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WO2000029477A1 - Poly(alpha-1,4-d-glucan) et melanges polymeres thermoplastiques le contenant - Google Patents

Poly(alpha-1,4-d-glucan) et melanges polymeres thermoplastiques le contenant Download PDF

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Publication number
WO2000029477A1
WO2000029477A1 PCT/EP1999/008474 EP9908474W WO0029477A1 WO 2000029477 A1 WO2000029477 A1 WO 2000029477A1 EP 9908474 W EP9908474 W EP 9908474W WO 0029477 A1 WO0029477 A1 WO 0029477A1
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WO
WIPO (PCT)
Prior art keywords
glucan
poly
starch
thermoplastic
polymer
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.)
Ceased
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PCT/EP1999/008474
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German (de)
English (en)
Inventor
Holger Bengs
Arnold Schneller
Anette Brunner
Ivan Tomka
Rolf Müller
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Aventis Research and Technologies GmbH and Co KG
Celanese Ventures GmbH
Original Assignee
Aventis Research and Technologies GmbH and Co KG
Celanese Ventures GmbH
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Publication date
Application filed by Aventis Research and Technologies GmbH and Co KG, Celanese Ventures GmbH filed Critical Aventis Research and Technologies GmbH and Co KG
Priority to CA002343946A priority Critical patent/CA2343946A1/fr
Priority to JP2000582458A priority patent/JP2002530454A/ja
Priority to KR1020017003849A priority patent/KR20010075375A/ko
Priority to AU15045/00A priority patent/AU1504500A/en
Priority to EP99957283A priority patent/EP1135439A1/fr
Publication of WO2000029477A1 publication Critical patent/WO2000029477A1/fr
Priority to NO20012429A priority patent/NO20012429D0/no
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0208—Tissues; Wipes; Patches
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A61K8/732—Starch; Amylose; Amylopectin; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8135—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers, e.g. vinyl esters (polyvinylacetate)
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8147—Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/85—Polyesters
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/14—Particulate form, e.g. powders, Processes for size reducing of pure drugs or the resulting products, Pure drug nanoparticles
    • A61K9/16—Agglomerates; Granulates; Microbeadlets ; Microspheres; Pellets; Solid products obtained by spray drying, spray freeze drying, spray congealing,(multiple) emulsion solvent evaporation or extraction
    • A61K9/1605—Excipients; Inactive ingredients
    • A61K9/1629—Organic macromolecular compounds
    • A61K9/1652—Polysaccharides, e.g. alginate, cellulose derivatives; Cyclodextrin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/70—Web, sheet or filament bases ; Films; Fibres of the matrix type containing drug
    • A61K9/7023—Transdermal patches and similar drug-containing composite devices, e.g. cataplasms
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/10—Antimycotics
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof

Definitions

  • the present invention relates to poly ( ⁇ -1,4-D-glucan) with a degree of polymerization of at least 40, preferably 50 and more preferably> 60, a thermoplastic polymer mixture containing at least poly ( ⁇ -1,4-D-glucan), a method for producing a thermoplastic polymer mixture and a use of a thermoplastic polymer mixture, at least containing poly ( ⁇ -1, 4-D-glucan) as a carrier matrix for active substances, such as pesticides, fungicides, insecticides, herbicides, fertilizers, pharmaceutical and / or cosmetic active ingredients , and a method for producing an agrochemical, pharmaceutical and / or cosmetic composition.
  • active substances such as pesticides, fungicides, insecticides, herbicides, fertilizers, pharmaceutical and / or cosmetic active ingredients
  • active substances such as pesticides, fungicides, insecticides, herbicides, fertilizers, pharmaceutical and / or cosmetic active ingredients
  • active substances such as pesticides, fungicides, insecticides, herbicide
  • starch in oral, pharmaceutical forms of administration is documented in the Pharmacopea Helvetica, among others.
  • thermoplastic and destructurized starch is described in EP 118 240, EP 304 401, WO 89/12492, WO 90/14938 and US 5, 095, 054.
  • These publications describe the strand or profile extrusion of thermoplastic formulations or polymer mixtures based on starch, plasticizers which are compatible with oral ingestion, such as water and the like, and preferred administration forms being disclosed.
  • the high shear melt viscosity and the pronounced structural viscosity of the starch formulations lead to shear and heat reduction in the administration forms, in particular tablets.
  • the degradation of the starch is mentioned in order to improve the processability.
  • the breakdown of the starch is controlled by heat, hydrogen ions or chloride ions.
  • the resulting thermoplastic formulations are either too brittle or too sticky, depending on the proportion of low molecular weight plasticizers.
  • thermoplastic starch and its production are described in further publications such as WO90 / 05161 and EP 0 479 964.
  • Thermoplastic starch and polymer mixtures thereof have useful mechanical properties, but the processing temperatures are usually all in one Range of approx. 180 - 230 ° C, which is much too high for the processing of a large number of pharmaceutically active substances.
  • the use of thermoplastic starch in the production of pharmaceutical compositions described in EP 0468 003 has not led to the desired success due to the processing temperature being too high.
  • the thermoplastic starch described is largely amorphous, since the starch loses its crystallization potential as a result of the thermomechanical transformation in the manufacturing process of the thermoplastic starch from native starch. Due to the lack of crystalline components, the thermoplastic starch is much too hygroscopic, ie water is absorbed from a humid ambient atmosphere. This is an important one
  • thermoplastically in particular as a thermoplastic carrier substance for active substances - pesticides, fungicides, insecticides, herbicides, fertilizers, pharmaceuticals and / or cosmetic active substances - are suitable.
  • Poly ( ⁇ -1,4-D-glucan) with a degree of polymerization of at least approx. 40, preferably at least approx. 50 and more preferably of at least approx. 60 has proven to be suitable for solving the problem , in particular when used in thermoplastic polymer mixtures containing at least the aforementioned poly ( ⁇ -1, 4-D-glucan).
  • Linear poly (-1, 4-D-glucan) s are polysaccharides consisting of glucose monomers, the latter being largely exclusively connected to one another by ⁇ 1,4-glycosidic bonds. The most naturally occurring ⁇
  • amylose is amylose, a component in vegetable starch.
  • linear ⁇ 1, 4-glucans has become more and more important. Due to its physio-chemical properties, amylose can be used to produce films that are colorless, odorless and tasteless, as well as non-toxic and biodegradable. bar.
  • a number of possible applications are already known today, for example in the food industry, the textile industry, the glass fiber industry and in the production of paper.
  • Water-insoluble linear polysaccharides such as the polyglucan proposed according to the invention, such as poly ( ⁇ -1,4-D-glucan) are preferred.
  • the degree of branching in the 6 position is ⁇ 4%, preferably a maximum of 2%, and in particular a maximum of 0.5%, and the degree of branching in the other position not involved in the linear linkage, e.g. the 2- or 3-position, in the case of the preferred poly ( ⁇ -1,4-D-glucan) preferably in each case at most 2%, and in particular at most 1%.
  • poly ( ⁇ -1,4-D-glucan) s which have no branches or whose degree of branching is so minimal that it can no longer be detected using conventional methods.
  • the prefixes “ ⁇ ” or “D” relate solely to the linkages which form the polymer backbone and not to branches.
  • water-insoluble polysaccharides is understood to mean poly ( ⁇ -1,4-D-glucan) s which, according to the definition of the German pharmaceutical book according to classes 4 to 7, belong to the categories “slightly soluble”, “Hardly soluble”, “very poorly soluble” or “practically insoluble” compounds fall.
  • sparingly soluble to practically insoluble compounds especially very sparingly soluble to practically insoluble compounds are preferred, such as e.g. sparingly soluble to practically insoluble poly ( ⁇ -1,4-D-glucan) s with a degree of polymerization> 40, preferably> 50, and even more preferably> 60.
  • Room temperature and separation by centrifugation can be recovered taking into account the experimental losses at least 66% of the amount used.
  • linear poly ( ⁇ -1,4-D-glucan) The production with regard to the isolation of linear poly ( ⁇ -1,4-D-glucan) is described, for example, in WO95 / 31553. Proteins are described which have an enzymatic activity of an amylosucrase which is encoded by a DNA sequence, characterized in one of claims 1 and 2 of the international patent application mentioned. These proteins are suitable for the production of linear poly ( ⁇ -1, 4-D-glucan) s. Other proteins with activity for the synthesis of poly ( ⁇ -1, 4-D-glucan), such as phosphorylases, glycogen synthetases, glucan transferases, starch sythases, are suitable for the production of polyglucans in the sense of the present invention.
  • polyglucans by means of genetically modified organisms such as bacteria, fungi or algae, or higher plants which contain the proteins mentioned, i.e. Phosphorylases, glycogen synthetases, glucan transferases, starch sythases or amylosucrases with the activity for the synthesis of polyglucans preferably contained, suitable.
  • Phosphorylases i.e. Phosphorylases, glycogen synthetases, glucan transferases, starch sythases or amylosucrases with the activity for the synthesis of polyglucans preferably contained, suitable.
  • poly ( ⁇ -1, 4-D-glucan) or also referred to as polyanhydro-D-glucose (PADG) in a range of the degree of polymerization (DP) of approx. 40-300, such as 60-100, for example is preferred, there is a remarkable tendency towards the formation of regular conformation, double helix molecular morphology and a high crystalline fraction detectable by means of nuclear magnetic resonance spectroscopy and X-ray diffraction.
  • the change in crystal structure due to thermal transformation is analogous to that in potato starch.
  • the kinetics of these transformations is faster than that of potato starch.
  • the formation of molecular complexes with suitable low molecular weight Ren mixed components, such as fatty acids, is coupled with the partial conformational conversion to the monohelical V structure, known in the case of amylose, and partially to a secondary unidentified, unknown structure.
  • the ability to form complexes is approximately 3 times higher than that of amylose.
  • the new poly ( ⁇ -1, 4-D-glucan) s combine the ability of the two starch components - amylose and amylopectin - to optionally form regular conformational characteristics characteristic of these two components.
  • the poly ( ⁇ -1,4-D-glucan) s proposed according to the invention advantageously combine the good processability of degraded starch and the desired properties of crystalline starch.
  • the high crystallinity of poly ( ⁇ -1, 4-D-glucan) paired with the low molecular mass of the poly ( ⁇ -1, 4-D-glucan) lead to a structure in which the compound molecules of the crystallites absence.
  • the linking molecules can be introduced by adding thermoplastic starch to the poly ( ⁇ -1, 4-D-glucan).
  • the desired volume fraction ratio of the crystalline and amorphous phase can be adjusted by mixing poly ( ⁇ -1, 4-D-glucan) and thermoplastic starch.
  • Another aspect is the processability of plasticized starch.
  • the ratio between the average degree of polymerization of starch and of poly ( ⁇ -1,4-D-glucan) is preferably at least a power of 10.
  • the limit value of the shear viscosity at a sufficiently low shear rate is called zero
  • Shear viscosity denotes ( ⁇ ( ⁇ ) o, where ⁇ is the viscosity and ⁇ is the shear rate).
  • the zero shear viscosity is proportional to the 3.4th power of the weight average molecular weight.
  • thermoplastic mixtures of one part of poly ( ⁇ -1,4-D-glucan) with 3 parts of thermoplastic starch show a 6 to 7-fold increase in elongation at break and a 2 to 3-fold increase in energy absorption when broken compared to the corresponding values of pure thermoplastic starch.
  • the shear viscosity of the same mixture which is dependent on the shear rate, is a factor 2 lower at the processing temperature of the thermoplastic starch than that of the thermoplastic starch itself.
  • thermoplastic starch The mixture of one part thermoplastic starch and three parts poly ( ⁇ -1, 4-D-glucan) still shows the same energy absorption at break as with thermoplastic starch, but the shear viscosity dependent on the shear rate is more than 10 times lower than that of thermoplastic starch.
  • thermoplastic processability of poly ( ⁇ -1, 4-D-glucan) is an important one
  • thermoplastic poly ( ⁇ -1, 4-D-glucan) mixture supports the control of the release of active ingredients, e.g. drug release; the swelling time, the disintegration time and the dissolution time of these shaped particles define the release time of the active ingredient.
  • the thermoplastic parts or particles made of it must be small enough so that the kinetic process mentioned has a standard deviation that is smaller than the corresponding mean values.
  • the uniform, homogeneous distribution of the active ingredient in the thermoplastic melt can be simplified by counter-rotating twin-screw extruders provided with suitable mixing elements. In conclusion, it can be said that this is now possible since all the necessary requirements have been met:
  • Plasticized poly ( ⁇ -1,4-D-glucan) can be made, for example, by using glycerin as a plasticizer; - Glycerin is on the list of physiologically safe additives for pharmaceutical / pharmaceutical formulations;
  • thermoplastic starch can be reduced by adding poly ( ⁇ -1, 4-D-glucan), at least by 40 ° C.
  • thermoplastic polymer mixture in which the proportion of starch, such as in particular thermoplastic starch, is between 20-80% by weight, based on the proportion of polymer including polyglucan and optionally other thermoplastically processable polymers.
  • thermoplastic is again used
  • Polymer mixture proposed, the proportion of poly ( ⁇ -1,4-D-glucan) being 20-80% by weight, based on the proportion of polymer including the starch and optionally other thermoplastically processable polymers.
  • poly ( ⁇ -1,4-D-glucan) can be mixed with thermoplastic starch according to the present invention and used in particular for the production of a thermoplastic carrier matrix, for example for agrochemical, pharmaceutical and / or cosmetic active ingredients.
  • any biologically active substance and combination of substances in the broadest sense, is regarded as an active substance, preferably pharmaceutical active substances, agrochemical active substances which can be used in agriculture, horticulture and forestry.
  • agrochemical includes fertilizers, herbicides, fungicides, insecticides, pesticides and other pesticides and pesticides, storage protection agents, plant growth and inhibitors, silage additives, preservatives and soil conditioners. Even feed additives, animal hygiene and pharmaceuticals or flavorings and fragrances cannot be excluded.
  • known active substances can be used, as described, for example, by Weed Research 26, 441-445 (1986) or "The Pesticide Manual", Ist edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 1997 and the literature cited therein.
  • Known herbicides which can be added to the active ingredient carrier according to the invention are, for example, the following active ingredients (note: the compounds are either with the "common name” according to the International Organization for Standardization (ISO) or with the chemical name, if necessary (together with a common code number): atrazine; metotachlor; propiconazole; metalaxyl; dicamba (products, brands and trademarks of Novartis); bensulfuron; nicosulfuron; methomyl; flusilazole; benomyl (Du Pont products, brands and trademarks); glyphosate; alachlor; acetochlor; butachlor; triallate (products, brands and trademarks of Monsanto); paraquat; L-cyhalothrin; fluazifop; cypermethrin; EPTC (Zeneca products, brands and trademarks); fenoxaprop; deltametrin; phenmedipham; endosulfan;
  • Rhone Poulenc brands and trademarks of Rhone Poulenc); bentazone; epoxiconazole; sethoxydim; hormones; metazachlor (products, brands and trademarks of BASF); acetochlor; acifluorfen; aclonifen; AKH 7088, ie [[[1- [5- [2-chloro-4- (trifluoromethyl) phenoxyl-2-nitrophenyll-2-methoxyethylidenel-aminol-oxy] - acetic acid and - acetic acid methyl ester; alachlor; alioxydim; ametryn; amidosulfuron; amitroi; AMS, ie ammonium sulfamate; anilofos; asulam; atrazine; azimsulfurone (DPX-A8947); aziprotryn; azoxystrobin; barban; BAS 516 H, ie 5-fluoro
  • Ester derivatives eg clodinafop-propargyl); clomazone; clomeprop; cloproxydim; copyralid; cumyluron (JC 940); cyanazine; cycloate; cyclosulfamuron (AC 104); cy-cloxydim; cycluron; cyhalofop and its ester derivatives (eg butyl ester, DEH-112); cyperquat; cyprazine; cyprazole; daimuron; 2,4-DB; dalapon; desmedipham; desme- tryn; di-allate; dicamba; dichlobenil; dichlorprop, dicloiop and its esters such as dicl-ofop-methyl; diethatyl; difenoxuron; difenzoquat; diflufenican; dimefuron; dimethachlor; dimethametryn; dimethen
  • NC 31 0, i.e. 4- (2,4-dichlorobenzoyl) -1-methyl-5-benzyloxypyrazole; neburon; nico-sulfuron; nipyraclophen; nitraline; nitrofen; nitrofluorfen; norflurazon; orbencarb; oryzalin; oxadiargyl (RP-020630); oxadiazon; oxyfluorfen; paraquat, pebulate-, pendimethalin; perfluidone; phenisopheme; phenisopharm; phenmedipharm; picloram; piperophos; piributicarb; pirifenop-buty: pretilachlor; primisulfuron-methyl; procayzine; prodiamine, profluraline; proglinazine-ethyl; prometon; prometryn; propachlor; propane; propaquizafop and its esters;
  • propargyl esters quinclorac; quinmerac; quinofop and its ester derivatives, quizalofop and quizalofop-P and their ester derivatives e.g. quizalofop-ethyl; quizalofop-P-tefuryl and ethyl; renriduron; rimsulfuron (DPX-E 9636); S 275, i.e. 2- [4-chloro-2-fluoro-5- (2-propynyloxy) phenyl-4,5,6,7-tetrahydro-2H-indazole; secbumeton; sethoxydim; siduron; simazine; simetryn; SN
  • Suitable pharmaceutical active ingredients include:
  • Estrogen derivatives such as estradiol
  • Progestin derivatives such as levonorge strel or norethisterone acetate
  • testosterone e.g. testosterone
  • non-steroidal anti-inflammatory drugs such as Flurbiprofen, Diciofenac, Ketoprofen, Ketololac,
  • ⁇ -adrenoceptor agonists like clonidine, especially also so-called ⁇ -blockers like propranolol, mepindolol and others.
  • - Peptides such as insulin, leuprolide, enkephalin, oxytocin, Ramorelix, caicitonin, buselrelin and their descendants
  • Cytostatics e.g. 5-fluorouracil
  • Parkinson's therapies in particular monoamine oxidase inhibitors such as selegelin, in particular also dopamine D 2 agonists, in particular also parasympathomimetics, in particular cholinesterase inhibitors such as physostigmine
  • Potential active ingredients for oral use include:
  • ß-receptor blockers such as metoprolol, acebutolol, atenolol and others -
  • Anti-Parkinson agents such as levodopa, benserazide, biperiden or combinations of various anti-Parkinson agents
  • Calcium antagonists e.g. Nifedipine, diltiazem and others
  • ACE inhibitors such as Captopril, lisinopril, perindopril and others
  • narcotic analgesics e.g. Morphine sulfate
  • Antiallergics such as Terfenadine, Loratadine and others
  • Antiarrhythmics e.g. Mexitil
  • Anti-epileptics e.g. Carbamazepine
  • Diuretics e.g. Furosemide, piretanide
  • lipid-lowering agents e.g. Clofibrate, lovastatin
  • Antidepressants such as Amytriptyline
  • thermoplastically processable polymers which are preferably biocompatible , as also preferably physiologically compatible.
  • these can be, for example, vinyl compounds, such as ethylene-vinyl alcohol, or copolymers of vinyl acetate and vinyl acrylate with ethylene.
  • suitable polymers are, for example, polyalkanoates, such as, in particular, aliphatic polyesters.
  • the complexation can optionally also be used to bind pharmaceutical, cosmetic, agricultural and similar active substances to the poly ( ⁇ -1,4-D-glucan) by complexation. It is proposed that between 2 and 20% by weight of a complexing agent be added to the poly ( ⁇ -1,4-D-glucan).
  • thermoplastic starch To investigate the suitability of mixtures of poly ( ⁇ -1, 4-D-glucan) with thermoplastic starch, the entire series of mixtures of poly ( ⁇ -1, 4-D-glucan) and thermoplastic starch has now been examined with regard to crystallinity and mechanical properties examined.
  • Glycerin is used because this material has proven to be very suitable and, as already mentioned above, this material can also be safely used in relation to pharmaceutical and / or cosmetic preparations.
  • Poly ( ⁇ -1,4-D-glucan) is mixed at about 170 ° C. with the plasticizer, such as the glycerin mentioned.
  • the plasticized poly ( ⁇ -1,4-D-glucan) with thermoplastic starch is again mixed in a temperature range of approx. 160 ° to 180 ° C in an extruder, the residence time depending on the composition being between 1 and 5 minutes , at 50 to 200 revolutions per minute, preferably 100 rpm.
  • the plasticizing or mixing work per kg of poly ( ⁇ -1, 4-D-glucan) introduced into the extruder is between 0.2 and 0.4 kWh.
  • thermoplastic starch used for the preparation of the mixtures with poly ( ⁇ -1, 4-D-glucan) was produced by mixing with a plasticizer or plasticizer, such as, for example, with 35% glycerol in a temperature range from approx. 160 ° C. to 180 ° C, which is now an essential feature for the production of the thermoplastic starch during the mixing process in the melt
  • thermoplastic mixtures it is also possible to interpose the thermoplastic mixtures
  • thermoplastic starch Prepare poly ( ⁇ -1, 4-D-glucan) and thermoplastic starch in one step by adding poly ( ⁇ -1, 4-D-glucan) and native starch together with 35% glycerin in an extruder at approx. 170 ° C are melted and deformed, again for the formation of the thermoplastic starch moisture must be removed from the melt, to a value below 5% by weight, based on the amount of native starch and a proportionate amount of plasticizer such as 35% glycerin added to the starch.
  • Poly ( ⁇ -1, 4-D-glucan) therefore does not cause an increase in the crystallinity of the thermoplastic starch phase and conversely the TPS portion does not result in a decrease in the crystallinity of poly ( ⁇ -1, 4-D-glucan).
  • the structure found is a mixture of V-amylose and a structure which has not been identified to date, for which reference is made to FIG. 2.
  • Example 1 1, 00 52.7 +/- 7 2.8 +/- 0.5 11, 7 +/- 2 0.458
  • Example 3 0.75 46.2 +/- 6 5.6 +/- 0.7 26.2 +/- 5 0.382
  • Example 5 0.50 18.1 +/- 2 3.5 +/- 0.2 42.0 +/- 7 0.247
  • Example 6 0.25 24.2 +/- 7 4.6 +/- 0.4 79.0 +/- 6 0.072
  • Example 7 0 184 +/- 34 9.4 +/- 0.5 15.8 +/- 5 0.045
  • TPS and poly ( ⁇ -1, 4-D-glucan) are comparable. 25% poly ( ⁇ -1, 4-D-glucan), however, causes a significant improvement in the elongation at break to 79%.
  • glycerin is a suitable plasticizer for poly ( ⁇ -1,4-D-glucan), whereby, for example, by using 35% glycerol practically identical properties can be achieved as in thermoplastic starch, also softened with 35%. Glycerin. In principle, however, all those materials can be used for plasticizing poly ( ⁇ -1, 4-D-glucan) which are also suitable for plasticizing or plasticizing thermoplastic starch.
  • Glycerin, DMSO, citric acid monohydrate, sorbitol, etc. are suitable, to name but a few.
  • all substances are suitable with a solubility parameter of more than 30 Mpa, whereby these have to be physiologically harmless in the field of pharmaceutical applications.
  • thermoplastic polymer mixture suitable as a carrier matrix for agrochemical, active pharmaceutical and / or cosmetic substances, either mixtures between the plasticized poly ( ⁇ -1, 4-D-glucan) and thermoplastic starch can be used, as well as mixtures between the polyglucan and other suitable polymers, such as vinyl compounds, polyalkanoates, to only a few to call. It is of course essential that these other polymers can be processed thermoplastically, are physiologically compatible and preferably are biologically compatible. Mixtures between polyglucan, thermoplastic starch and other polymers can of course also be used for the production of the carrier matrix mentioned.
  • thermoplastic polymer mixture can also be chosen freely, ie the thermoplastic starch to which the plasticized polyglucan is added or a polymer mixture of another polymer can be used. polymer with the thermoplastic starch to which the polyglucan is added in the extruder, etc.
  • agrochemical or pharmaceutical or cosmetic active substance (s) and further physiologically tolerable additives, fillers and the like are added to the melt to produce the agrochemical, pharmaceutical and / or cosmetic composition for the thermoplastic polymer mixture mentioned. It is essential that the temperature in the extruder or when mixing in the melt is not chosen too high, so that the active pharmaceutical or cosmetic substances cannot be damaged.
  • Example 8 Preparation of a transdermal therapeutic system
  • one part of poly ( ⁇ -1,4-D-glucan) is first mixed with two parts of thermoplastic starch in an extruder at about 170 ° C., where Both materials each contain 35% glycerin as a plasticizer or plasticizer.
  • the polymer melt is then cooled to approx. 140 ° C. and nicotine and approx. 5% water are added as the active pharmaceutical substance, and the pharmaceutical polymer melt obtained is then extruded into films with a layer thickness of 200 ⁇ .
  • the dosage of the nicotine is such that 7 cm 2 , cut out of the extruded film, usually contain about 35 mg of nicotine.
  • the amylose film obtained in this way is not used directly to check the release, but rather so-called nicotine amylose 24-hour patches are produced, which have the following structure:
  • amylose film or reservoir of active ingredient produced according to the invention such as the above-mentioned nicotine, polyglucan / TPS mixture containing 35% glycerol,
  • Release medium citrate phosphate buffer pH 5.9; 900 ml.
  • UV detection 290 nm.
  • FIG. 4 shows the cumulative in vitro release of nicotine from the nicotine amylose 24 hour patch or from the amylose / TPS matrix patch.
  • the release profile is usually based on Higuchi's square root law for matrix patches.
  • Example 9 Extrusion pellets for oral administration of active ingredients
  • a poly ( ⁇ -1,4-D-glucan) / TPS polymer mixture is used as a matrix for extrusion pellets for the oral application of active substances according to the principle of "multiple unit dosage forms".
  • a film is again produced, analogous to the amylose / TPS film, which contained active ingredients for transdermal application as a component.
  • active ingredients for transdermal application as a component.
  • only potential active ingredients, suitable for oral use, are incorporated into the polymer melt and extruded as a film.
  • the film obtained in this way is cut into strips of approximately 1-2 mm in width and then reduced in size so that approximately 1 mm 2 large pieces of film are created.
  • the cutlets thus obtained, containing the pharmaceutical active ingredient are pressed in tablet form or else filled into hard gelatin capsules.
  • pellets that are formulated with a combination of suitable pharmaceutical additives or measures an active ingredient release kinetics with almost zero order can be achieved with the use of pellets (for example Beloc-Zok).
  • poly ( ⁇ -1, 4-D-glucan) in combination with, for example, thermoplastic starch the active ingredient release of pellets can be controlled via their geometry and application form (tablet or capsule). The use of other auxiliary substances is not absolutely necessary.
  • the pellets or schnitzel can be filled into a capsule, which can be provided with an enteric coating.
  • the chips or pellets can also be coated with gastric juice-resistant material in that the extruded film is coated accordingly with gastric juice-resistant materials. This can be done, for example, by coextruding multilayer films, the amylose / TPS layer containing the pharmaceutical active ingredient for oral applications being selected as the central layer. If these pellets or chips are not filled into a capsule, they are usually compressed into a tablet, as already mentioned above. This can in turn be provided with a coating for gastric juice resistance or control of the release of the active ingredient.
  • a part of poly ( ⁇ -1,4-D-glucan) is first mixed with two parts of thermoplastic starch in the melt in an extruder at approximately 170 ° C., both materials each Contain 35% glycerin as plasticizer or plasticizer.
  • the film thus obtained is then shredded by means of pecking to form particles.
  • the particles produced in this way can now be applied outdoors, for example at a dosage of approx. 30-100 g per hectare.
  • the great advantage of using these amylose film particles containing the agrochemical active substance is that good dosing becomes possible and the release is delayed.
  • the delayed release can depend on the drug loading
  • the active substance loading in the present example is only 5%, but higher active substance loads of up to 50% are of course also possible.
  • thermoplastic poly ( ⁇ -1, 4-D-glucan) or the thermoplastic polymer mixtures containing poly ( ⁇ -1, 4-D-glucan) described above are of course only Examples to illustrate the present invention.
  • the invention is of course not limited to the applications mentioned or to the active substances, process parameters, polymer component partners for poly ( ⁇ -1, 4-D-glucan) etc. mentioned in the examples, but can be in any way be added or modified by adding further components, by selecting other process parameters, etc.

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Abstract

L'invention concerne des poly( alpha -1,4-D-Glucan)s ayant un degré de polymérisation minimum d'environ 40, notamment d'environ 50 et, de préférence, d'environ 60. Des poly( alpha -1,4-D-Glucan)s plastifiés, ayant les degrés de polymérisation ou les mélanges thermoplastiques mentionnés et contenant des poly( alpha -1,4-D-Glucan)s thermoplastiques plastifiés, sont particulièrement adaptés comme matrice excipient destiné aux principes actifs utiles dans l'agriculture, pharmaceutiques et/ou cosmétiques.
PCT/EP1999/008474 1998-11-17 1999-11-05 Poly(alpha-1,4-d-glucan) et melanges polymeres thermoplastiques le contenant Ceased WO2000029477A1 (fr)

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CA002343946A CA2343946A1 (fr) 1998-11-17 1999-11-05 Poly(alpha-1,4-d-glucan) et melanges polymeres thermoplastiques le contenant
JP2000582458A JP2002530454A (ja) 1998-11-17 1999-11-05 ポリ（α−１，４−Ｄ−グルカン）およびそれを含有する熱可塑性ポリマー混合物
KR1020017003849A KR20010075375A (ko) 1998-11-17 1999-11-05 폴리(알파-1,4-ｄ-글루칸) 및 폴리(알파-1,4-ｄ-글루칸)을포함하는 열가소성 중합체 혼합물
AU15045/00A AU1504500A (en) 1998-11-17 1999-11-05 Poly(alpha-1,4-d-glucan) and thermoplastic polymer mixtures containing the same
EP99957283A EP1135439A1 (fr) 1998-11-17 1999-11-05 Poly(alpha-1,4-d-glucan) et melanges polymeres thermoplastiques le contenant
NO20012429A NO20012429D0 (no) 1998-11-17 2001-05-16 Poly(<alfa>-1,4-glukan) og termoplastiske polymerblandinger av samme

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DE19852826A DE19852826A1 (de) 1998-11-17 1998-11-17 Poly(alpha-1,4-D-Glucan)
DE19852826.4 1998-11-17

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KR20020083538A (ko) * 2001-04-26 2002-11-04 주식회사 더멋진 바이오텍 초임계 유체 추출법을 이용한 고순도 효모 글루칸의제조방법
JP2005508359A (ja) * 2001-10-23 2005-03-31 インノゲル アクチエンゲゼルシャフト 澱粉ゲルを基剤とする成形体の製造
EP1171101B1 (fr) * 1999-04-22 2007-03-14 Euro-Celtique S.A. Procede de realisation d'une matrice a action prolongee amorphe insoluble dans l'eau
CN101928411A (zh) * 2010-03-26 2010-12-29 李云政 淀粉基可生物降解组合物及其制备方法和应用
JP4885408B2 (ja) * 2000-07-17 2012-02-29 江崎グリコ株式会社 酵素合成アミロースから得られる生分解性物品
CN114316424A (zh) * 2021-11-22 2022-04-12 金发科技股份有限公司 一种透明耐候pp/ps复合材料及其制备方法

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DE19860371A1 (de) 1998-12-28 2000-06-29 Aventis Res & Tech Gmbh & Co Kosmetische oder medizinische Zubereitung für die topische Anwendung
ATE349204T1 (de) * 2000-11-09 2007-01-15 Celanese Ventures Gmbh Weichkapseln umfassend ein stärkegemisch verringerten verzweigungsgrades
WO2002043768A1 (fr) * 2000-11-30 2002-06-06 Celanese Ventures Gmbh Composes d'inclusion moleculaires constitues de polysaccharides lineaires insolubles dans l'eau fabriques de maniere biocatalytique et d'acides gras ou de derives d'acides gras
DE10214327A1 (de) 2001-10-23 2003-05-22 Innogel Ag Zug Netzwerk auf Polysaccharidbasis und Verfahren zu dessen Herstellung
JP2005509052A (ja) * 2001-10-23 2005-04-07 インノゲル アクチエンゲゼルシャフト 多糖類を基剤とする網状構造およびその製造方法
EP1438033B1 (fr) * 2001-10-23 2008-06-11 InnoGEL AG Capsules dures a base de gel d'amidon et procede permettant de les utiliser
JP5097368B2 (ja) * 2006-08-09 2012-12-12 関東天然瓦斯開発株式会社 ヨウ素含有成型物
EP2552402B1 (fr) * 2010-03-26 2016-11-23 Dow Global Technologies LLC Film multicouche extrudé à l'état fondu
CN102892815B (zh) * 2010-03-26 2016-05-18 陶氏环球技术有限责任公司 熔体挤出的膜

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Publication number Priority date Publication date Assignee Title
EP1171101B1 (fr) * 1999-04-22 2007-03-14 Euro-Celtique S.A. Procede de realisation d'une matrice a action prolongee amorphe insoluble dans l'eau
JP4885408B2 (ja) * 2000-07-17 2012-02-29 江崎グリコ株式会社 酵素合成アミロースから得られる生分解性物品
KR20020083538A (ko) * 2001-04-26 2002-11-04 주식회사 더멋진 바이오텍 초임계 유체 추출법을 이용한 고순도 효모 글루칸의제조방법
JP2005508359A (ja) * 2001-10-23 2005-03-31 インノゲル アクチエンゲゼルシャフト 澱粉ゲルを基剤とする成形体の製造
CN101928411A (zh) * 2010-03-26 2010-12-29 李云政 淀粉基可生物降解组合物及其制备方法和应用
CN101928411B (zh) * 2010-03-26 2012-06-13 李云政 淀粉基可生物降解组合物及其制备方法和应用
CN114316424A (zh) * 2021-11-22 2022-04-12 金发科技股份有限公司 一种透明耐候pp/ps复合材料及其制备方法
CN114316424B (zh) * 2021-11-22 2023-08-25 金发科技股份有限公司 一种透明耐候pp/ps复合材料及其制备方法

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