which dissolve in the polymer solution or suspension with the formation of hydrogen are used, or precious metals and gaseous hydrogen which is passed over these precious metals.
  • the hydrogen here is intended to reduce the peroxides.
  • gaseous hydrogen and/or hydrogen-forming metals that are reactive with water is a safety risk which should not be underestimated in an industrial plant and therefore signifies higher costs.
  • Antioxidants are sufficiently known to the skilled person in all areas of polymer chemistry.
  • antioxidants are added to oxidation-sensitive substances in order to protect these against further oxidation, possibly by atmospheric oxygen (see for example R.E.King III.
  • antioxidants are added and mixed in after the polymerization or a post-treatment following the polymerization and before optionally drying to give polymer powders.
  • the amounts required for this are given as 0.00001 to 30% by weight, based on the polymer solids content.
  • amounts used in the examples are 0.1 % by weight of hydroquinone and also 0.5 and 1 % by weight of another antioxidant, in each case based on the polymer solids content.
  • a further option for suppressing the autoxidation of oxidation-sensitive polymers is to store the polymers after work-up in an oxygen-impermeable packaging.
  • EP-B 873 130 recommends spray drying polyvinylpyrrolidones to prevent the formation of peroxide under a nitrogen atmosphere and storing them in air-tight containers.
  • the packaging material used for oxidation-sensitive substances is also composite films made of polyethylene and aluminum. Although in principle such films have good barrier properties because they are essentially impermeable to oxygen, they have the disadvantage that during handling, mechanical damage to the barrier layer can in practice not be avoided, as a result of which the barrier property can be severely impaired. Even microcracks suffice to impair the oxygen impermeability of the films.
  • J P-A 09-226070, J P-A 2000-44756, J P-A 09-216653 or J P-A 2002-3609 disclose composite films with polyvinyl alcohol layers and their use for oxygen-impermeable packaging of foods, cosmetics, detergents, chemicals or fuel.
  • WO 2006/015765 discloses hose-shaped multilayer thermoplastic composite films for the packaging of foods.
  • WO 2010052088 discloses packaging forms made of multilayer films, the packaging of low- peroxide polymer and packaging methods.
  • the polymer here should have very low to undetectable peroxide contents and at the same time increased stability to oxidation and renewed peroxide formation. Likewise, it should offer adequate protection against the formation of peroxide even in the event of short- term handling in air such as, for instance, the removal of the polymer from the packaging.
  • the polymers obtained should be suitable for contact with the human and/or animal body and its fluids.
  • the polymers obtained should be
  • an oxidation-sensitive, low-peroxide polymer contained in a sealed, protective-gas- filled packaging form comprising, per kilogram of polymer solid, at least one inorganic phosphorus compound in amounts such that the total phosphorus content is 2 * 10 "5 to 0.02 mol, has been found.
  • a method for stabilizing oxidation-sensitive polymer against peroxide formation wherein, during or after the polymerization, at least one inorganic phosphorus compound is added in one or more portions in amounts such that the total phosphorus content per kilogram of polymer solid content of the finished polymer is 2 * 10 -5 to 0.02 mol, and the polymer treated in such a way is placed into a protective-gas-filled, sealed packaging form, has likewise been found.
  • polymer according to the invention in cosmetic or pharmaceutical preparations, preparations of agrochemical active ingredients, preparations in the field of food, animal feed, food supplementation or animal feed supplementation, and for medical applications has been found.
  • inorganic phosphorus compound (within the context of this invention also abbreviated and referred to synonymously as "phosphorus compound”) means at least one oxo acid of phosphorus with phosphorus in oxidation states +1 , +2, +3, +4 or mixed oxidation states, and also salts thereof. Accordingly, the use of individual acids, individual salts or mixtures of two or more different acids and/or salts is possible and encompassed by the invention.
  • Oxo acids of phosphorus with phosphorus in oxidation states +1 , +2, +3, +4 or mixed oxidation states are the substances of this class known to the skilled person. These are for example acids and salts of ortho acids and diacids, meta acids and polyacids of phosphorus with phosphorus in oxidation states +1 to +4, where the phosphorus atoms in polynuclear acids/salts can also have different oxidation states ("mixed" oxidation states).
  • phosphinic acid oxygen species
  • phosphinates +1
  • hypophosphites hypodiphosphonic acid (+2)
  • diphosphonic acid (+3) diphosphonates (+3), hypodiphosphoric acid (+4), hypodiphosphates (+4).
  • oligomeric derivatives polyphosphoric acids
  • metal salts ring form
  • mixed acids such as diphosphoric-(ll,IV) acid and diphosphoric-(lll,V) acid, and the salts of all of the aforementioned substances.
  • phosphorus compound preference is given to one or more substances selected from phosphinic acid (oxidation stage of phosphorus: +1 ), phosphinate (+1 ), hypodiphosphonic acid (+2), hypodiphosphinate (+2), phosphonic acid (+3), phosphonate (+3), diphosphonic acid (+3) and diphosphonate (+3), and salts thereof.
  • phosphorus compound particular preference is given to one or more substances selected from phosphinic acid (oxidation stage of phosphorus: +1 ), phosphinate (+1 ), phosphonic acid (+3), phosphonate (+3), diphosphonic acid (+3) and diphosphonate (+3), and salts thereof.
  • phosphorus compound very particular preference is given to one or more substances selected from phosphinate (oxidation state of phosphorus: +1 ), phosphonate (+3) and diphosphonate (+3).
  • Salts of the oxo acids of phosphorus are ammonium salts and also all metal salts of metals which are pharmacologically acceptable for people and/or animals. The limit for the
  • the allowable amount of metal in the polymer thus arises from the allowable daily dose of this metal and the allowable daily dose of polymer.
  • the allowable amount of metal accordingly arises from the allowable amount of polymer per day and kg of bodyweight of person or animal (depending on the intended application and possible administration routes into the body): if, for example, 1 g of polymer solid and 1 mg of zinc are in each case allowable per day and if these maximum values are both to be utilized at the same time, then the maximum amount of zinc in the polymer can be at most a value of 0.1 percent or 100 ppm of zinc, based on polymer solid content.
  • Preferred salts are accordingly one or more pharmacologically acceptable metals selected from lithium, sodium, potassium, magnesium, calcium, zinc and iron and also ammonium.
  • Sodium is especially preferred.
  • the polymers according to the invention comprise the phosphorus compound in amounts such that the total phosphorus content per kilogram of polymer solid is 2 * 10 "5 (corresponding to "0.00002") to 0.02 mol.
  • the phosphorus compound is used in one or more portions in amounts such that the total phosphorus content per kilogram of polymer solid content of the finished polymer is 2 * 10 -5 to 0.02 mol.
  • the polymers comprise, per kilogram of polymer solid content of the finished polymer, 0.0005 to 0.01 mol, particularly preferably 0.001 to 0.005 mol and very particularly preferably from 0.0015 to 0.004 mol total phosphorus content.
  • Total phosphorus content refers to the fraction of phosphorus, calculated as elemental phosphorus, in the finished polymer solid. If, accordingly, an inorganic phosphorus compound is used which comprises one phosphorus atom per molecule, the molar amount of phosphorus, calculated as elemental phosphorus, accordingly corresponds to the molar amount of this molecule, for instance phosphinic acid.
  • a polymer according to the invention has a peroxide content determined at the time of the preparation of not more than 50 ppm, preferably not more than 20 ppm and particularly preferably not more than 10 ppm, such as, for example less than 5 ppm or less than 1 ppm of peroxides and/or a peroxide content determined at any desired time within up to three months after preparation of not more than 100 ppm, preferably not more than 50 ppm, particularly preferably not more than 20 ppm and very particularly preferably not more than 10 ppm, such as, for example, not more than 5 ppm or even not more than 1 ppm.
  • the polymer according to the invention has residual monomer contents, for each of the monomers used, of not more than 100 ppm, preferably not more than 50 ppm, particularly preferably not more than 20 ppm, very particularly preferably not more than 10 ppm and in particular not more than 5 ppm, such as, for example, less than 1 ppm.
  • the peroxide content is determined here by means of the titanyl sulfate method in accordance with European Pharmacopeia edition 7. However, determination by means of the alternative method by means of iodometry as described in Ph. Eur. produces comparable values.
  • the oxidation state of the phosphorus compound according to the invention accordingly changes as a function of the amount and type of phosphorus compound, and also the amount of oxidizing agent relative to the amount of phosphorus compound.
  • the inorganic phosphorus compound can be detected in the polymer by means of customary analytical methods, for instance ICP-MS method (mass spectroscopy by means of inductively coupled plasma) to detect the content of, for example, phosphorus and sodium in a sample. Phosphinate, phosphate etc. can be determined via ion chromatography. Consequently, in a polymer sample, the content of alkali metals and of phosphorus compounds such as phosphinate, phosphonate and phosphate can be detected.
  • all oxidation-sensitive homopolymers and copolymers can be subjected to the process according to the invention for the stabilization of oxidation-sensitive, low-peroxide polymer.
  • polymer comprises, for example, linear, water- solubly crosslinked and water-insolubly crosslinked polymers.
  • water-insolubly crosslinked polymer also comprises the so-called popcorn polymers, which are referred to as “proliferous polymers” or, as in the case of polyvinylpyrrolidone, also as "PVPP".
  • popcorn polymers which are referred to as “proliferous polymers” or, as in the case of polyvinylpyrrolidone, also as "PVPP”.
  • the preparation of such popcorn polymers takes place by the free-radical polymerization known as "popcorn polymerization” or "proliferous polymerization".
  • Crosslinked means polymer which, viewed from a statistical point of view, has at least one branching point per polymer chain. In this connection, despite its branching and irrespective of the number of branching points per polymer chain, a polymer may still be soluble in suitable solvents. “Crosslinked” means in particular a polymer which, on the basis of the number of branching points per polymer chain or its physical structure, is insoluble in all solvents.
  • water-insoluble and “insoluble” means that the polymer has a solubility at 20°C of less than 1 part of polymer in 100 parts of water or solvent.
  • Polymer comprises homopolymers, copolymers, graft homopolymers and graft copolymers which, in each case, may be present as linear, solubly crosslinked or insolubly crosslinked polymers, in particular water-insolubly crosslinked polymers.
  • vinyllactam polymer may therefore also be a vinyllactam copolymer of two or more different vinyllactams.
  • Suitable vinyllactams are, for example:
  • N-vinyllactams such as N-vinylpyrrolidone ("NVP", “VP”), N-vinylpiperidone, N-vinylcaprolactam (“VCap”), derivatives thereof substituted with C1 to C8-alkyl groups, such as 3-methyl-, 4-methyl- or 5-methyl-N-vinylpyrrolidone.
  • Preferred vinyllactams are N-vinylpyrrolidone, 3-methyl-N-vinylpyrrolidone, 4-methyl-N- vinylpyrrolidone, 5-methyl-N-vinylpyrrolidone, N-vinylpiperidone and N-vinylcaprolactam.
  • Particularly preferred vinyllactams are N-vinylpyrrolidone and N-vinylcaprolactam. Very particular preference is given to N-vinylpyrrolidone.
  • Preferred vinyllactam polymers are vinylpyrrolidone polymers (polyvinylpyrrolidones), vinylpyrrolidone copolymers and vinylpyrrolidone-popcorn polymers.
  • Preferred vinyllactam copolymer comprising only vinyllactams comprises N-vinylpyrrolidone and N-vinylcaprolactam.
  • Suitable monomers a) are, for example:
  • N-vinylamides such as N-vinylformamide and the N-vinylamine thereof obtainable following polymerization by hydrolysis, N-vinyl-N-methylacetamide; amines such as N-vinyl- or allyl- substituted heterocyclic compounds, preferably N-vinylpyridine, or N-allylpyridine, N- vinylimidazoles, which may also be substituted in the 2, 4 or 5 position with C1 -C4-alkyl, in particular methyl or phenyl radicals, such as 1-vinylimidazole, 1 -vinyl-2-methylvinylimidazole, and quaternized analogs thereof, such as 3-methyl-1 -vinylimidazolium chloride, 3-methyl-1 - vinylimidazolium methylsulfate, N-C1 - to C24-alkyl-substituted diallylamines or quaternized analogs thereof, such as diallylammonium chloride or diallyl
  • Preferred monomers a) are vinylamides such as vinylformamide, and also the vinylamine obtainable by hydrolysis following polymerization, N-vinylimidazole, 1 -vinyl-3- methylimidazoliumchloride, 1 -vinyl-3-methylimidazoliumsulfate, and vinylmethylamide.
  • Very particularly preferred monomers a) are vinylformamide and also the vinylamine obtainable by hydrolysis after the polymerization, and N-vinylimidazole.
  • Polymers according to the invention may accordingly also be copolymers of at least one vinyllactam and at least one monomer a), for example copolymers of N-vinylpyrrolidone and N- vinylimidazole, copolymers of N-vinylpyrrolidone and N-vinylformamide or copolymers of N- vinylpyrrolidone, N-vinylcaprolactam and N-vinylimidazole.
  • Preferred copolymers are copolymers of N-vinylpyrrolidone and N-vinylimidazole.
  • Suitable monomers b) are all monomers referred to in WO 2010/072640 from page 6, line 8 to page 8, line 17 as monomers b), to which reference is expressly made here.
  • Preferred monomers b) are maleic acid, maleic anhydride, isopropylmethacrylamide, acrylamide, methacrylamide, isopropylacrylamide, N-tert-butylacrylamide,
  • 2-hydroxyethyl(meth)acrylamide and 2-hydroxyethylethylacrylamide also vinyl esters of aliphatic C2-C18-carboxylic acids, such as vinyl acetate, and also the vinyl alcohol obtainable therefrom by hydrolysis after the polymerization, vinyl propionate, vinyl butyrate, vinyl laurate, vinyl stearate, vinyl neonate "VEOVA 9" and vinyl neodecanoate "VEOVA 10", also
  • (m)ethyl (meth)acrylate and variants thereof comprising only “(m)” or “(meth)” within the context of this invention means "methyl acrylate", “ethyl acrylate”, “methyl methacrylate” and “ethyl methacrylate”. Derivatives comprising "(m)ethyl (meth)acrylate” arise analogously therefrom.
  • Particularly preferred monomers b) are methacrylamide, vinyl acetate, and also the vinyl alcohol obtainable by hydrolysis after the polymerization, vinyl propionate, vinyl neonoate VEOVA 9 and vinyl neodecanoate VEOVA 10, dimethylamino(m)ethyl (meth)acrylate,
  • Polymers which are copolymers and comprise monomers b) can comprise one or more of the monomers b). Usually, however, not more than five different monomers b) are present in one copolymer.
  • Preferred polymers further include copolymers which comprise at least one vinyllactam, at least one monomer a) and at least one monomer b).
  • Polymers according to the invention can accordingly also be copolymers of N-vinylpyrrolidone and vinyl acetate, copolymers of N-vinylpyrrolidone, vinylcaprolactam and vinyl acetate or copolymers of N-vinylcaprolactam and vinyl acetate.
  • crosslinkers are all those described in WO 2009/024457 on page 7, line 1 to page 9, line 2, to which reference is expressly made here.
  • Preferred crosslinking monomers c) are pentaerythritol triallyl ether, methylene bisacrylamide, ⁇ , ⁇ '-divinylethylene urea, ⁇ , ⁇ '-divinylpropylene urea, divinylbenzene, ethylidene bis-3-(N- vinylpyrrolidone), 1 -vinyl-3-ethylidene pyrrolidone, 3-vinyl-N-vinylpyrrolidone, 4-vinyl-N- vinylpyrrolidone, 5-vinyl-N-vinylpyrrolidone, allyl (meth)acrylate, triallylamine, acrylic acid esters of glycol, butanediol, trimethylolpropane and glycerol, acrylic acid esters of glycol, butanediol, trimethylolpropane or glycerol reacted with ethylene oxide and/or epichlorohydrin, and mixtures of
  • ⁇ , ⁇ '-divinylethylene urea ethylidene bis-3-(N-vinylpyrrolidone), 1 -vinyl-3-ethylidene pyrrolidone, 3-vinyl-N-vinylpyrrolidone, 4-vinyl-N-vinylpyrrolidone, 5-vinyl-N- vinylpyrrolidone, and mixtures of the aforementioned substances, of which very particular preference is given to ⁇ , ⁇ '-divinylethylene urea.
  • the vinyllactams, monomers a), b) and c) used for the polymerization can be, independently of one another, a single or mixtures of two or more vinyllactams, two or more monomers a), b) and/or c), where the respective combined quantitative fraction of the vinyllactams, monomers a), b) or c) gives the quantitative fraction specified in each case for vinyllactam, monomer a), for monomer b) and for monomer c), respectively, in the polymer.
  • the quantitative fractions in percent by weight based on the total mass of the polymer are here for vinyllactams usually at least 20% by weight, preferably at least 30% by weight, particularly preferably at least 50% by weight, very particularly preferably at least 60% by weight and in particular at least 97% by weight, such as, for example, homopolymers of 100% of a vinyllactam or polymers of for example 98% by weight of vinyllactam and 2% by weight of monomer c).
  • the quantitative fractions in percent by weight based on the total mass of the polymer are here for monomers a) and the monomers b), independently of one another, usually up to 80% by weight, preferably up to 70% by weight, particularly preferably up to 50% by weight, very particularly preferably up to 40% by weight and in particular up to 20% by weight and are, for example, not present at all in the polymer.
  • the total amounts of vinyllactam, monomer a), monomer b) and monomer c) always add up here to 100% by weight based on the polymer.
  • the quantitative fractions of the crosslinking monomers c) in percent by weight based on the total mass of the polymer are usually 0.001 to 20% by weight, preferably 0.01 to 10% by weight, particularly preferably 0.05 to 5% by weight and very particularly preferably 0.1 to 1 % by weight.
  • the quantitative fractions of the crosslinking monomers c) in percent by weight based on the total mass of the polymer are usually 0.001 to 10% by weight, preferably 0.01 to 5% by weight, particularly preferably 0.1 to 4% by weight and very particularly preferably 0.5 to 2.5% by weight, such as, for example, 1 .4 to 2.3% by weight.
  • a typical popcorn polymer comprises vinyllactam, for instance in the case of a preferred water-insolubly crosslinked polyvinylpyrrolidone, only vinylpyrrolidone, in the quantitative fraction from 95 to 99.8% by weight, preferably 97.5 to 99.5% by weight, and also a crosslinking monomer c) in the quantitative fraction from 0.2 to 5% by weight, preferably 0.5 to 2.5% by weight, for example 98.1 % by weight vinyllactam and 1.9% by weight monomer c), where, in the case of water-insolubly crosslinked polyvinylpyrrolidone, N,N'-divinylethyleneurea is particularly preferred as monomer c).
  • Polyvinylpyrrolidones are, for example, polymers with K values from 10 to 200, preferably K15 to K150, for example 15, 17, 25, 30, 60, 85, 90, 95, 100, 1 15 or K120.
  • the K value is a measure of the molar mass and is determined via the solution viscosity of an aqueous solution with defined polymer concentration (see Volker Buhler in "polyvinylpyrrolidone excipients for the pharmaceutical industry", 9th revised edition, BASF, page 26 to 29). It can only be determined for polymers which have adequate solubility in water.
  • Vinylpyrrolidone copolymers are, for example, copolymers with N-vinylcaprolactam (Vcap), vinyl acetate (VAc), N-vinylimidazole (VI) or mixtures thereof, such as copolymers of
  • N-vinylpyrrolidone (VP) and vinyl acetate having a VP/VAc weight ratio of from 20:80 to 80:20, for example 30:70, 50:50, 60:40, 70:30, with K values of from 10 to 150, preferably from 15 to 80 and particularly preferably from 20 to 50.
  • N-vinylpyrrolidone and vinyl acetate have a K value of from 25 to 60 and a VP to VAc weight ratio of from 55:45 to 70:30, such as, for example, 60:40, 50:50 and 65:35.
  • Further preferred copolymers are copolymers of VP and VI, and copolymers of VP and VCap in each case with K values of from 15 to 150, preferably from 20 to 100 and in particular from 30 to 90, and also weight ratios of the monomes VP to VI or VP to VCap of from 80:20 to 20:80, preferably from 70:30 to 30:70, particularly preferably from 60:40 to 40:60 and for example also 50:50.
  • the preparation of vinyllactam polymers by free-radical polymerization with or without using crosslinking monomers c) is known per se.
  • the polymerization here produces linear or crosslinked polymers which, depending on monomer solubility and optionally on the number of crosslinking points and/or the physical structure (the arrangement of the polymer chains three- dimensionally), are water-soluble, gel-forming in water or insoluble in water.
  • polyvinylpyrrolidones can take place for example as solution polymerization or precipitation polymerization in a suitable solvent such as water, mixtures of water and organic solvents, for example ethanol/water or isopropanol/water mixtures or in purely organic solvents such as methanol, ethanol or isopropanol.
  • suitable solvent such as water, mixtures of water and organic solvents, for example ethanol/water or isopropanol/water mixtures or in purely organic solvents such as methanol, ethanol or isopropanol.
  • Preferred water-insolubly crosslinked polymers are polymers of vinylpyrrolidone or polymers of vinylpyrrolidone and/or vinylcaprolactam with vinylimidazole and/or vinyl acetate which have been prepared by means of the so-called “popcorn” polymerization (also referred to as proliferous polymerization), for whcih reason the polymers are also referred to as "proliferous polymer”.
  • Water-insolubly crosslinked N-vinylpyrrolidone homopolymers are also referred to as "PVPP" or - in the pharmaceutical sector - as "crospovidone".
  • Popcorn polymerization and popcorn polymers are described for example by Barabas in Encyclopedia of Polymer Science and Engineering, Second Edition, Volume 17, 1989, page 212, 3rd paragraph to page 213, 3rd paragraph, or Haaf, Sanner and Straub, Polymer Journal 1985, Vol. 17, No. 1 , pages 143 to 152; especially on pages 148 to 151 .
  • crosslinkers used for preparing popcorn polymers are formed in situ by a reaction or reaction step prior to the actual polymerization reaction or are added as a defined compound (see Haaf et al.).
  • popcorn polymers contemplated according to the invention such as, in particular, water-insolubly crosslinked polyvinylpyrrolidone (PVPP) with the addition of crosslinkers is described for example also in EP-A 88964, EP-A 438 713 or WO 2001/068727.
  • PVPP water-insolubly crosslinked polyvinylpyrrolidone
  • the preparation of popcorn polymers such as PVPP by generating crosslinkers in situ in a reaction prior to the actual popcorn polymerization and their polymerization with the specified monomers to yield crosslinked, water-insoluble popcorn polymers is known, for example, also from US 3,277,066 or US 5,286,826.
  • such a generation of the crosslinker from the monomer takes place here in the presence of a strong base.
  • the preparation according to the present invention takes place by the first- mentioned method with the addition of crosslinkers.
  • Preferred popcorn polymers are obtained from in situ prepared crosslinker and
  • N-vinylpyrrolidone N-vinylimidazole, N-vinylcaprolactam and/or N-vinyl acetate.
  • Particularly preferred popcorn polymers are obtained using divinylethylene urea as crosslinking monomer c) and N-vinylpyrrolidone and/or N-vinylcaprolactam as vinyllactams, and optionally N-vinylimidazole and/or N-vinyl acetate as monomers a).
  • the quantitative ratios VP to VI here in the case of a VP/VI popcorn polymer are 0.5:9.5 up to 5:5, preferably 1 :9.
  • Very particularly preferred popcorn polymers are obtained from ⁇ , ⁇ '-divinylethylene urea and N-vinylpyrrolidone or from ⁇ , ⁇ '-divinylethyleneurea, N-vinylpyrrolidone and N-vinylimidazole.
  • popcorn polymers of ⁇ , ⁇ '-divinylethyleneurea and N-vinylpyrrolidone are preferred.
  • the quantitative fractions of the crosslinker in the entire monomers are here in each case 0.5 to 3% by weight, preferably 1 .4 to 2.3% by weight and very particularly preferably 1 .9 to 2.1 % by weight.
  • Water-insolubly crosslinked polymers are also commercially available, for example as Kollidon® CL, Kollidon® CL-F or Kollidon® CL-SF, and, as micronized product, Kollidon® CL-M from BASF SE, or as Polyplasdone® XL, Polyplasdone® XL-10 or
  • Popcorn polymers which comprise N-vinylpyrrolidone and N-vinylimidazole in the weight ratio 1 :9 are also commercially available for example as Divergan® HM from BASF SE.
  • the polymers are obtained by the polymerization of the stated monomers and can therefore also comprise residual amounts of these monomers.
  • Customary residual amounts are for example not more than 100 ppm of one or all monomers based on the polymer solids content.
  • the polymers are obtained without the use of such measures.
  • the polymers are obtained without the use of such measures.
  • only washing takes place.
  • polyvinylpyrrolidone polymers such as polyvinylpyrrolidone popcorn polymers.
  • Polymers comprising inorganic phosphorus compound that are particularly preferred according to the present invention are accordingly the polyvinylpyrrolidones having K values of 10 to 200, preferably K15 to K150, for example 15, 17, 25, 30, 60, 85, 90, 95, 100, 1 15 or K120, and polymers that are very particularly preferred are the water-insolubly crosslinked, low-peroxide vinylpyrrolidone polymers of 0.5 to 2.5% by weight of ⁇ , ⁇ '-divinylethylene urea and 97.5 to 99.5% by weight of N-vinylpyrrolidone which - in each case based on the polymer solids content - have a peroxide content determined at the time of the preparation of not more than 50 ppm, preferably not more than 20 ppm and particularly preferably not more than 10 ppm and/or a peroxide content determined at any desired time within up to three months following preparation of not more than 100 ppm, preferably not more than 50 ppm and particularly preferably of not more than
  • the peroxide content here is determined by means of the titanyl sulfate method in accordance with European Pharmacopeia edition 7.
  • These vinyllactam polymers, based on the polymer solids content - likewise have residual monomer contents, for each of the monomers used, of not more than 100 ppm, preferably not more than 50 ppm, particularly preferably not more than 20 ppm, very particularly preferably not more than 10 ppm and in particular not more than 5 ppm, such as, for example, less than 1 ppm.
  • the method according to the invention for the stabilization of oxidation-sensitive, low-peroxide polymer against peroxide formation is one wherein, during or after the polymerization, at least one inorganic phosphorus compound is added in one or more portions in amounts such that the total phosphorus content per kilogram of polymer solid content of the finished polymer is 2 * 10 -5 to 0.02 mol, and the polymer treated in such a way is placed into a protective-gas-filled, sealed packaging form.
  • the protective gas has less than 0.5% by volume of oxygen.
  • the inorganic phosphorus compound is selected from the group of the oxo acids of phosphorus with phosphorus in oxidation states +1 , +2, +3, +4 or mixed oxidation states, and salts thereof.
  • the polymer is selected from (i) homopolymers and copolymers of N-vinyl compounds, water-soluble or water-insolubly crosslinked
  • the phosphorus compound is added at a time at which the polymerization is at least 90% complete, preferably at least 95% complete, particularly preferably at least 98% complete and very particularly preferably at least 99.9% complete, for example 99.99% or even complete conversion has been reached.
  • the conversion refers here always to the polymerizable constituents in the reaction mixture, i.e. the vinyllactams, monomers a), b) and c), if used for the polymerization.
  • the phosphorus compound is only added after the end of the polymerization, after the end of a subsequent post-polymerization or after the end of a subsequent post-treatment such as acidic hydrolysis, stripping, steam distillation or thermal distillation.
  • the latest time for the addition is after bottling a polymer solution or polymer suspension to the bottled polymer product in the packaging form. If a drying of the resulting polymer solution or polymer suspension to give a solid polymer is envisaged, then the addition of the phosphorus compound takes place at the latest during drying, for example as addition during spray drying.
  • the addition to the solution or suspension to be dried directly prior to drying is preferred, so that the phosphorus compound is evenly distributed in the solution or suspension.
  • the process for the preparation of the polymer takes place by customary preparation methods, in the case of vinyl monomers usually by polymerization in water, organic solvent or mixtures thereof, but can also be carried out in the absence of solvents as bulk polymerization.
  • Typical representatives of the organic solvents are, for example, C1 - to C8-alcohols, such as methanol, ethanol, n-propanol, isopropanol, butanol, glycol, glycerol, diethyl ether. Preference is given to using methanol, ethanol and/or isopropanol.
  • Water may be water of varying quality: water of technical-grade quality, water of naturally occurring quality such as surface water, river water or groundwater, and also purified water.
  • Purified (“pure”) water can be purified by purification methods such as single or multiple distillation, demineralization, diffusion, adsorption, by means of ion exchangers and also activated carbons or other absorbents, by means of a filtration method such as ultrafiltration or dialysis.
  • Purified water is the term usually used here to refer to singly or multiply distilled water and also completely demineralized water.
  • the polymerization generally takes place as free-radical polymerization, in most cases initiated by adding radical-forming substances.
  • the so-called popcorn polymerization generally takes place spontaneously without the addition of such substances.
  • the polymerization can be started here by means of all methods known to the skilled person, for example by adding radical formers such as azo initiators, peroxides, redox systems and also UV light and/or radiation. Preference is given to the addition of radical formers, in particular of azo initiators, organic peroxides and/or hydrogen peroxide.
  • radical formers such as azo initiators, peroxides, redox systems and also UV light and/or radiation.
  • the preparation takes place in the case of the soluble crosslinked polymers preferably in solution, in the case of water-soluble crosslinked polymers particularly preferably in aqueous solution.
  • the preparation takes place without a diluent or as precipitation polymerization.
  • the precipitation polymerization starting from an aqueous solution or dispersion of the monomers, a polymer dispersion (in most cases a suspension) in water is obtained.
  • their preparation is by means of precipitation polymerization ("popcorn
  • Suitable reaction vessels are all vessels suitable for such reactions known to the skilled person, such as stirred reactors, tubular reactors, extruders, kneaders or fluidized-bed reactors.
  • the precipitation polymerization takes place in stirred reactors.
  • the bulk of the precipitation polymerization takes place in stirred reactors.
  • polymerization preferably takes place in stirred reactors or kneaders.
  • the polymer solutions or dispersions prepared usually have a solids content of from 5 to 80% by weight, preferably 5 to 60% by weight. In the case of dispersions, the solids content is particularly preferably 5 to 25% by weight and in particular 8 to 15% by weight.
  • the skilled person will ascertain, usually by reference to the relevant regulations, firstly the permissible total ash content and the particular upper limits for the respective polymer and then calculate the permissible amount of the individual phosphorus compound and the total phosphorus content. Likewise, he will determine by generally known methods the actual total ash content and the respective content amount of the polymer without the treatment. From the difference in contents without the treatment and the permissible upper limits according to the relevant regulations, a skilled person can directly calculate the maximum addition amount of phosphorus compound for this polymer. Usually, for the addition amount, he will establish a safety margin of about 5 to 10% based on the maximum addition amount in order to be able to take into consideration fluctuations in production. It is easy for a person skilled in the field to determine the normal variations in the chosen process and then set an appropriate safety margin for this process.
  • reducing agent and/or antioxidant can additionally be added to the low-peroxide polymer.
  • the stability against oxidation and/or further peroxide formation can be again improved.
  • Antioxidant may be an individual compound or a mixture of two or more antioxidants. Such compounds are also referred to as free-radical scavengers and, within the context of this invention, encompassed by the term "antioxidant”.
  • Reducing agent may be an individual compound or a mixture of two or more reducing agents. If reducing agents and further antioxidant are used, this addition can take place in parallel or sequentially. Preferably, the addition takes place sequentially. Particularly preferably, firstly the addition of reducing agent takes place and then the addition of further antioxidant.
  • reducing agents are added, the addition thereof takes place prior to the addition of the phosphorus compound. If antioxidant is used, the addition thereof takes place prior to or after the addition of the phosphorus compound, preferably afterwards.
  • Reducing agent and/or antioxidant and phosphorus compound can be added to the polymer, which is present in liquid, in solid form, dispersed or dissolved in a suitable solvent.
  • a preferred solvent is the same as the liquid used in each case for the preparation. Particular preference is given to water.
  • the addition of phosphorus compound and optionally reducing agent and/or antioxidant generally takes place at temperatures of from 10 to 100°C, preferably 15 to 80°C and particularly preferably 20 to 60°C.
  • the preferred pH range for the addition is 3 to 1 1 , preferably 5 to 10, particularly preferably 6 to 9.
  • a waiting time generally follows, expediently at elevated temperature. Within this waiting time, the polymer solution or dispersion is kept at elevated temperature from 20 to 90°C, preferably at 40 to 80°C, and preferably thoroughly mixed.
  • This waiting time usually lasts a few minutes up to several hours, preferably at least 5 minutes, particularly preferably at least 30 minutes and very particularly preferably at least 60 minutes, but usually not longer than 4 hours, preferably not longer than 2 hours.
  • the addition of phosphorus compound is optionally followed by a further waiting time, preferably likewise with thorough mixing.
  • This further waiting time after adding phosphorus compound usually lasts a few minutes up to several hours, preferably at least 5 minutes, particularly preferably at least 10 minutes and very particularly preferably at least 15 minutes, but is usually not more than 2 hours and preferably not more than 1 hour.
  • the optional addition of antioxidant is optionally followed by a further waiting time, preferably likewise with thorough mixing.
  • This further waiting time after adding antioxidant usually lasts a few minutes up to several hours, preferably at least 5 minutes, particularly preferably at least 15 minutes and very particularly preferably at least 30 minutes, but is usually not more than 2 hours and preferably not more than 1 hour.
  • the specified times are already suitable for commercial production in a stirred reactor in a scale of several tonnes of polymer.
  • Reducing agents in the context of this invention are sulfur dioxide, sulfurous acid or sulfites, preferably alkali metal or alkaline earth metal sulfites, for example potassium sulfite, potassium hydrogen sulfite, lithium sulfite, lithium hydrogen sulfite, sodium sulfite or sodium hydrogen sulfite, and ammonium sulfite and ammonium hydrogen sulfite, particular preference being given to sodium sulfite, sodium hydrogen sulfite and sulfur dioxide. Very particular preference is given to sulfur dioxide as aqueous solution.
  • Reducing agent can be used, for example, in amounts of from 0.005 to 1 % by weight, based on solid polymer, preferably at least 0.01 % by weight and particularly preferably at least 0.03% by weight, preferably up to 0.5% by weight and particularly preferably up to 0.20% by weight.
  • Antioxidant can be used, for example, in amounts of from 0.01 to 1 % by weight, based on solid polymer, preferably at least 0.03% by weight and particularly preferably at least 0.05% by weight, preferably up to 0.5% by weight and particularly preferably up to 0.25% by weight.
  • Suitable antioxidant which can be used according to the invention is known, for example, as antioxidant from WO2010/072640 on page 25, to which reference is expressly made here. Suitable as antioxidant are therefore, for example: ascorbic acid, erythorbic acid,
  • nordihydroguaiaretic acid ethoxyquin, bisabolol, ascorbyl palmitate or BHT ("butylhydroxy- toluene”: 2,6-di-tertiary-butyl-4-methylphenol), derivatives and salts of these substances or mixtures of the aforementioned substances.
  • BHT butylhydroxy- toluene
  • ammonium, alkali metal, alkaline earth metal salts of, for instance, ascorbic acid such as ammonium ascorbate, sodium ascorbate or magnesium ascorbate or mixtures thereof.
  • Esters of, for example, ascorbic acid with inorganic or organic acids such as ascorbyl carbonate, ascorbyl phosphate, ascorbyl sulfate, ascorbyl stearate or ascorbyl palmitate, and also the ammonium, alkali metal, alkaline earth metal salts thereof, for example sodium ascorbyl phosphate or sodium ascorbyl palmitate, are likewise suitable.
  • the analogous compounds of erythorbic acid can likewise be used. Mixtures of all of the
  • antioxidant preference is given to using ascorbic acid, erythorbic acid, alkali metal, alkaline earth metal or ammonium salts of these acids, derivatives thereof, such as esters, ethers or amides or mixtures of the aforementioned substances. Particular preference is given to using ascorbic acid or erythorbic acid, and very particular preference is given to using just ascorbic acid.
  • reducing agent and antioxidant particular preference is given to using sulfur dioxide as reducing agent and ascorbic acid and/or erythorbic acid as further antioxidant, in particular just sulfur dioxide and ascorbic acid.
  • the polymer according to the invention particularly preferably comprises only phosphorus compound and antioxidant and no reducing agent.
  • the polymer according to the invention accordingly very particularly preferably comprises only phosphorus compound and no antioxidant and no reducing agent.
  • phosphorus compound optional reducing agent and optional antioxidant takes place in each case preferably with thorough mixing such as stirring.
  • thorough mixing such as stirring.
  • a gas for example a protective gas
  • static mixers for thorough mixing.
  • the polymerization may, but does not have to be, followed by a post-polymerization.
  • free-radical former initiator
  • All initiators known to the skilled person are suitable in principle.
  • a chemical post-treatment such as an acidic or basic hydrolysis for reducing residual monomer, for instance.
  • a physical post-treatment is possible, such as distillation, steam distillation and/or stripping.
  • water-insolubly crosslinked popcorn polymer such as in particular PVPP is usually separated off from the solvent, in most cases by filtering. This is usually followed by washing one or more times, generally with purified water such as distilled water. Then, in most cases, the water content is reduced by, for instance, pressing the polymer.
  • the amount of phosphorus compound and optional antioxidant and also optional reducing agent remaining in the polymer may be lower as a result of the washing, the amount of phosphorus compound and optional antioxidant and optional reducing agent in the polymer can be ascertained directly before drying and after washing and squeezing by means of a simple determination.
  • the amount remaining in the polymer for the drying is lower than desired, through repeated adjustment of the amounts of phosphorus compound in the polymer before the drying and determination of the amounts of phosphorus compound in the solid polymer, it is readily possible to adjust the amount of phosphorus compound remaining in the solid polymer.
  • Adjustment of the amount of phosphorus is possible for instance by increasing the amount added before or during the washing step, by means of an addition directly prior to the squeezing or by means of the addition of phosphorus compound after squeezing, for instance as solid or as solution or dispersion, for example by spraying on.
  • the polymerization and optionally a physical and/or chemical post-treatment such as acidic hydrolysis, stripping, distillation, adsorption, post-treatment with reducing agent and/or antioxidant and the addition of phosphorus compound takes place expediently under a protective-gas atmosphere.
  • the polymer can - if desired - be converted to solid polymer, for example pourable polymer, by drying following polymerization and optional post-treatment. Drying methods are known to the skilled person.
  • the drying can take place, for example, by spray-drying, drum-drying or another warm-air or contact-heat drying. Drying by means of vacuum-drying or freeze-drying is also possible. All other methods for drying are in principle likewise suitable. Drying methods with spraying such as spray-drying and by means of contact surfaces such as drum drying are preferred drying methods.
  • Protective-gas atmosphere is the term used to refer to the complete or partial replacement of air by protective gas (synonymous with "inert gas”) such as, for example, nitrogen, helium, argon and/or carbon dioxide or mixtures thereof.
  • protective gas such as, for example, nitrogen, helium, argon and/or carbon dioxide or mixtures thereof.
  • a suitable protective gas is preferably nitrogen.
  • protective gas in particular nitrogen
  • the oxygen content in the system is less than 50 000 ppm, preferably less than 20 000 ppm, particularly preferably less than 10 000 ppm and very particularly preferably less than 5000 ppm.
  • an oxygen content of less than 1000 ppm or even less than 500 ppm can be achieved (ppm: based on gas volume; 5000 ppm correspond to 0.5% by volume).
  • the polymer is prepared under a nitrogen protective-gas
  • atmosphere with less than 20 000 ppm, particularly preferably less than 5000 ppm, very particularly preferably less than 1000 ppm, of oxygen.
  • the post-polymerization, the physical, chemical or other post- treatment such as washing and/or the post-treatment with reducing agent and/or antioxidant and the addition of phosphorus compound takes place under a nitrogen protective-gas atmosphere with less than 20 000 ppm, particularly preferably less than 5000 ppm, very particularly preferably less than 1000 ppm, of oxygen, such as, for example, less than 500 ppm.
  • drying In order to avoid the renewed formation of peroxides due to oxygen during drying and consequently to achieve even lower peroxide contents, it is also advisable for drying to be carried out under protective gas, in particular under protective gas with a low residual oxygen content in the drying gas of, for example, less than 50 000 ppm, preferably less than 20 000 ppm, particularly preferably less than 10 000 ppm, very particularly preferably less than
  • polyvinylpyrrolidone preferably takes place by means of warm drying gas, in particular with protective gas such as nitrogen with a low residual oxygen content.
  • the stabilization method according to the invention takes place such that, in the sealed packaging form, the oxidation-sensitive, low-peroxide polymer, comprising at least one inorganic phosphorus compound in amounts such that the total phosphorus content per kilogram of polymer solid content of the finished polymer is 2 * 10 -5 to 0.02 mol, is present under a protective gas atmosphere which has an oxygen content of less than 20 000 ppm, preferably less than 5000 ppm, particularly preferably less than 2000 ppm, very particularly preferably less than 1000 ppm and in particular less than 500 ppm.
  • Solid polymer is usually packaged directly after drying and optional subsequent sieving and/or screening steps in suitable packaging materials. Polymer solutions and dispersions are usually packaged directly in suitable packaging forms.
  • the packaging of the polymer can of course also additionally take place with nitrogen or noble-gas gassing or by means of vacuum application.
  • inert packaging materials such as in particular of materials and films which have little or virtually no permeability for oxygen also further improves the stability of the polymer against oxidation and peroxide build-up.
  • Packaging under protective gas in such inert packaging materials naturally further improves the result.
  • the polymer at the end of the stabilization method is present under a protective gas atmosphere in a sealed packaging form.
  • Suitable packaging materials and packaging methods are known, for example, from DE
  • the present invention encompasses the use of the multilayer films for packaging forms disclosed in WO 2010052088 A1 , the packaging forms disclosed therein, the outer packagings disclosed therein and also the packaging methods disclosed therein, disclosed on page 12, line 12 to page 25, line 14 and also the drawings 1 to 9 and their explanation on page 25, line 16 to page 28, line 7, the disclosure of which is hereby incorporated in its entirety.
  • the cited specification discloses therein multilayer films with barrier layer properties which comprise barrier layers with regard to gas, in particular oxygen, permeability with specific maximum oxygen permeabilities and with specific maximum water vapor permeabilities.
  • the layer structure and the production and the feed materials of such multilayer films used for this purpose is disclosed.
  • packaging forms made of these multilayer films, the forms such as side-gusset bag, hose and endless hose, properties of such packaging forms. Likewise disclosed are various options for closing such packagings. Furthermore disclosed are also the methods for filling polymers as powder, solution or dispersion into such packaging forms, especially under inert conditions. Outer packagings for such packaging forms are also disclosed. Drawings 1 to 9 show the structure of the multilayer films, of the packaging forms and of the outer packagings.
  • the embodiments preferred in WO 2010052088 A1 are also the preferred embodiments of the multilayer films and the other feed materials for the films, the packaging forms and the packaging method, where, additionally within the context of this invention, aluminum instead of EVOH is also preferred as material for the barrier layer.
  • barrier layers are accordingly also the polyvinyl alcohol polymers disclosed therefor in WO 2010/072640 on page 14, lines 2 to 12, in particular the ethylene-vinyl alcohol polymers on page 14, lines 14 to 24.
  • barrier layer If aluminum is used as barrier layer, then in principle the same procedure for preparation and use can be contemplated as disclosed in WO 2010052088 A1. Preference is given here to a layer structure made of at least three layers with the aluminum layer as the middle layer and two polymer layers, preferably water-repellent polymer layers, on both sides. It is also possible to use adhesive layers between polymer layer and aluminum layer, thus giving rise to a four- layered or five-layered film. Suitable polymers for these polymer layers on both sides of the barrier layer are in principle all polymers disclosed for this in WO 2010052088 A1 on page 13, lines 31 to 42. Preference is given to polymers selected from polyesters, polyamide, polyvinyl chloride, cellophane or polyolefins. Particular preference is given to polyolefins, very particularly preferably polyethylene and in particular the soft, relatively flexible film-suitable grades such as LDPE and LLDPE.
  • Suitable adhesive layers are preferably the polymers disclosed therefor in WO 2010052088 A1 on page 14, line 26 to page 15, line 12.
  • barrier layers in one laminate film are likewise possible.
  • one or more layers of aluminum and one or more layers of ethylene-vinyl alcohol polymer or combinations of those made of aluminum and ethylene-vinyl alcohol polymer can be used.
  • an at least seven-layered film then typically results, made of outer layer, adhesive layer, first barrier layer, adhesive layer, second barrier layer, adhesive layer and internal layer.
  • multilayer films as endless hose as described in WO 2010052088 A1 on page 18, line 23, to page 19, line 3.
  • a further aspect of the present invention is the use of oxidation-sensitive, low-peroxide polymer in cosmetic or pharmaceutical preparations, preparations in the field of agriculture, beverages, food, animal feed, food supplementation or animal feed supplementation, and also for medical applications.
  • the polymer can be used here as active ingredient or auxiliary. Allergic reactions or other incompatibilities, as can arise as a result of heavy metals or enzymes or sulfur compounds, are thereby avoided.
  • Oxidation-sensitive, low-peroxide vinyllactam polymer for pharmaceutical formulations such as solid dosage forms is particularly suitable.
  • Vinyllactam polymer preferred for such a use in pharmaceutical formulations is water-soluble and water-insolubly crosslinked vinylpyrrolidone polymer such as polyvinylpyrrolidone and PVPP and water-soluble vinylpyrrolidone-vinyl acetate polymer.
  • water-soluble and water-insolubly crosslinked vinylpyrrolidone polymer such as polyvinylpyrrolidone and PVPP and water-soluble vinylpyrrolidone-vinyl acetate polymer.
  • polyvinyl-pyrrolidone polymers In particular, preference is given to water-insolubly crosslinked polyvinylpyrrolidone popcorn polymer.
  • such formulations usually also comprise further auxiliaries customary and known to the skilled person such as binders, disintegration promoters, tablet disintegrants, surfactants, taste masking agents, lubricants, film coatings, fillers and/or sweeteners. All of these substances are in principle suitable for joint use with the polymer according to the invention.
  • active ingredients are suitable as active ingredients. Possible active ingredients are disclosed, for example, in US 2008-0181962 in paragraph [0071 ], from the seventh-last line to the end of this paragraph, to which reference is expressly made here.
  • an oxidation-sensitive, low-peroxide polymer obtainable by the process according to the invention also has a clearly measurable, but temporally limited stabilization against the rise in peroxide content during storage, even if the packaging materials are oxygen-permeable to a greater extent, if the packaging is not completely tight against the entry of oxygen - for instance in the case of damage to the packaging - and/or the polymer is located in an atmosphere with relatively high oxygen content of more than 2% by volume ranging to normal air and its known oxygen content.
  • the result of using the stabilization method according to the invention with the packaging of the polymer in the sealed, protective-gas-filled packaging forms can be yet further improved: thus, while carrying out process steps prior to bottling under a protective-gas atmosphere, in particular when carrying out drying under protective gas, the peroxide content measurable following preparation drops yet further compared with the preparation and handling, in particular drying without protective gas or with higher oxygen contents, and remains at a significantly lower level even during storage, thus shows no or only a very slowed increase in the peroxide values.
  • the present invention therefore in particular minimizes the peroxide content in the polymer and also improves stability upon thermal stress and stability in oxygen-containing medium.
  • antioxidants are usually added to the polymers to be protected by a skilled person as protection against oxidation over a prolonged period.
  • the effect from the sole use of an inorganic phosphorus compound, which as a skilled person is aware does not have an antioxidative effect, and what is more in such small amounts as in the present invention, was therefore completely unexpected.
  • One advantage of the low-peroxide polymer according to the invention is its stability, i.e. the properties such as peroxide content, molar mass, color and/or odor which it exhibits directly after preparation barely change over the course of time, if at all.
  • the determination of the peroxide content in particular serves as a measure of the grade of the polymer.
  • odor and/or color and - in the case of water-solubly crosslinked polymers - also molar mass, K value and viscosity of solutions can be used.
  • the peroxide content in the polymer, in particular vinyllactam polymer is determined here by means of iodometry, by means of titanyl sulfate reagent or by means of cerium reagent.
  • the methods are known to the skilled person, for example from Ph.Eur.7. All methods in principle produce comparable results.
  • Oxidation-sensitive, low-peroxide polymer according to the invention in particular vinyllactam polymer such as polyvinylpyrrolidone polymers, according to the invention has here, in each case based on the polymer solids content, a peroxide content determined after preparation of not more than 20 ppm, preferably not more than 10 ppm and particularly preferably not more than 5 ppm, and/or a peroxide content determined at any desired time within up to three months after preparation of not more than 50 ppm, preferably not more than 30 ppm, particularly preferably not more than 10 ppm and very particularly preferably not more than 5 ppm, such as, for example, not more than 1 ppm, the peroxide content being determined by the titanyl sulfate method in accordance with European Pharmacopeia edition 7.
  • such a polymer according to the invention has residual monomer contents - based on the polymer solids content - of each monomer used of not more than 100 ppm, preferably not more than 50 ppm, particularly preferably not more than 20 ppm, very particularly preferably not more than 10 ppm and in particular not more than 5 ppm, such as, for example, less than 1 ppm.
  • the K value (Fikentscher K value; see for example Buhler, "Polyvinylpyrrolidone - Excipient for Pharmaceuticals", Springer, 2005, page 40 to 41 ) is a measure of the solution viscosity under defined conditions. Consequently, it is a direct measure of the molar mass. If the molar mass changes, for example as a result of oxidative processes, this leads to a build-up in molar mass (leads to K value increase) or to molar mass reduction (leads to K value decrease) and thus to a change in the K value.
  • the build-up and degradation of peroxides in the polymer is one such oxidative process.
  • polymer according to the invention and polymer obtainable by the process according to the invention also has a stability of the K value and thus of the molar mass upon storage. Since the molar mass and thus the K value are directly linked to the solution viscosity, the solution viscosity also consequently does not change or changes only to a very much lower extent than without the process according to the invention.
  • Polymer according to the invention and polymer obtainable by the process according to the invention exhibits, following storage at room temperature, a change in K value, determined at any desired time within 3 months following preparation, of usually less than 10%, preferably less than 5%, particularly preferably less than 2% and very particularly preferably less than 1 %, based on the starting K value of the polymer, the starting K value being determined following preparation of the polymer in accordance with Fikentscher.
  • the color of the polymer is important depending on the application and should usually be as slight as possible, preferably completely colorless.
  • the color can be determined for example by means of spectroscopic methods and be stated for example as Hazen color number or iodine color number or as color classification according to the German Pharmacopeia. These determinations are familiar to the skilled person.
  • Oxidative processes during build-up and degradation of peroxides in the polymer also produce color-imparting components which change, usually impair, the color of the polymer, i.e.
  • polymer according to the invention in particular vinyllactam polymer, and polymer obtainable by the process according to the invention also achieves a stability in the color of the polymer upon storage.
  • Polymer according to the invention in particular vinyllactam polymer, and polymer obtainable by the process according to the invention therefore exhibits, following storage at room temperature, a color number increase in the case of the Hazen color (also called “Hazen color number” or “cobalt platinum color number”), determined at any desired time within 3 months after preparation, of usually less than 10%, preferably less than 5%, particularly preferably less than 3% and very particularly preferably of 1 % or less, based on the starting color value, which is determined after preparation.
  • Hazen color number also called "Hazen color number” or "cobalt platinum color number”
  • the color according to Hazen is important only for soluble polymers and here in particular for cosmetic applications.
  • the color is determined in accordance with the requirements in the pharmacopeia and monographs.
  • the color of the polymers according to the invention which can be achieved corresponds here to the requirements of all relevant provisions in Japan, USA and Europe in the most current version from 2010 and may even significantly surpass the requirements, i.e. have less of a color than required. These requirements and the relevant measurement methods are sufficiently known to the skilled person.
  • Polymer according to the invention in particular vinyllactam polymer, and polymer obtainable by the process according to the invention therefore exhibits, following storage at room temperature, a color number increase for the color according to Ph. Eur. 7 determined at any desired time within 3 months after preparation, of usually less than 3 scale values, preferably less than 2 scale values, particularly preferably less than 1 scale value and very particularly preferably no deviation, based on the starting color value, which is determined after preparation.
  • the odor of the polymer is likewise important depending on the application.
  • the polymer should not have a bad odor. Likewise, no bad odor should arise upon storage.
  • the odor of the polymer can be determined for example by headspace GC method using odor profiles or by olfactory means, for example using the human nose (for instance by people trained for this purpose, such as perfumers).
  • headspace GC method using odor profiles or by olfactory means, for example using the human nose (for instance by people trained for this purpose, such as perfumers).
  • Polymer according to the invention in particular vinyllactam polymer, and polymer obtainable by the process according to the invention exhibits only a very reduced or virtually no change to undesired odors, determined at any desired time within 3 months after preparation.
  • the following examples illustrate the invention in an exemplary and nonlimiting manner.
  • the peroxide content was determined for all samples by the titanyl sulfate method as in European Pharmacopeia edition 7 (Ph. Eur. 7).
  • the numbers stated refer to the ppm values (1 ppm corresponds to 1 mg of peroxide/kg of polymer), calculated and stated as hydrogen peroxide equivalent.
  • the content of phosphorus, sodium and potassium in the polymer was determined quantitatively by means of ICP-MS method (mass spectroscopy by means of inductively coupled plasma). Phosphinate, phosphonate and phosphate were determined quantitatively via ion
  • the sodium and potassium salts of phosphonic acid (sodium or potassium phosphonates; obsolete name: phosphites), of diphosphonic acid (sodium diphosphonate) and also of phosphinic acid (sodium and potassium phosphinate) were used.
  • Packaging forms/films according to the invention 1 , 2, 3
  • Packaging form 1 (film 1 ), packaging form 2 (film 2):
  • Coextruded films in the form of a flexible, non-self-supporting film bag Barrier layer EVOH polymer, thickness 15 ⁇ (+-3 ⁇ tolerance)
  • Pressure-sensitive adhesive maleic anhydride-modified polyethylene, Adoma SF 700, Mitsui Petrochemical Industries
  • the film bags with an antistatic finish on the outer side had the form of side-gusset bags.
  • the hose covering was heat-sealed at the bottom (in the region from 10 to 20 mm above the lower hose edge).
  • Packaging form 1
  • Barrier layer aluminum, thickness 15 ⁇ (+-2 ⁇ tolerance)
  • Pressure-sensitive adhesive surface-modified polyethylene, Mitsui Petrochemical Industries Polyethylene: LDPE
  • the film bags with an antistatic finish on the outer side had the form of side-gusset bags.
  • the hose covering was heat-sealed at the bottom (in the region from 10 to 20 mm above the lower hose edge).
  • Layer structure polyethylene/adhesive layer/aluminum/adhesive layer/polyethylene
  • the laminated layer consisted of aluminum/adhesive layer/polyester/adhesive layer/PE.
  • the following internal layer of PE which was in contact with the product, was a nonlaminated film (internal covering).
  • This internal covering was inserted into the outer covering; both coverings were jointly heat-sealed at the bottom end (in the region from 10 to 20 mm above the lower hose edge).
  • the two coverings were joined together by means of ten strips of an adhesive 10 to 15 cm in length spread at equal distances, executed in the direction from the lower hose edge to the upper hose edge.
  • the firm bonding of both films at the upper hose end was carried out after pouring in the product by heat- sealing the bag at the upper hose end.
  • the film bags had the form of so-called side-gusset bags.
  • Packaging form 4 (film 4)
  • Adhesive layer natural base
  • Adhesive layer natural base
  • HDPE Polyethylene
  • Example 1 polyvinylpyrrolidone, K value 30, solid powder;
  • Example 3 polyvinylpyrrolidone, K value 90, solid powder
  • Example 4 polyvinylpyrrolidone (water-insolubly crosslinked; "PVPP", prepared from 1 .99 % by weight of crosslinker divinylethyleneurea and vinylpyrrolidone), solid powder;
  • PVPP polyvinylpyrrolidone
  • Example 5 poly(vinylpyrrolidone-co-vinyl acetate), K value 38,
  • Examples 1 to 5 were polymerized by known processes (Examples 1 and 2: hydrogen peroxide as initiator, water as solvent, solid contents 40 and 45 % by weight, respectively;
  • Example 3 Wako V59 as initiator, water as solvent, solid content 23% by weight;
  • example 5 di-tert-butyl perpivalate as initiator, isopropanol/water 90:10 as solvent;
  • Example 4 prepared by means of popcorn polymerization in water from 2% by weight of divinylurea as crosslinker and 98% by weight of N-vinylpyrrolidone) and kept during all process steps of the polymerization via the washing (only Example 4) and drying up to the heat-sealing of the packaging form filled with polymer under a nitrogen protective-gas atmosphere with an oxygen content of less than 1 % by volume.
  • Example 4 the phosphorus compound was added in an amount of 300 mg after the post-polymerization and stirred for 35 minutes (polymer batch size: 5 cubic meters reactor volume), then filtered, post-washed twice with phosphorus compound-containing water (500 mg per liter of washing solution) and filtered in each case and then the polymer was squeezed off. The amount of phosphorus compound was then determined in the wet polymer directly prior to drying and again after drying.
  • packaging forms 1 to 5 were inserted into a paper carton as outer packaging, packaging form 6 was inserted into an HD-PE drum with tightened lid (elastomer seal in the inside edge), filled, evaporated and then gassed with nitrogen (99.8% by volume purity for Examples 1 to 5, 99% by volume purity for the comparative examples), heat-sealed and then stored in the cardbox or the drum closed with the lid under the stated storage conditions for the stated time.
  • the number of packs stored corresponded to the envisaged measuring points: at each measuring point, a pack was then used which had never been opened since its filling up until the measurement in order to avoid contamination or falsification as a result of opening and reclosing.
  • Gas contents achieved in the packaging following preparation of Examples 1 to 5 nitrogen 99.7% by volume, oxygen less than 0.03% by volume.
  • the initial value of peroxides was determined after the filling and after storage after the number of months stated in each case.
  • the peroxide content was determined by UV-photometric determination according to the titanyl sulfate method in accordance with European
  • Example 3 Polyvinylpyrrolidone, K value 90, solid powder
  • Packaging form 2 (example 3b) and 3 (example 3c)
  • Phosphorus content 0.00224 mg per kg of polymer
  • sodium content 0.0902 mg per kg of polymer
  • Phosphinate and phosphate were able to be determined quantitatively. Phosphonate could only be determined qualitatively on account of the small amount.
  • film 1 /packaging form 1 film 1 /packaging form 1
  • film 2/packaging form 2 film 2/packaging form 2
  • Packaging form 6 (corresponds to packaging form 5 of WO 2010052088)
  • Packaging form 4 (corresponds to packaging form 3 of WO 2010052088)
  • Packaging form 5 (corresponds to packaging form 4 of WO 2010052088)
  • Packaging form 4 (corresponds to packaging form 3 of WO 2010052088)
  • Packaging form 4 (corresponds to packaging form 3 of WO 2010052088)

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Preparation (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Cosmetics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

L'invention concerne un polymère pauvre en peroxyde, sensible à l'oxydation contenu dans une forme d'emballage scellé rempli de gaz de protection, comprenant par kilogramme de polymère solide, au moins un composé inorganique du phosphore en des quantités telles que la teneur totale en phosphore est de 2*10-5 à 0,02 mole, et des procédés de stabilisation du polymère sensible à l'oxydation contre la formation de peroxyde. Selon l'invention, pendant ou après la polymérisation, au moins un composé inorganique du phosphore est ajouté en une ou plusieurs portions en des quantités telles que la teneur totale en phosphore par kilogramme de la teneur en polymère solide du polymère fini est de 2*10-5 à 0,02 mole et le polymère traité de telle manière est placé dans une forme d'emballage scellé rempli d'un gaz de protection. L'invention concerne également l'utilisation de ces polymères.
PCT/IB2012/051734 2011-04-12 2012-04-10 Polymère pauvre en peroxyde, sensible à l'oxydation comprenant au moins un composé inorganique du phosphore Ceased WO2012140561A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE112012001679.3T DE112012001679B4 (de) 2011-04-12 2012-04-10 Abgeschlossene, schutzgasgefüllte Verpackungsform, enthaltend ein oxidationsempfindliches, peroxidarmes Polymer, dessen Verwendung und Verfahren zur Stabilisierung von oxidationsempfindlichen Polymeren gegen Peroxidbildung
CN201280017917.1A CN103459480B (zh) 2011-04-12 2012-04-10 包含至少一种无机磷化合物的氧化敏感性低过氧化物聚合物

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP11161981.3 2011-04-12
DE202011005055.6 2011-04-12
DE202011005055U DE202011005055U1 (de) 2011-04-12 2011-04-12 Peroxidarmes Polymer enthaltend Phosphorverbindung
EP11161981A EP2511331A1 (fr) 2011-04-12 2011-04-12 Polymère pauvre en peroxyde comprenant un composé phosphore

Publications (1)

Publication Number Publication Date
WO2012140561A1 true WO2012140561A1 (fr) 2012-10-18

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PCT/IB2012/051734 Ceased WO2012140561A1 (fr) 2011-04-12 2012-04-10 Polymère pauvre en peroxyde, sensible à l'oxydation comprenant au moins un composé inorganique du phosphore

Country Status (3)

Country Link
CN (1) CN103459480B (fr)
DE (1) DE112012001679B4 (fr)
WO (1) WO2012140561A1 (fr)

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DE112012001679B4 (de) 2023-05-04
DE112012001679T5 (de) 2014-02-06
CN103459480B (zh) 2017-02-22

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