SK19422000A3 - Process for preparing a polyvinyl alcohol gel and mechanically highly stable gel produced by this process - Google Patents
Process for preparing a polyvinyl alcohol gel and mechanically highly stable gel produced by this process Download PDFInfo
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- SK19422000A3 SK19422000A3 SK1942-2000A SK19422000A SK19422000A3 SK 19422000 A3 SK19422000 A3 SK 19422000A3 SK 19422000 A SK19422000 A SK 19422000A SK 19422000 A3 SK19422000 A3 SK 19422000A3
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- polyvinyl alcohol
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- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 68
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000243 solution Substances 0.000 claims abstract description 32
- 238000001035 drying Methods 0.000 claims abstract description 25
- 239000000654 additive Substances 0.000 claims abstract description 18
- 230000000996 additive effect Effects 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 239000012736 aqueous medium Substances 0.000 claims abstract description 5
- 230000007062 hydrolysis Effects 0.000 claims abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 4
- 102000004190 Enzymes Human genes 0.000 claims description 13
- 108090000790 Enzymes Proteins 0.000 claims description 13
- 238000001879 gelation Methods 0.000 claims description 12
- 239000000835 fiber Substances 0.000 claims description 10
- 239000011942 biocatalyst Substances 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 239000011149 active material Substances 0.000 claims description 6
- 239000012620 biological material Substances 0.000 claims description 6
- 238000005191 phase separation Methods 0.000 claims description 5
- 239000008399 tap water Substances 0.000 claims description 5
- 235000020679 tap water Nutrition 0.000 claims description 5
- 150000002170 ethers Chemical class 0.000 claims description 4
- 244000005700 microbiome Species 0.000 claims description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical group FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 3
- 235000015097 nutrients Nutrition 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical group C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 239000012876 carrier material Substances 0.000 claims description 2
- 238000005266 casting Methods 0.000 claims description 2
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 2
- 229920001521 polyalkylene glycol ether Polymers 0.000 claims description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims 1
- 229920003086 cellulose ether Polymers 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 claims 1
- 239000012266 salt solution Substances 0.000 claims 1
- 239000011780 sodium chloride Substances 0.000 claims 1
- 239000008346 aqueous phase Substances 0.000 abstract 1
- 239000012071 phase Substances 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 51
- 229920000642 polymer Polymers 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 230000008014 freezing Effects 0.000 description 9
- 238000007710 freezing Methods 0.000 description 9
- 239000002609 medium Substances 0.000 description 8
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 230000000977 initiatory effect Effects 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 239000001963 growth medium Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 241001465318 Aspergillus terreus Species 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 241000605159 Nitrobacter Species 0.000 description 2
- 241000605122 Nitrosomonas Species 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000011001 backwashing Methods 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000013587 production medium Substances 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000010257 thawing Methods 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000193171 Clostridium butyricum Species 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- HTTJABKRGRZYRN-UHFFFAOYSA-N Heparin Chemical compound OC1C(NC(=O)C)C(O)OC(COS(O)(=O)=O)C1OC1C(OS(O)(=O)=O)C(O)C(OC2C(C(OS(O)(=O)=O)C(OC3C(C(O)C(O)C(O3)C(O)=O)OS(O)(=O)=O)C(CO)O2)NS(O)(=O)=O)C(C(O)=O)O1 HTTJABKRGRZYRN-UHFFFAOYSA-N 0.000 description 1
- 241000605121 Nitrosomonas europaea Species 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 230000003698 anagen phase Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000495 cryogel Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000002538 fungal effect Effects 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 229960002897 heparin Drugs 0.000 description 1
- 229920000669 heparin Polymers 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000001546 nitrifying effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use 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 alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
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- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
- Colloid Chemistry (AREA)
- Medicinal Preparation (AREA)
- Materials For Medical Uses (AREA)
- Catalysts (AREA)
Abstract
Description
Spôsob výroby biokatalyzátora z polyvinylalkoholu a mechanicky vysokostabilný biokatalyzátor z polyvinylalkoholu vyrobený týmto spôsobomProcess for producing a polyvinyl alcohol biocatalyst and a mechanically high-stability polyvinyl alcohol biocatalyst produced by this process
Oblasť technikyTechnical field
Vynález sa týka spôsobu prípravy gélu z polyvinylalkoholu. Vynález sa ďalej týka týmto spôsobom pripraveného, mechanicky vysokostabilného gélu.The invention relates to a process for preparing a gel from polyvinyl alcohol. The invention further relates to a mechanically high-stability gel prepared in this manner.
Doterajší stav technikyBACKGROUND OF THE INVENTION
Je známe, že roztoky, ktoré obsahujú polyvinylalkohol (PVA), pri státí vykazujú zvýšenie viskozity. Tiež je známe, že PVA-roztoky sa dajú premeniť na gél, keď sa roztok zmrazí a následne sa zasa roztopí (FR 2 107 711 A). Takto pripravené gély však vykazujú pomerne malú pevnosť.It is known that solutions containing polyvinyl alcohol (PVA) exhibit an increase in viscosity on standing. It is also known that PVA solutions can be converted into a gel when the solution is frozen and then thawed again (FR 2 107 711 A). However, the gels thus prepared exhibit relatively low strength.
Z EP 0 107 055 B1 je ďalej známe, že pevnosť zmrazením pripravených PVA-gélov sa zvýši tým, že proces zmrazenia a roztopenia sa opakuje najmenej raz, výhodne dva- až päťkrát. Pritom sa použije PVA-roztok so stupňom zmydelnenia > 95 % mol., výhodne > 98 % mol. Horná hraničná teplota pre zmrazenie roztoku je -3 °C, rýchlosť chladenia môže byť medzi 0,1 °C/min. a 50 °C/min., rýchlosť roztápania medzi 1 °C/min. a 50 °C/min. Použitý PVA má stupeň polymerizácie najmenej 700. Koncentrácia PVA v roztoku by mala byť nad 6 % hmotn. a výhodne je medzi 6 a 25 % hmotn.. PVA-gél, pripravený viackrát opakovaným zmrazením a roztopením, má dobrú mechanickú pevnosť a vysoký obsah vody, ktorý sa zachová aj pri mechanickom zaťažení. Pripravený gél je vysokoelastický, netoxický a dá sa použiť na mnohé, najmä medicínske účely.It is further known from EP 0 107 055 B1 that the freezing strength of the prepared PVA gels is increased by repeating the freezing and thawing process at least once, preferably two to five times. In this case, a PVA solution having a saponification degree of> 95 mol%, preferably> 98 mol%, is used. The upper limit temperature for freezing the solution is -3 ° C, the cooling rate may be between 0.1 ° C / min. and 50 ° C / min, a melting rate between 1 ° C / min. and 50 ° C / min. The PVA used has a degree of polymerization of at least 700. The concentration of PVA in the solution should be above 6% by weight. The PVA gel, prepared several times by repeated freezing and thawing, has good mechanical strength and high water content, which is retained even under mechanical loading. The gel is highly elastic, non-toxic and can be used for many, especially medical purposes.
K tomuto gélu sa dajú primiešať rozličné látky a materiály, ktoré na jednej strane môžu zvýšiť pevnosť, napríklad glykol, glycerín, sacharóza, glukóza, agar, želatína, metylcelulóza atď. Pridaním účinných látok, ako je napríklad heparín, sa dajú uskutočniť medicínske použitia, pri ktorých sa účinná látka odovzdáva z gélu kontinuálne a rovnomerne v priebehu dlhej doby. Gél sa dá ďalej zmiešať s mikroorganizmami a enzýmami, aby sa vytvoril biologicky aktívny systém.A variety of substances and materials can be admixed to this gel which, on the one hand, may increase strength, for example glycol, glycerin, sucrose, glucose, agar, gelatin, methylcellulose, etc. By the addition of active substances, such as heparin, medical applications can be carried out in which the active substance is transferred from the gel continuously and uniformly over a long period of time. The gel can be further mixed with microorganisms and enzymes to form a biologically active system.
·· ·· · · ···· ·· • · · ·· · ··· • ·· · · · · · ·· ··· · ··· · ·· ·· ·· ·· · -2Z US-PS 4 663 358 je známe, že sa k vodnému roztoku polyvinylalkoholu pridávajú organické rozpúšťadlá, aby sa takto znížila teplota zmrazenia roztoku. Tým sa dosiahne, že sa pri teplotách želatinácie, ktoré sú pod -10 °C, výhodne pri asi -20 °C, zabráni zamrznutiu vody, čím sa dosiahne homogénnejší a tým transparentnejší gél. Nízka teplota želatinácie sa použije na vytvorenie jemnokryštalických gélov, ktoré majú dostatočnú mechanickú pevnosť.······· · · · · · · · · · · · · · · · · · · · · · · · · · · · U.S. Pat. No. 4,663,358 discloses that organic solvents are added to an aqueous solution of polyvinyl alcohol to reduce the freezing temperature of the solution. This achieves that water freezing is prevented at gelation temperatures below -10 ° C, preferably at about -20 ° C, thereby achieving a more homogeneous and thus more transparent gel. The low gelatinization temperature is used to form fine-crystalline gels having sufficient mechanical strength.
Príprava PVA-gélov technikou mrazenia je nákladná a časovo náročná.The preparation of PVA gels by the freezing technique is expensive and time consuming.
Z DE 43 27 923 C2 je známy spôsob, ktorým sa dajú pripraviť PVA-gély bez procesu mrazenia. Použitím PVA-roztoku so stupňom hydrolýzy > 99 % mol. a pridaním rozpustenej prísady, ktorá vykazuje nevodné OH-, resp. NH2-skupiny, sa dá dosiahnuť želatinácia PVA pri teplotách nad 0 °C. Proces želatinácie pritom vyžaduje doby niekoľko hodín, ktoré sa prípadne predĺžia ďalšou mnohohodinovou dobou skladovania za účelom vytvrdnutia na plnú stabilitu gélových teliesok. To je pre prípravu väčších množstiev gélových teliesok v priemyselnom meradle prirodzene nevýhodné.DE 43 27 923 C2 discloses a process by which PVA gels can be prepared without the freezing process. By using a PVA solution having a degree of hydrolysis of > 99 mol%. and adding a solubilized additive that exhibits non-aqueous OH- and OH-containing, respectively. NH 2 -group, PVA gelatinization at temperatures above 0 ° C can be achieved. The gelation process requires a period of several hours, which can optionally be extended by a further storage period of several hours in order to cure to the full stability of the gel bodies. This is naturally disadvantageous for the preparation of larger quantities of gel bodies on an industrial scale.
Úlohou predloženého vynálezu je dokázať pripraviť PVA-gélové telieska jednoducho a rýchlo a pritom ešte podľa možnosti zlepšiť kvalitu pripravených gélových teliesok.It is an object of the present invention to be able to prepare PVA gel bodies in a simple and fast manner while still improving the quality of the gel bodies prepared.
Podstata vynálezuSUMMARY OF THE INVENTION
Podstatou vynálezu je spôsob prípravy biokatalyzátora s biologickým materiálom vo forme mikroorganizmov, enzýmov, spór a/alebo buniek, včleneným do gélu z polyvinylalkoholu, ktorý zahrnuje nasledujúce kroky spôsobu:The present invention provides a process for preparing a biocatalyst with biological material in the form of microorganisms, enzymes, spores and / or cells incorporated into a polyvinyl alcohol gel, comprising the following process steps:
a) použitie vodného roztoku polyvinylalkoholu so stupňom hydrolýzy > 98 % mol.,(a) use of an aqueous solution of polyvinyl alcohol with a degree of hydrolysis> 98 mol%;
b) pridanie prísady, ktorá je po pridaní vo vodnom roztoku polyvinylalkoholu rozpustená a pri skoncentrovaní tvorí oddelenú, jemne rozdelenú a vodu obsahujúcu fázu,(b) addition of an additive which, when added in an aqueous solution of polyvinyl alcohol, is dissolved and, when concentrated, forms a separate, finely divided and water-containing phase;
c) sušenie vodného roztoku až do obsahu zvyškovej vody maximálne 50 % hmotn. na vyvolanie oddelenia fáz a s tým spojenej želatinácie polyvinylalkoholu,c) drying the aqueous solution up to a residual water content of no more than 50% by weight; to induce phase separation and the associated gelation of polyvinyl alcohol,
d) spätné napučiavanie polyvinylalkoholu vo vodnom médiu.(d) back-swelling of the polyvinyl alcohol in an aqueous medium.
*· tt • · ·· •· ·· • · ·· • · ·· • ·e ·* Tt • e · t · e · t ·
-3Spôsob podľa tohto vynálezu umožňuje prekvapujúcim spôsobom želatináciu polyvinylalkoholu v priebehu niekoľkých minút pri teplote miestnosti alebo dokonca pri vyšších teplotách. Pridaním vo vode rozpustnej prísady a skoncentrovaním odparením vody sa vyvolá oddelenie fáz na jemné častice, v dôsledku ktorého sa želatinácia vnútri PVA-fázy podarí vo veľmi krátkom čase. Predpokladom na to je, že aj vo vode rozpustná prísada vytvára fázu, ktorá obsahuje vodu, takže oddelením fáz sa PVA-fáze v priebehu veľmi krátkeho času odoberie zodpovedajúci podiel vody, čím sa spôsobí želatinácia polyvinylalkoholu. Je účelné, ak vo vode rozpustná prísada vykazuje afinitu k vode, ktorá je prinajmenšom porovnateľná s afinitou PVA k vode.Surprisingly, the process according to the invention allows the gelation of polyvinyl alcohol within a few minutes at room temperature or even at higher temperatures. Addition of the water-soluble additive and concentration by evaporation of water induces phase separation into fine particles, which results in the gelation within the PVA phase being achieved in a very short time. The assumption is that the water-soluble additive also forms a water-containing phase, so that by separating the phases, the corresponding proportion of water is withdrawn within a very short time, causing the polyvinyl alcohol to gelatinize. Suitably, the water-soluble additive exhibits an affinity for water which is at least comparable to that of PVA for water.
PVA-fáza, ktorá je pri želatinácii nedostatočne zásobená vodou, naberá pri nasledujúcom spätnom napučiavaní vodu, čim sa zlepší elasticita a mechanická stabilita PVA-gélu bez toho, aby sa želatinácia zrušila. Ukázalo sa, že pri spätnom napučiavaní vedie určitý podiel elektrolytov vo vodnom médiu k vyššej stabilite PVAgélu, takže spätné napučiavanie sa výhodne uskutoční vo vode z vodovodu alebo lepšie v soľnom roztoku.The PVA phase, which is insufficiently supplied with water during gelation, receives water the next time it is swelled, thereby improving the elasticity and mechanical stability of the PVA gel without abolishing the gelation. It has been shown that, when back-swelling, a certain proportion of electrolytes in the aqueous medium leads to a higher stability of the PVA gel, so that back-swelling preferably takes place in tap water or preferably in brine.
Spôsob podľa tohto vynálezu poskytuje výhodu, že umožňuje prípravu PVAgélu bez veľkých nákladov, najmä bez procesu mrazenia a bez opakovaných procesov sušenia, v priebehu krátkej doby, takže je možné extrémne hospodárne zhotovenie PVA-gélových teliesok. Gélové telieska podľa tohto vynálezu sa okrem toho vyznačujú vysokou elasticitou a stabilitou, najmä pevnosťou v ťahu, a z tohto hľadiska výrazne prevyšujú PVA-gélové telieska, ktoré sa dajú zhotoviť doterajšími spôsobmi.The process according to the invention provides the advantage that it enables the preparation of PVA gel without great expense, in particular without the freezing process and without repeated drying processes, within a short time, so that extremely economical production of PVA-gel bodies is possible. In addition, the gel bodies according to the invention are characterized by high elasticity and stability, in particular tensile strength, and in this respect significantly exceed the PVA gel bodies which can be produced by the prior art.
K ďalšiemu zvýšeniu stability a elasticity PVA-gélových teliesok prispieva, keď sa na ich výrobu použije dodatočne zmydelnený vodný PVA-roztok.To further increase the stability and elasticity of the PVA gel bodies, a post-saponified aqueous PVA solution is used to produce them.
Výhodnou vo vode rozpustnou prísadou je polyetylénglykol, ktorý sa pridá v koncentrácii 4 až 30 % hmotn., výhodne 4 až 20 % hmotn., najmä 6 až 16 % hmotn.. Inými príkladmi možných prísad sú estery celulózy, étery celulózy, estery škrobu, étery škrobu, polyalkylénglykolétery, polyalkylénglykoly, alkanoly s dlhými reťazcami (CnH2n+iOH s n > 8), estery cukrov, étery cukrov.A preferred water-soluble additive is polyethylene glycol, which is added at a concentration of 4 to 30% by weight, preferably 4 to 20% by weight, in particular 6 to 16% by weight. starch ethers, polyalkylene glycol ethers, polyalkylene glycols, long-chain alkanols ( Cn H2n + iOH sn> 8), sugar esters, sugar ethers.
Zvlášť výhodná oblasť použitia PVA-gélových teliesok spočíva v ich vytváraní ako biologicky, fyzikálne alebo chemicky aktívnych teliesok, teda vo včlenení ·· ····A particularly preferred field of application of PVA-gel bodies is to form them as biologically, physically or chemically active bodies, i.e.
-4biologicky, fyzikálne alebo chemicky aktívneho materiálu do PVA-gélu. PVA-gél je takto vynikajúcim spôsobom vhodný napríklad na výrobu chemického alebo biologického katalyzátora.- Biologically, physically or chemically active material into a PVA gel. Thus, the PVA gel is excellent in the production of a chemical or biological catalyst, for example.
Sušenie vodného roztoku za účelom oddelenia fáz a s tým spojenej želatinácie sa uskutočňuje po obsah zvyškovej vody maximálne 50 % hmotn.. Spodná hranica obsahu zvyškovej vody asi 10 % hmotn. je určená tým, že pripravený PVA-gél by mal byť ešte úplne spätne napúčavý, že pod obsahom zvyškovej vody asi 10 % hmotn. dochádza k zníženej elasticite gélových teliesok a že pod uvedeným obsahom zvyškovej vody sa prípadne včlenené biologické materiály môžu poškodiť. Výhodná oblasť pre obsah zvyškovej vody je medzi 10 a 30 % hmotn..The drying of the aqueous solution to separate the phases and the associated gelation is carried out to a residual water content of not more than 50% by weight. It is determined that the prepared PVA gel should still be completely swellable so that below a residual water content of about 10 wt. there is a decrease in the elasticity of the gel bodies and that below the residual water content, possibly incorporated biological materials can be damaged. The preferred range for residual water content is between 10 and 30 wt%.
Sušenie sa dá pohodlne uskutočniť v krátkej dobe odparením vody na vzduchu pri teplote okolia, ak sa vodný roztok rozdelí na malé časti, najmä také časti, v ktorých roztok vykazuje len malú hrúbku. Tak je najmä výhodne možné nakvapkať roztok na tvrdý podklad tak, aby priemer kvapiek bol najmenej dvakrát tak veľký ako výška kvapiek. Niečo podobné sa dá dosiahnuť naliatím roztoku do lejacej formy a/alebo ako povlaku na nosný materiál. Vytvorením tenkej vrstvy alebo dokonca filmu sa odparenie na požadovaný obsah zvyškovej vody dosiahne v priebehu niekoľkých minút, napríklad v priebehu 15 minút. Zrýchlenie procesu sušenia - a tým procesu želatinácie - sa dá dosiahnuť uskutočnením sušenia v sušiacej peci pri zvýšenej teplote.Drying can conveniently be carried out in a short time by evaporating water in air at ambient temperature if the aqueous solution is divided into small portions, especially those in which the solution has only a small thickness. Thus, it is particularly advantageous to drop the solution onto a hard substrate such that the drop diameter is at least twice as large as the drop height. Something similar can be achieved by pouring the solution into the casting mold and / or as a coating on the carrier material. By forming a thin layer or even a film, evaporation to the desired residual water content is achieved within minutes, for example within 15 minutes. Acceleration of the drying process - and thus the gelation process - can be achieved by performing drying in an oven at an elevated temperature.
Soľný roztok, použitý výhodne na spätné napučiavanie, výhodne obsahuje viacmocné anióny.The saline solution, preferably used for back-swelling, preferably contains polyvalent anions.
Najmä na imobilizáciu biologicky aktívneho materiálu je pri spôsobe podlá tohto vynálezu výhodné, že sa dá uskutočniť pre biologický materiál neobyčajne šetrne, takže biologický materiál vykazuje v porovnaní s inými spôsobmi imobilizácie výrazne vyššiu začiatočnú aktivitu.In particular for the immobilization of a biologically active material, it is advantageous in the method according to the invention that it can be carried out in an extremely gentle manner for the biological material, so that the biological material exhibits a significantly higher initial activity compared to other methods of immobilization.
To sa dá podporiť ešte tým, že vodné médium, v ktorom sa uskutočňuje spätné napučiavanie PVA-gélu, je súčasne živným roztokom pre biologicky aktívny materiál.This can be further supported by the fact that the aqueous medium in which the PVA gel is back-swelled is simultaneously a nutrient solution for the biologically active material.
·· ······ ····
-5Hustota PVA-gélu, pripraveného podľa tohto vynálezu, sa dá modifikovať vhodnými prísadami. Tak sa dá špecifická hmotnosť napríklad zvýšiť pridaním oxidu titaničitého a znížiť pridaním čo najmenších dutých sklených guľôčok.The density of the PVA gel prepared according to the invention can be modified with suitable additives. Thus, for example, the specific gravity can be increased by the addition of titanium dioxide and reduced by the addition of the smallest possible hollow glass beads.
Želatinácia podľa tohto vynálezu je - ako sme uviedli - možná pri teplote miestnosti, môže sa však uskutočniť pri nižších alebo vyšších teplotách. Biologickým materiálom, ktorý je uzavretý v PVA-géle, môžu byť enzýmy, mikroorganizmy, spóry a bunky.The gelation according to the invention is, as mentioned above, possible at room temperature, but can be carried out at lower or higher temperatures. The biological material encapsulated in the PVA gel may be enzymes, microorganisms, spores, and cells.
Spôsob podľa tohto vynálezu sa dá realizovať v mnohých formách uskutočnenia. Tak je napríklad možné nechať prebehnúť sušenie kvapky na vytvorenie fáz v chladiacej veži počas procesu pádu, takže želatinácia po oddelení fáz sa uskutoční už pred dopadom kvapky na podklad. Tento spôsob prípravy je vhodný najmä na výrobu PVA-gélových teliesok ako materiálu pre chromatografiu, ktorý môže mať priemer na laboratórne účely 10 až 100 pm a ináč 100 až 800 pm. Ďalej je možné sušiť východiskovú kvapalinu, nastavenú na vyššiu viskozitu, pri pretláčaní vllákna a pritom uskutočniť želatináciu PVA.The method of the invention can be practiced in many embodiments. For example, it is possible to dry the droplet to form the phases in the cooling tower during the fall process, so that the gelation after the phase separation occurs before the droplet falls on the substrate. This preparation method is particularly suitable for the production of PVA-gel bodies as a material for chromatography, which may have a diameter for laboratory purposes of 10 to 100 µm and otherwise 100 to 800 µm. Furthermore, it is possible to dry the starting liquid, which is set to a higher viscosity, during the extrusion of the filament, and at the same time to gelatinize the PVA.
Gélové teliesko, vyrobené spôsobom podľa tohto vynálezu, vykazuje oproti predtým známym gélovým telieskam lepšiu mechanickú stabilitu, najmä čo sa týka oderuvzdornosti a pevnosti v ťahu.The gel body produced by the method according to the invention exhibits improved mechanical stability over the previously known gel bodies, in particular with regard to abrasion resistance and tensile strength.
Tieto lepšie mechanické vlastnosti umožňujú najmä vyrábať gélové telieska podľa tohto vynálezu v reakčno-kineticky výhodnom tvare šošoviek, v ktorom doteraz známe gélové telieska nevykazovali dostatočnú mechanickú stabilitu, najmä stabilitu pri miešaní. Gélové teliesko podľa tohto vynálezu je naproti tomu mnoho mesiacov stabilné a oderuvzdorné aj pri vysokootáčkových procesoch miešania. Tvar šošovky s veľkým priemerom a malou výškou spôsobuje, že chemicky, fyzikálne alebo biologicky aktívny materiál je vždy usporiadaný v blízkosti povrchu, z čoho vyplýva reakčno-kineticky výhodná situácia.In particular, these improved mechanical properties make it possible to produce the gel bodies according to the invention in a reaction-kinetically advantageous lens shape, in which the gel bodies known hitherto did not show sufficient mechanical stability, in particular stirring stability. The gel body according to the invention, on the other hand, is stable and abrasion-resistant for many months even in high speed mixing processes. The shape of the lens with a large diameter and low height causes the chemically, physically or biologically active material to always be arranged near the surface, resulting in a reaction-kinetically advantageous situation.
Predložený vynález umožňuje jednoduchým spôsobom pridať do telieska z polyvinylalkoholu magnetickú prísadu, aby sa gélové telieska prípadne dali magnetmi bez ťažkostí pozberať z kvapaliny.The present invention makes it possible in a simple manner to add a magnetic additive to the polyvinyl alcohol body, so that the gel bodies can optionally be removed from the liquid by the magnets without difficulty.
Ukázalo sa, že pórovitá štruktúra polyvinylalkoholových gélových teliesok podľa tohto vynálezu sa dá riadiť molekulovou hmotnosťou pridanej, oddelenie fáz spôsobujúcej prísady. Riadením molekulovej hmotnosti pridaného polyetylénglykolu, ·· ····It has been shown that the porous structure of the polyvinyl alcohol gel bodies of the present invention can be controlled by the molecular weight of the additive phase separation additive. By controlling the molecular weight of the added polyethylene glycol, ·· ····
-6ktorého molekulová hmotnosť je výhodne medzi 800 a 1350, sa dajú nastaviť veľkosti pórov polyvinylalkoholového gólového telieska medzi 1 a 15 pm.Whether the molecular weight is preferably between 800 and 1350, the pore sizes of the polyvinyl alcohol goal body can be adjusted between 1 and 15 µm.
Pre prípravu vodného roztoku polyvinylalkoholu a prísady podľa tohto vynálezu sa ukázalo, že pri použití destilovanej vody je potrebný vyšší stupeň vysušenia, aby sa dosiahli rovnaké mechanické výsledky. Tieto výsledky sa okamžite zlepšia, keď sa použije bežná voda z vodovodu s určitým stupňom tvrdosti. V dôsledku toho treba predpokladať, že určitý obsah solí vo vode je pre spôsob podľa tohto vynálezu výhodný.For the preparation of an aqueous solution of polyvinyl alcohol and an additive according to the invention, it has been shown that a higher degree of drying is required when using distilled water in order to obtain the same mechanical results. These results are immediately improved when using ordinary tap water of some degree of hardness. As a result, it has to be assumed that a certain salt content in water is advantageous for the process according to the invention.
Vynález v ďalšom bližšie objasníme pomocou príkladov uskutočnenia.The invention is explained in more detail below by means of examples.
Príklady uskutočnenia vynálezuDETAILED DESCRIPTION OF THE INVENTION
Príklad 1Example 1
K 2 g PVA a 1,2 g polyetylénglykolu (PEG 1000) sa pridá 16,8 g vody. Roztok sa zahrieva na 90 °C tak dlho, kým sa všetky komponenty úplne nerozpustia, takže sa získa viskózny, bezfarebný roztok. Po ochladení na 30 °C sa polymérny roztok injekčnou striekačkou s použitím tlaku rozkvapká na polypropylénovú dosku. Rozkvapkanie sa pritom uskutoční naklepávaním kanyly na PP-dosku rýchlosťou asi 1 až 2 /s; veľkosť kvapiek je v priemere asi 3 mm a na výšku asi 1 mm. Po nakvapkaní sa na povrchu kvapiek vytvorí biely voskovítý film. Po tom, čo sa pri teplote miestnosti odparí 89 % hmotn. vody, sa gélové telieska nechajú spätne napučiavať vo vode alebo v soľnom médiu. Získané gélové telieska majú priemer 3 až 4 mm a výšku asi 200 až 400 pm.To 2 g of PVA and 1.2 g of polyethylene glycol (PEG 1000) were added 16.8 g of water. The solution is heated to 90 ° C until all components have completely dissolved to give a viscous, colorless solution. After cooling to 30 ° C, the polymer solution was dropped onto a polypropylene plate using a syringe using pressure. Dripping is performed by tapping the cannula onto the PP plate at a rate of about 1/2 / s; the droplet size is about 3 mm in diameter and about 1 mm in height. Upon dropping, a white waxy film is formed on the surface of the droplets. After evaporation at room temperature, 89 wt. water, the gel bodies are allowed to swell back in water or in brine. The gel bodies obtained have a diameter of 3 to 4 mm and a height of about 200 to 400 µm.
Príklad 2Example 2
Po ochladení polymérnej suspenzie (zloženie: 2 g PVA, 1,2 g PEG 1000 aAfter cooling the polymer slurry (composition: 2 g PVA, 1.2 g PEG 1000 a
15,8 g vody) sa 1 ml nitrifikujúcej zmiešanej kultúry (Nitrosomonas europaea a Nitrobacter winogradsky) pridá do 20 g polymérneho roztoku a disperguje, takže sa dosiahne obsah suchej biomasy (BTM) 0,06 % hmotn.. Výroba gélových teliesok sa uskutoční podľa príkladu 1. Získané gélové telieska sa nechajú spätne napučiavať v štandardnom médiu s minerálnymi solämi (STMN) pre nitrifikátory. Takto pripravené imobilizáty vykazujú priamo po imobilizácii začiatočnú aktivitu asi 70 % pre ·· ····15.8 g of water), 1 ml of nitrifying mixed culture (Nitrosomonas europaea and Nitrobacter winogradsky) is added to 20 g of polymer solution and dispersed to obtain a dry biomass (BTM) content of 0.06% by weight. EXAMPLE 1. The gel bodies obtained were re-swelled in standard mineral salt medium (STMN) for nitrifiers. The immobilizates thus prepared show an initial activity of about 70% directly after immobilization for
Nitrosomonas spp. a 100 % pre Nitrobacter spp. v porovnaní s rovnakým množstvom voľných nitrifikátorov.Nitrosomonas spp. and 100% for Nitrobacter spp. compared to the same amount of free nitrifiers.
Pri včlenení nitrifikátorov do PVA-kryogélov je pri -20 °C začiatočná aktivita pre Nitrosomonas spp. asi 1 %, pri -10 °C asi 25 % pri znižujúcej sa mechanickej stabilite PVA-hydrogélov.When incorporating nitrifiers into PVA cryogels, at -20 ° C the initial activity for Nitrosomonas spp. about 1%, at -10 ° C about 25% with decreasing mechanical stability of the PVA-hydrogels.
Inkubácia imobilizátov sa uskutoční v rovnakom médiu pri 30 °C. Ak sa inkubuje 10 mg gélových teliesok v 30 ml STMN, tak sa po 19 dňoch dosiahne maximálna rýchlosť odbúravania amónia medzi 7 a 8 pmol NH4 +/(gkaťmin).Incubation of the immobilisates is performed in the same medium at 30 ° C. When 10 mg of gel bodies are incubated in 30 ml STMN, after 19 days the maximum rate of ammonium degradation is reached between 7 and 8 pmol NH 4 + / (gkaťmin).
Príklad 3Example 3
V 12,8 g H2O sa rozpustí 1,6 g polyetylénglykolu (PEG 1000), následne sa pridá 1,6 g PVA a ďalej sa postupuje ako v príklade 1. Po ochladení polymérneho roztoku na 30 °C sa 4 ml kultúry striktne anaeróbnej baktérie Clostridium butyricum NRRL B-1024, ktorá konvertuje glycerín na 1,3-propándiol (PD), pričom táto kultúra rástla cez noc v bezkyslíkovej atmosfére, dispergujú v tomto roztoku (množstvo buniek v polymérnom roztoku: 6 x 107 na ml). Výroba gélových teliesok sa uskutoční podľa príkladu 1. Po tom, čo sa pri teplote miestnosti odparí 70 % hmotn. vody, sa imobilizáty nechajú spätne napučiavať v médiu s minerálnymi soľami (20-násobný nadbytok). Inkubácia gélových teliesok, obsahujúcich bunky, sa uskutoční v rovnakom médiu (40-násobný nadbytok) pri 30 °C. Na dostatočné zásobovanie imobilizovanej biomasy živinami sa médium v začiatočnej fáze rastu viackrát vymení.The 12.8 g of H 2 O are dissolved 1.6 g of polyethylene glycol (PEG 1000), followed by 1.6 g PVA and the further procedure is as in Example 1. After cooling the polymer solution at 30 DEG C., 4 ml of culture strictly anaerobic bacterium Clostridium butyricum NRRL B-1024, which converts glycerin to 1,3-propanediol (PD), which is grown overnight in an oxygen-free atmosphere, dispersed in this solution (number of cells in polymer solution: 6 x 10 7 per ml) . The gel bodies are prepared according to Example 1. After evaporation at room temperature of 70 wt. of water, immobilizates are allowed to swell back in mineral salt medium (20-fold excess). Incubation of the gel bodies containing the cells is performed in the same medium (40-fold excess) at 30 ° C. In order to provide sufficient nutrient supply to the immobilized biomass, the medium is changed several times in the initial growth phase.
Ak sa 0,25 g takto získaného imobilizovaného biokatalyzátora vloží do 40 ml média s minerálnymi soľami s 24,4 g g/l glycerínu, koncentrácia 1,3-PD sa v priebehu 3,25 h zvýši o 2,8 g/l. To zodpovedá aktivite katalyzátora 0,14 g 1,3-PD na g kat. a hodinu. Po odpočítaní aktivity vyrastených buniek sa získa aktivita katalyzátora 0,08 g 1,3-PD (gkaťh).When 0.25 g of the immobilized biocatalyst thus obtained is introduced into 40 ml of mineral salt medium with 24.4 g / l glycerin, the concentration of 1,3-PD is increased by 2.8 g / l over 3.25 h. This corresponds to a catalyst activity of 0.14 g 1,3-PD per g cat. and an hour. After counting the activity of the grown cells, a catalyst activity of 0.08 g of 1,3-PD (gcat) is obtained.
Príklad 4Example 4
K 2 g PVAL a 1,2 g polyetylénglykolu (PEG 1000) sa pridá 15,8 g vody a ďalej sa postupuje ako v príklade 1.To 2 g of PVAL and 1.2 g of polyethylene glycol (PEG 1000) were added 15.8 g of water and the procedure was as in Example 1.
-8·· ·· ·· ···· ·· ···· ·· · ··· • · ·· · · · · · • ·· ··· · ··· · ♦ · · · · · · · · · ·· ·· ·· ·· ·· ·-8 ········································· · · · · · · · · · · · · · · ·
Po ochladení polymérnej suspenzie na asi 30 až 37 °C sa 1 ml definovanej suspenzie spór huby Aspergillus terreus pridá k 20 g polymérneho roztoku a disperguje sa. Suspenzia spór sa zvolí tak, aby po 5 dňoch rastu vzniklo v rastovom médiu množstvo suchej biomasy 0,005 % hmotn..After cooling the polymer suspension to about 30-37 ° C, 1 ml of a defined spore suspension of Aspergillus terreus is added to 20 g of polymer solution and dispersed. The spore suspension is selected such that after 5 days of growth an amount of dry biomass of 0.005% by weight is produced in the growth medium.
Po tom, čo sa pri teplote miestnosti odparilo 70 % hmotn. vody, sa imobilizáty nechajú spätne napučiavať v médiu s minerálnymi soľami pre Aspergillus terreus (20-násobný nadbytok).After evaporation at room temperature 70 wt. of water, the immobilisates are back-swelled in a mineral salt medium for Aspergillus terreus (20-fold excess).
Inkubácia imobilizátov sa uskutoční v rastovom médiu. Na produkciu kyseliny itakónovej sa rastové médium nahradí produkčným médiom.The immobilisates are incubated in growth medium. For the production of itaconic acid, the growth medium is replaced with the production medium.
Pripravené imobilizáty vykazujú priamo po imobilizácii začiatočnú aktivitu asi % v porovnaní s rovnakým množstvom voľných buniek húb. Ak sa 0,2 g gólových teliesok inkubuje v 100 ml produkčného média so 60 g/l glukózy, po 7 dňoch sa dosiahnu produktivity 35 mg kyseliny itakónovej/(gka*h).Prepared immobilisates show an initial activity of about% compared to the same amount of free fungal cells directly after immobilization. When 0.2 g goal bodies are incubated in 100 ml production medium with 60 g / l glucose, after 7 days productivity of 35 mg itaconic acid / (gka * h) is achieved.
Príklad 5Example 5
Väčšie množstvá gólových teliesok sa získajú rozkvapkaním polymérneho roztoku (zloženie podľa príkladu 1) multidýzovým systémom na dopravný pás.Larger amounts of goal bodies are obtained by dripping a polymer solution (composition according to Example 1) with a multi-nozzle system onto a conveyor belt.
Podľa princípu pásovej sušičky sa kvapky PVA vysušia v sušiacom tuneli až na definovaný obsah zvyškovej vlhkosti a následne sa stieračom pozberajú do záchytnej nádoby a tam sa nechajú spätne napučať a premyjú sa.According to the belt dryer principle, the PVA droplets are dried in a drying tunnel to a defined residual moisture content and are subsequently collected by a scraper in a collection container, where they are swollen back and washed.
Príklad 6Example 6
Pri výrobe podľa príkladu 1 sa polymérny roztok nerozkvapká, ale naleje sa do vopred pripravených polootvorených foriem s vnútorným priemerom 1 až 10 mm a ľubovoľnou dĺžkou.In the preparation of Example 1, the polymer solution does not drip, but is poured into preformed semi-open molds having an internal diameter of 1 to 10 mm and any length.
Po spätnom napučaní vo vode sa vlákna dajú natiahnuť na 3- až 4-násobok svojej dĺžky bez toho, aby sa pretrhli. Dĺžkové natiahnutie je nevratné. Takto zhotovené vlákno sa dá zaťažiť závažím 500 g bez toho, aby sa pretrhlo.After back-swelling in water, the fibers can be stretched to 3 to 4 times their length without breaking. Lengthwise stretching is irreversible. The fiber produced in this way can be loaded with a weight of 500 g without breaking.
Príklad 7Example 7
Vlákna, pripravené podľa príkladu 6, sa po dobe skladovania 14 dní vo vode z vodovodu mechanicky charakterizujú. V tomto okamihu vlákna vykazujú šírku asiThe fibers prepared according to Example 6 are mechanically characterized after storage for 14 days in tap water. At this point, the fibers have a width of about
mm a výšku asi 1 mm. Stupeň spätného napučania zohľadňuje pokles hmotnosti po spätnom napučaní a 14-dennom skladovaní vo vode, vztiahnuté na celkovú hmotnosť použitého polymémeho roztoku pred procesom sušenia. Vlákna vykazujú až do pretiahnutia pri pretrhnutí 40% elasticitu.mm and a height of about 1 mm. The degree of back-swelling takes into account the weight loss after back-swelling and 14-day storage in water, based on the total weight of the polymer solution used before the drying process. The fibers exhibit 40% elasticity until elongation at break.
Mechanická charakterizácia vyrobených vláken pri rozličných stupňoch vysušenia pre zloženie 10 % hmotn. PVA a 6 % hmotn. PEG 1000:Mechanical characterization of the fibers produced at different drying stages for a composition of 10 wt. % PVA and 6 wt. PEG 1000:
Mechanická charakterizácia vláken pri stupni vysušenia 80 % hmotn. pre zloženie % hmotn. PVA a 8 % hmotn. PEG pre rozličné druhy PEG:Mechanical characterization of the fibers at a drying degree of 80 wt. % for the composition wt. % PVA and 8 wt. PEG for different types of PEG:
Mechanické vlastnosti PVA-hydrogélových vláken pre rozličné koncentrácie PVA s pridaním 6 % hmotn. PEG 1000 pri stupni vysušenia (množstvo vody, odparenej počas procesu sušenia) 80 % hmotn.:Mechanical properties of PVA-hydrogel fibers for different concentrations of PVA with addition of 6 wt. PEG 1000 at the degree of drying (amount of water evaporated during the drying process) 80% by weight:
Mechanické vlastnosti vláken pri stupni vysušenia 80 % hmotn. pre zloženie 10 % hmotn. a 6 % hmotn. PEG 1000 pre rozličné médiá spätného napučiavania:The mechanical properties of the fibers at a drying degree of 80 wt. % for a composition of 10 wt. and 6 wt. PEG 1000 for various back-swelling media:
Príklad 8Example 8
Gélové telieska sa pripravia podľa príkladu 1 a nechajú sa spätne napučiavať v deionizovanej vode (5 pS H2O). Stupeň spätného napučania gélových teliesok sa určí priamo po procese spätného napučiavania pre rozličné stupne vysušenia. PriThe gel bodies were prepared according to Example 1 and allowed to swell back in deionized water (5 pS H 2 O). The degree of backwashing of the gel bodies is determined directly after the backwashing process for the various drying stages. At
stupni spätného napučania 100 % hmotn. je hmotnosť gélových teliesok pred procesom sušenia a po spätnom napučiavaní rovnaká, ako sa dá vidieť na priloženom obrázku na výkrese.100% wt. the mass of the gel bodies before and after the back-swelling process is the same as can be seen in the attached drawing in the drawing.
Claims (25)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE19827552A DE19827552C1 (en) | 1998-06-20 | 1998-06-20 | Process for producing a gel from polyvinyl alcohol and mechanically highly stable gel produced by the process |
PCT/DE1999/000975 WO1999067320A1 (en) | 1998-06-20 | 1999-03-30 | Process for preparing a polyvinyl alcohol gel and mechanically highly stable gel produced by this process |
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SK19422000A3 true SK19422000A3 (en) | 2001-07-10 |
SK284467B6 SK284467B6 (en) | 2005-04-01 |
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SK1942-2000A SK284467B6 (en) | 1998-06-20 | 1999-03-30 | Process for preparing a biocatalyst with a polyvinyl alcohol and a highly mechanically stable biocatalyst with a polyvinyl alcohol produced by this process |
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EP (1) | EP1091996B1 (en) |
JP (1) | JP2002518570A (en) |
KR (1) | KR20010053046A (en) |
AT (1) | ATE285433T1 (en) |
AU (1) | AU746982B2 (en) |
BG (1) | BG64957B1 (en) |
BR (1) | BR9911393A (en) |
CA (1) | CA2334661A1 (en) |
CZ (1) | CZ294179B6 (en) |
DE (2) | DE19827552C1 (en) |
DK (1) | DK1091996T3 (en) |
ES (1) | ES2230856T3 (en) |
HK (1) | HK1032410A1 (en) |
HU (1) | HU227366B1 (en) |
IL (1) | IL140337A (en) |
MX (1) | MX229185B (en) |
PL (1) | PL194759B1 (en) |
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EP1713851A2 (en) * | 2004-02-04 | 2006-10-25 | Cambridge Polymer Group, Inc. | Systems and methods for controlling and forming polymer gels |
KR101411073B1 (en) * | 2006-03-13 | 2014-06-27 | 렌티카츠, 아.에스. | A method for industrial production of biocatalysts in the form of enzymes or microorganisms immobilized in polyvinyl alcohol gel their use and devices for their production |
US7731988B2 (en) * | 2007-08-03 | 2010-06-08 | Zimmer, Inc. | Multi-polymer hydrogels |
KR20140074967A (en) * | 2011-10-07 | 2014-06-18 | 이가 바이오 리사치 가부시키가이샤 | Method and apparatus for decomposing biological substance |
JP6380003B2 (en) * | 2014-10-29 | 2018-08-29 | Jnc株式会社 | Microorganism culture equipment and microorganism detection method |
EP3173146A1 (en) | 2015-11-27 | 2017-05-31 | InstrAction GmbH | Porous polymeric material for binding metal-containing ions or for the purification of organic molecules |
CN105315589A (en) * | 2015-12-01 | 2016-02-10 | 惠安华晨贸易有限公司 | Production process of plastics for producing garbage bags |
EP3535377B1 (en) | 2016-11-01 | 2022-02-09 | Novozymes A/S | Multi-core granules |
DE102019105019B4 (en) | 2019-02-27 | 2022-08-25 | Ostthüringische Materialprüfgesellschaft Für Textil Und Kunststoffe Mbh | Use of a liquid formulation to form elastic, stable, biodegradable polymer films |
NL2024726B1 (en) | 2020-01-22 | 2021-09-09 | Biomosae B V | Enzymatic crop protection and process for preparing biological crop protection composition |
US20230034857A1 (en) * | 2020-09-15 | 2023-02-02 | Lg Chem, Ltd. | Microcarrier for cell culture and method for preparing the same |
CN113214584B (en) * | 2021-05-07 | 2023-03-28 | 珠海鹏鲲生物医药科技有限公司 | Composite hydrogel and preparation method thereof |
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JP3055963B2 (en) * | 1991-04-18 | 2000-06-26 | 株式会社クラレ | Polymer gel for biocatalyst-immobilized moldings |
JP3165734B2 (en) * | 1992-05-19 | 2001-05-14 | テルモ株式会社 | New high water absorption shape memory material |
DE4327923C2 (en) * | 1993-08-19 | 1997-01-09 | Arbo Medizin Technologie Gmbh | Polyvinyl alcohol gel and process for its preparation |
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- 1999-03-30 SK SK1942-2000A patent/SK284467B6/en not_active IP Right Cessation
- 1999-03-30 KR KR1020007014493A patent/KR20010053046A/en not_active Application Discontinuation
- 1999-03-30 CA CA002334661A patent/CA2334661A1/en not_active Abandoned
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DE59911335D1 (en) | 2005-01-27 |
BG64957B1 (en) | 2006-10-31 |
SK284467B6 (en) | 2005-04-01 |
PL344595A1 (en) | 2001-11-05 |
WO1999067320A1 (en) | 1999-12-29 |
HK1032410A1 (en) | 2001-07-20 |
BG105133A (en) | 2001-09-28 |
CA2334661A1 (en) | 1999-12-29 |
MX229185B (en) | 2005-07-15 |
HU227366B1 (en) | 2011-04-28 |
ATE285433T1 (en) | 2005-01-15 |
IL140337A0 (en) | 2002-02-10 |
HUP0102098A2 (en) | 2001-10-28 |
CZ294179B6 (en) | 2004-10-13 |
KR20010053046A (en) | 2001-06-25 |
AU3926199A (en) | 2000-01-10 |
DE19827552C1 (en) | 2000-03-02 |
EP1091996A1 (en) | 2001-04-18 |
EP1091996B1 (en) | 2004-12-22 |
BR9911393A (en) | 2001-03-20 |
IL140337A (en) | 2005-08-31 |
CZ20004603A3 (en) | 2001-10-17 |
AU746982B2 (en) | 2002-05-09 |
PL194759B1 (en) | 2007-07-31 |
JP2002518570A (en) | 2002-06-25 |
ES2230856T3 (en) | 2005-05-01 |
HUP0102098A3 (en) | 2002-06-28 |
DK1091996T3 (en) | 2005-01-24 |
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