WO2021148064A1 - Mousse de polyuréthane biodégradable, matériau à base de mousse de polyuréthane biodégradable pour la production d'enzyme de clivage de saccharide, procédé de synthèse et utilisation de celui-ci - Google Patents

Mousse de polyuréthane biodégradable, matériau à base de mousse de polyuréthane biodégradable pour la production d'enzyme de clivage de saccharide, procédé de synthèse et utilisation de celui-ci Download PDF

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Publication number
WO2021148064A1
WO2021148064A1 PCT/CZ2021/050007 CZ2021050007W WO2021148064A1 WO 2021148064 A1 WO2021148064 A1 WO 2021148064A1 CZ 2021050007 W CZ2021050007 W CZ 2021050007W WO 2021148064 A1 WO2021148064 A1 WO 2021148064A1
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WIPO (PCT)
Prior art keywords
saccharide
polyurethane foam
biodegradable polyurethane
poly
cleaving enzyme
Prior art date
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PCT/CZ2021/050007
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English (en)
Inventor
Hynek Benes
Sonia BUJOK
Aleksandra PARUZEL
Veronika ZAJICOVA
Tereza HNATKOVA
Guuske Frederike Busscher
Alex Alois Joseph SCHMEETS
Original Assignee
Ustav Makromolekularni Chemie Av Cr, V.V.I.
Biomosae
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Application filed by Ustav Makromolekularni Chemie Av Cr, V.V.I., Biomosae filed Critical Ustav Makromolekularni Chemie Av Cr, V.V.I.
Priority to EP21701881.1A priority Critical patent/EP4093797A1/fr
Publication of WO2021148064A1 publication Critical patent/WO2021148064A1/fr

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    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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    • C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
    • C08G18/163—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
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    • C08G18/6633—Compounds of group C08G18/42
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Definitions

  • Biodegradable polyurethane foam biodegradable polyurethane foam-based material for saccharide-cleaving enzyme production, method of synthesis and use thereof
  • the present invention relates to a biodegradable polyurethane foam, which is suitable as a porous carrier for the immobilization of production strains of microorganisms, method of synthesis and use thereof, particularly in production biotechnologies to increase the yield of industrial extracellular enzymes.
  • Open-porous materials are nowadays highly desirable in many biotechnological processes as substrates and carriers of microbial biomass.
  • natural media e.g. soil, bark, peat and compost
  • the necessary nutrients for biomass growth are usually provided by the material itself, which is, however, very inhomogeneous and often difficult to adjust for specific biotechnology operations.
  • synthetic materials such as vermiculite, perlite, polyethylene or expanded polyurethane are biologically inactive, i.e. they provide only a surface for the immobilization of biomass and biofilm formation, the growth of microorganisms being ensured by the added nutrient solution.
  • the ideal biomass carrier should have a high specific surface area, a high open pore content facilitates flow, maintain its structural integrity during long-term operation, and should also allow effective immobilization of microorganisms and nutrient supply.
  • polyurethane foams Due to their variable chemical composition, low density, adjustable rigidity and desired cell morphology (interconnected open pores vs. closed isolated cells), polyurethane foams can be considered as the most promising cellular plastics for the production of porous biomass carriers.
  • the nature and variability of the chemical composition of the polyurethane foam makes it possible to incorporate certain substances into the structure of the material, which can then act as inhibitors or inducers of the activity of the biofilm formed on the polyurethane carrier.
  • the synthesis of polyurethane foams is based on two basic reactions.
  • the first reaction is a polyaddition between an alcohol bearing two or more hydroxyl (OH) groups (polyol) and an isocyanate carrying two or more isocyanate (NCO) groups (polyisocyanate), resulting in the production of polyurethanes and the formation of a chemically crosslinked structure. Therefore, this reaction is often called a "gelling reaction”.
  • the second reaction (“blowing reaction”) takes place between the polyisocyanate and water to form carbon dioxide and a primary amine. The amine formed reacts very quickly with other isocyanate (NCO) groups to form disubstituted urea. The carbon dioxide produced is therefore responsible for foaming.
  • aromatic polyisocyanates are practically exclusively used for the production of polyurethane foams because they are much more reactive to OH groups than aliphatic.
  • Fast and well-controlled foaming is the main advantage and reason why polyurethane foams are so popular compared to other polymer foams that require intense mechanical agitation, gas supply, or excessive heating.
  • conventional polyurethane foams have several disadvantages, e.g. difficult recyclability (due to chemically crosslinked structure), possible presence of residual toxic aromatic isocyanates or production of toxic compounds during foam degradation (typically formation of aromatic diamines during foam photo-oxidation) hazardous to the environment.
  • these foams are not biologically active (they do not serve as a source of nutrients for microorganisms or do not biodegrade).
  • the present invention eliminates the above-mentioned disadvantages of biotechnological enzyme production by using porous polyurethane as a biomass carrier with built-in carbohydrate units that serve as an inducer of enzymatic activity, allowing efficient immobilization of bacteria and increased enzymatic production at reduced operating costs of the fermentation process.
  • the invention is based on the experimental finding that, using specific foaming conditions, a polyurethane foam with open porous structure can be prepared.
  • the polyurethane foam is composed of aliphatic polyol and aliphatic polyisocyanate segments and a natural carbohydrate unit and exhibits biodegradability.
  • the porous material thereby prepared is very suitable for immobilizing a production microbial strain, e.g. of the genus Pseudomonas, and, moreover, serves as an effective source of carbon and nitrogen for the bacteria.
  • the porous material prepared can serve as a carrier for microbial biomass in production biotechnological cultures.
  • production of a particular type of enzyme is induced by appropriate selection of a carbohydrate unit, which thus serves as an inducer of enzymatic activity.
  • the prepared porous support with a bound/incorporated enzyme inducer thus provides the biotechnology process with the following advantages: (i) higher process productivity in a smaller bioreactor volume range - due to higher microbial population density, (ii) higher fermentation process stability through better protection of immobilized bacterial population (iii) repeated use of immobilized biomass.
  • the open porous structure ensures optimum carrier diffusion, high content and stability of the immobilized biomass, which makes it possible to significantly increase the yields of biotechnological processes over existing solutions.
  • the present invention thus provides a porous (biodegradable) carrier based on expanded polyurethanes containing an incorporated inducer of enzymatic activity, which serves to immobilize production strains of microorganisms in industrial biotechnologies.
  • the object of the present invention is a method of synthesis of a biodegradable polyurethane foam, comprising the following steps: i) mixing of at least one aliphatic isocyanate bearing at least two isocyanate (-NCO) groups with at least one saccharide in weight ratio of from 1:1 to 30:1 to form a saccharide-isocyanate precursor; ii) homogenization of the saccharide-isocyanate precursor from step i) with 20 to 70 % (w/w) of at least one biodegradable aliphatic polyester-ether polyol having molecular mass in the range of from 0 to 10000 g/mol and hydroxyl number from 10 to 100 mgKOH/g, 1 to 5 % (w/w) of water, and 1 to 10 % (w/w) of at least one blowing agent other than water, related to the total weight of the resulting mixture; iii) foaming of the homogenized mixture from step ii) at the temperature of from 20 to 100 °
  • step iii) is performed by pouring the homogenized mixture from step ii) into a mold and kept at the desired temperature.
  • the foaming process corresponds to the reaction between the isocyanate, water and the blowing agents other than water to form carbon dioxide, which is responsible for the foaming, and a primary amine.
  • the amine formed reacts very quickly with other isocyanate (-NCO) groups to form disubstituted urea.
  • the saccharide may be a monosaccharide (e.g. glucose, fructose, galactose), a disaccharide (e.g. sucrose, lactose) or a polysaccharide (e.g. starch, chitin, glycogen, inulin, cellulose, pectin).
  • a monosaccharide e.g. glucose, fructose, galactose
  • a disaccharide e.g. sucrose, lactose
  • a polysaccharide e.g. starch, chitin, glycogen, inulin, cellulose, pectin
  • the hydroxyl number is defined as the number of milligrams of potassium hydroxide required to neutralize the acetic acid taken up on acetylation of one gram of the polyol.
  • the incorporated saccharide means that the saccharide (monosaccharide, disaccharide or polysaccharide) is covalently and/or non-covalently bound into the polymer backbone of the biodegradable polyurethane foam.
  • the non-covalent binding is e.g. binding via van der Waals forces.
  • the resulting foam has incorporated saccharide, and its density is of less than 70 kg/m 3 , preferably from 10 to 50 kg/m 3 , more preferably from 20 to 40 kg/m 3 , most preferably 30 kg/m 3 ; and its open cell content, measured by pycnometer method according to ASTM D 6226-05, is in the range of from 70 % to 100 %, more preferable from 80 % to 100 % and most preferable from 90 % to 100 %.
  • the foam density was measured gravimetricahy according to ISO 845.
  • the cell size measured by optical microscopy, is in the range of from 0.1 to 9 mm, preferably from 0.2 to 3 mm. Such cell size means that about 90 % of the volume of the foam has such cell size, preferably at least about 95 % of the volume of the foam has such cell size.
  • the cell size can be measured by cutting the foam, and measuring the cell size (diameter) of 5 cm x 5 cm foam.
  • the weight ratio of aliphatic isocyanate and saccharide in step i) is from 2:1 to 25:1, more preferably from 5:1 to 20:1, even more preferably from 10:1 to 15:1.
  • the content of the biodegradable aliphatic polyester-ether polyol, related to the total weight of the resulting mixture of step ii), is from 25 to 65 % (w/w), more preferably from 35 to 55 % (w/w), even more preferably from 45 to 50 % (w/w).
  • the hydroxyl number of the biodegradable aliphatic polyester-ether polyol is in the range of from 20 to 80 mgKOH/g, more preferably from 30 to 70 mgKOH/g, even more preferably from 40 to 60 mgKOH/g, most preferably 50 mgKOH/g.
  • Water serves as a blowing agent during the foaming reaction.
  • the water content related to the total weight of the resulting mixture of step ii), is from 1.5 to 4 % (w/w), more preferably from 2 to 3.5 % (w/w), even more preferably from 2.5 to 3 % (w/w).
  • the content of the further blowing agent other than water, related to the total weight of the resulting mixture of step ii), is from 2 to 8.5 % (w/w), more preferably from 3 to 7 % (w/w), even more preferably from 4 to 6 % (w/w), most preferably 5 % (w/w).
  • Homogenization in step ii) may be done using conventional homogenization techniques, such as high speed stirring (e.g. 2000 rpm), sonification, static -dynamic two-component mixing system and dynamic mixing head.
  • a surfactant is added to the mixture to be homogenized in step ii).
  • the surfactant is a cationic surfactant, an anionic surfactant, a zwitterionic surfactant, or a nonionic surfactant.
  • the surfactant is selected from the group comprising a polysorbate (polysorbate 20, polysorbate 80), a lecithin, an alcohol ethoxylate, or PEG-40 hydrogenated castor oil, silicone surfactant, or a combination thereof.
  • the surfactant is added in an amount of from 0.5 to 1.5 % (w/w), related to the total weight of the resulting mixture of step ii), more preferably from 0.6 to 1.2 % (w/w), even more preferably from 0.7 to 1 % (w/w), most preferably from 0.8 to 0.9 % (w/w), related to the total weight of the resulting mixture of step ii).
  • a catalyst is added to the mixture to be homogenized in step ii).
  • the catalyst is preferably selected from the group comprising stannous octoate, dibutyltin dilaurate (DBTL), N,N-dimethylbenzylamine, N,N,N',N'',N''-pentamethyldiethylenetriamine (PMDTA), dimethylethanolamine, triethylenediamine (DABCO), 3-aminopropyldimethylamine, dimethylcyclohexylamine, propylene glycol, N-methylmorpholine, bis-(2-dimethylaminoethyl) ether, l,3,5-tris[3-(dimethylamino)propyl]hexahydro-l,3,5-triazine or a combination thereof.
  • DBTL dibutyltin dilaurate
  • PMDTA N,N-dimethylbenzylamine
  • PMDTA N,N,N',N
  • the catalyst is added in an amount of from 0.5 to 5 % (w/w), related to the total weight of the resulting mixture of step ii), more preferably from 0.7 to 3 % (w/w), even more preferably from 1 to 2 % (w/w), most preferably 1.5 % (w/w), related to the total weight of the resulting mixture of step ii).
  • the aliphatic isocyanate is selected from the group comprising pentamethylene diisocyanate (PD I), hexamethylene diisocyanate (HDI), dimers of pentamethylene diisocyanate, dimers of hexamethylene diisocyanate, trimers of pentamethylene diisocyanate, trimers of hexamethylene diisocyanate, cyclohexyl diisocyanate, methylene dicyclohexyl diisocyanate (HMDI), isophorone diisocyanate (IPDI), poly-isocyanates from vegetable oils (such as soy oil, castor oil, rapeseed oil, olive oil, palm oil, rice bran oil), methyl ester L-lysine diisocyanate, ethyl ester L-lysine diisocyanate, as depicted in Scheme 1.
  • PD I pentamethylene diisocyanate
  • HDI hexamethylene diisocyanate
  • the aliphatic isocyanates have the advantage of their low toxicity, therefore the resulting polyurethane foam is non-toxic during its production and also non-toxic to the culture of microorganisms, cultivated thereon.
  • the products of biodegradation of the polyurethane foam are non-toxic as well.
  • the saccharide is a monosaccharide or a saccharide selected from the group comprising saccharides of general formula (I)
  • R3 is (Ci-C6)alkyl, which can be linear or branched;
  • M is hydrogen, ammonium cation, alkaline metal cation (e.g. Li + , Na + , K + ) or alkaline earth metal cation (e.g. Mg 2+ , Ca 2+ ).
  • alkaline metal cation e.g. Li + , Na + , K +
  • alkaline earth metal cation e.g. Mg 2+ , Ca 2+ .
  • the saccharide is selected from the group comprising wheat B- starch (Amylon), wheat A-starch (Amylon), maltodextrin, preferably with a dextrose equivalent of from 20 to 30, glucose, cellulose, chitin.
  • the aliphatic polyester-ether polyol has molecular weight from 200 to 10000 g/mol, preferably from 400 to 8 000 g/mol, more preferably from 1000 to 6000 g/mol, even more preferably from 2000 to 4000 g/mol.
  • the aliphatic polyester-ether polyol is selected from the group comprising poly(diethyleneglycoladipate) diol, poly(triethyleneglycoladipate) diol, poly(tetraethyleneglycoladipate) diol, poly(diethyleneglycoladipate) triol, poly(triethyleneglycoladipate) triol, poly(tetraethyleneglycoladipate) triol, poly(diethyleneglycolsuccinate) diol, poly(triethyleneglycolsuccinate) diol, poly(tetraethyleneglycolsuccinate) diol, poly(diethyleneglycolsuccinate) triol, poly(triethyleneglycolsuccinate) triol, poly(tetraethyleneglycolsuccinate) triol.
  • the advantage of the use of aliphatic polyester-ether polyol in the biodegradable polyurethane foam synthesis is the increase of hydrophilicity (due to the ether part of the polyol), and at the same time preserving the biodegradability (due to the ester part of the polyol).
  • the aliphatic polyester-ether polyols are fully amorphous and do not crystallize, which is convenient from the view of processing (easy homogenization and foam growth) as well as from the rate of biodegradation (crystalline phase decrease rate of biodegradation).
  • polyetherdiol up to 20 % (w/w), relative to the total weight of the resulting mixture, of one or more polyetherdiol may be added to the mixture to be homogenized in step ii).
  • the polyetherdiol is preferably selected from the group comprising polyethylene glycol with a molecular weight of about 3000 Dalton or lower, preferably about 2000 or lower, such as for example about 400, about 500 or about 700.
  • the addition of the polyetherdiol further increases the hydrophilicity of the resulting biodegradable polyurethane foam.
  • the further blowing agent other than water is selected from the group comprising ammonium bicarbonate, sodium bicarbonate, mixture of citric acid and sodium bicarbonate, azodicarbonamide, carbon dioxide adducts from grafted polyethylenimines.
  • Another object of the present invention is a biodegradable polyurethane foam obtainable by the method according to the present invention.
  • Such foam has incorporated saccharide, and its density is of less than 70 kg/m 3 , preferably from 10 to 50 kg/m 3 , more preferably from 20 to 40 kg/m 3 , most preferably 30 kg/m 3 , and open cell content in the range of from 70 % to 100 %, more preferable from 80 % to 100 % and most preferable from 90 % to 100 %.
  • Cell size is in the range of from 0.1 to 9 mm, preferably from 0.2 to 3 mm.
  • Such cell size means that about 90 % of the volume of the foam has such cell size, preferably at least about 95 % of the volume of the foam has such cell size.
  • the cell size can be measured by cutting the foam, and measuring the cell size (diameter) of 5 cm x 5 cm foam.
  • the invention is further directed to a biodegradable polyurethane foam-based material for saccharide-cleaving enzyme production, and to a method of producing thereof.
  • the biodegradable polyurethane foam-based material for saccharide cleaving enzyme production comprises the biodegradable polyurethane foam according to the present invention, and an immobilized microbial biomass, such as bacteria strain, wherein the microbial biomass (e.g. bacteria strain) is capable of producing the saccharide-cleaving enzyme, preferably, the saccharide of general formula (I)-cleaving enzyme, more preferably the immobilized bacteria strain is capable of producing amylase, glucosidase, chitinase, glycogen phosphorylase, inulinase, cellulase, pectin degrading enzymes.
  • the microbial biomass e.g. bacteria strain
  • the immobilized bacteria strain is capable of producing amylase, glucosidase, chitinase, glycogen phosphorylase, inulinase, cellulase, pectin degrading enzymes.
  • the microbial biomass can be any known in the art, which are capable of producing the saccharide cleaving enzyme.
  • the biodegradable polyurethane foam according to the present invention allows the microorganisms to grow on its surface, and in the pores of this porous material, forming a biofilm. Because the biodegradable polyurethane foam according to the present invention comprises incorporated saccharide (as defined above), this saccharide induces production of the particular saccharide-cleaving enzyme in the microorganism. Moreover, the saccharide also serves as a source of nitrogen and carbon for the microorganism present, thereby ensuring and improving the immobilization of the enzyme -producing microorganism.
  • suitable microbial biomass for immobilization in the biodegradable polyurethane foam and enzyme production is selected from the group comprising bacteria strain of the genus Pseudomonas, Bacillus, Aeribacillus, Geobacillus, Rhodococcus, preferably the immobilised bacteria strain is Pseudomonas gessardii, Bacillus cereus, Aeribacillus pallidus, more preferably Pseudomonas gessardii CCM 8663 (deposited in the Czech Collection of Microorganisms (CCM), Masaryk university, Faculty of Science, Kamenice 5, 62500 Brno, Czech Republic, on 08.02.2016 under accession number CCM 8663).
  • the method of producing saccharide-cleaving enzymes using the biodegradable polyurethane foam-based material for saccharide-cleaving enzyme production comprises the following steps: i) providing the biodegradable polyurethane foam comprising incorporated saccharide according to the present invention; ii) immobilizing enzyme-producing microorganism in the biodegradable polyurethane foam from step i), thereby obtaining the biodegradable polyurethane foam-based material for saccharide cleaving enzyme production according to the present invention; The immobilization is induced by innoculating the biodegradable polyurethane foam from step i) by the saccharide-cleaving enzyme -producing microorganism, followed by cultivating the saccharide-cleaving enzyme- producing microorganism until biofilm is formed, thereby obtaining the biodegradable polyurethane foam-based material for saccharide-cleaving enzyme production with immobilized saccharide-cleaving enzyme-producing microorganism; the microorganisms
  • Fermenting the immobilized enzyme -producing microorganism usually takes place in a vessel, which is usually aerated during the fermentation process (aeration depends on the type of microorganism used - aerobic microorganism require aeration, anaerobic not), including the growth phase and the cultivation phase of the fermentation. Growth medium is provided to the immobilized microorganism during fermentation. Processing conditions generally include a temperature of at least 20 °C, e.g. 25 °C, 30 °C or 35 °C. Unless thermophilic microorganisms are used, the maximum temperature should be of about 45 °C.
  • the pH is usually in the range of from about 4 to about 9, therefore slightly acidic, neutral or slightly basic (pH about 6, about 7 or about 8). Generally, cultivation is performed for several days to achieve suitable amount of enzyme produced. ad iv) The saccharide-cleaving enzyme produced during fermentation is contained in the growth medium, which can be separated from the microorganism using filtration or decantation, and can be isolated from the growth medium by conventional isolating techniques.
  • Suitable growth media are known in the art, and comprise all essential elements and nutrients for the particular microorganism (carbon, nitrogen, sulphur, phosphorus etc.), example of suitable growths medium is Basal Salt Medium (BSM) supplemented with some C and/or N source. Example of such medium is in Table 1:
  • the saccharide may not only be present in the biodegradable polyurethane foam but may also be added into the growth medium, which enables a continuous enzyme production.
  • the saccharide-cleaving enzyme produced by the immobilized microorganism thus depends on the type of saccharide comprised in the biodegradable polyurethane foam. Therefore, starch or maltodextrin comprising foam is suitable for amylase production, chitin comprising foam is suitable for chitinase production, glycogen comprising foam is suitable for glycogen phosphorylase production, inulin comprising foam is suitable for inulinase production, cellulose comprising foam is suitable for cellulase production, glucose comprising foam is suitable for glucosidase production and pectin comprising foam is suitable for production of pectin degrading enzymes.
  • Another aspect of the present invention is the use of the biodegradable polyurethane foam according to the present invention in industrial microbiology.
  • Another aspect of the present invention is the use of the biodegradable polyurethane foam according to the present invention as a carrier for biomass immobilization, preferably for immobilization of industrial production microorganisms, more preferably for immobilization of bacteria from the genus Pseudomonas, Bacillus, Aeribacillus, Geobacillus, Rhodococcus, even more preferably Pseudomonas gessardii, Bacillus cereus, Aeribacillus pallidus, most preferably Pseudomonas gessardii CCM 8663.
  • Another aspect of the present invention is the use of the biodegradable polyurethane foam-based material with immobilized microorganisms according to the present invention for saccharide cleaving enzyme production, preferably the saccharide-cleaving enzyme is selected from the group comprising amylase, glucosidase, glycogen phosphorylase, inulinase, cellulase, pectin degrading enzymes.
  • Fig. 1 Photos of biofilms of Pseudomonas sp. (a, b), Bacillus cereus (c, d) and Aeribacillus pallidus (e, f), cultivated on the biodegradable polyurethane foam from Comparative example 2, with glucose substrate after 2 (a, c, e) and 5 (b, d, f) hours.
  • Examples
  • Cream time of polyurethane foam - detected by changing the volume of the material Polyurethane foam gel time - detected as the time when a polymeric string can be formed by immersing the test rod in the system, i.e. a three-dimensional structure is formed.
  • the bulk density of polyurethane foam was determined according to Czech national standard no. CSN EN ISO 845.
  • the open cell content of the polyurethane foam was determined using pycnometer method according to Standard Test Method for Open Cell Content of Rigid Cellular Plastics no. ASTM D 6226-05.
  • Example 1 The cell size distribution in the polyurethane foam was determined by optical microscopy.
  • Example 1 The cell size distribution in the polyurethane foam was determined by optical microscopy.
  • Example 2 The reaction mixture was then poured into an open mold and left freely foamed at 25 ° C and then post-cured at room temperature for 48 h.
  • the process characteristics of the foaming and the properties of the prepared foam are summarized in Table 2.
  • the prepared block of foam was cut to cubes of 10x10x10 mm, which were used as porous carriers of microbial biomass according to Examples 13.
  • Example 2 Example 2:
  • the reaction mixture was then poured into an open mold and left freely foamed at 45 ° C and then post-cured at room temperature for 48 h.
  • the process characteristics of the foaming and the properties of the prepared foam are summarized in Table 2.
  • the prepared block of foam was cut to cubes of 10x10x10 mm, which were used as porous carriers of microbial biomass according to Example 13.
  • the reaction mixture was then poured into an open mold and left freely foamed at 25 ° C and then post-cured at room temperature for 48 h.
  • the process characteristics of the foaming and the properties of the prepared foam are summarized in Table 2.
  • the prepared block of foam was cut to cubes of 10x10x10 mm, which were used as porous carriers of microbial biomass according to Example 13.
  • a mixture of 30 g of maltodextrin with a dextrose equivalent of 22 and 56 g of trimer of pentamethylene diisocyanate (Desmodur TM eco N 7300, Covestro) was homogenized in a plastic crucible for 10 min using a high speed stirrer (2000 rpm).
  • poly(diethylene glycol adipate) diol having a hydroxyl value of 49 mgKOH / g, 2.3 g of water, 8.7 g of ammonium bicarbonate, 0.9 g of Niax TM Silicone L-6900 (Momentive Performance Materials) silicone surfactant, 0.6 g of dibutyltin dilaurate (DBTL, Aldrich, Germany) and 0.5 g of N,N,N',N",N''- pentamethyldiethylenetriamine (Polycat TM 9, Air Products) were then added to the mixture, and the mixture was homogenized for a further 60 s.
  • DBTL dibutyltin dilaurate
  • Polycat TM 9 Air Products Polycat TM 9, Air Products
  • the reaction mixture was then poured into an open mold and left freely foamed at 30 ° C and then post-cured at room temperature for 48 h.
  • the process characteristics of the foaming and the properties of the prepared foam are summarized in Table 2.
  • the prepared block of foam was cut to cubes of 10x10x10 mm, which were used as porous carriers of microbial biomass according to Example 13.
  • a mixture of 30 g of wheat A- starch Soltex NP1 (Amy Ion) and 40 g of trimer of pentamethylene diisocyanate (Desmodur TM eco N 7300, Covestro) was homogenized in a plastic crucible for 10 min using a high speed stirrer (2000 rpm).
  • the reaction mixture was then poured into an open mold and left freely foamed at 55 ° C and then post-cured at room temperature for 48 h.
  • the process characteristics of the foaming and the properties of the prepared foam are summarized in Table 2.
  • the prepared block of foam was cut to cubes of 10x10x10 mm, which were used as porous carriers of microbial biomass according to Example 13.
  • the reaction mixture was then poured into an open mold and left freely foamed at 20 ° C and then post-cured at room temperature for 48 h.
  • the process characteristics of the foaming and the properties of the prepared foam are summarized in Table 2.
  • the prepared block of foam was cut to cubes of 10x10x10 mm, which were used as porous carriers of microbial biomass according to Example 13.
  • the reaction mixture was then poured into an open mold and left freely foamed at 75 ° C and then post-cured at room temperature for 48 h.
  • the process characteristics of the foaming and the properties of the prepared foam are summarized in Table 2.
  • the prepared block of foam was cut to cubes of 10x10x10 mm, which were used as porous carriers of microbial biomass according to Example 13.
  • the reaction mixture was then poured into an open mold and left freely foamed at 55 ° C and then post-cured at room temperature for 48 h.
  • the process characteristics of the foaming and the properties of the prepared foam are summarized in Table 2.
  • the prepared block of foam had 5 % (w/w) (8B) chitin content, and was cut to cubes of 10x10x10 mm, which were used as porous carriers of microbial biomass according to Example 13.
  • Analogously, biodegradable polyurethane foams with 2.5 (8A) and 7.5 % (w/w) (8C) of chitin were prepared, using 3.6 or 15 g of chitin, respectively, for the synthesis.
  • Example 9 Example 9:
  • the reaction mixture was then poured into an open mold and left freely foamed at 30 ° C and then post-cured at room temperature for 48 h.
  • the process characteristics of the foaming and the properties of the prepared foam are summarized in Table 2.
  • the prepared block of foam was cut to cubes of 10x10x10 mm, which were used as porous carriers of microbial biomass according to Example 13.
  • the reaction mixture was then poured into an open mold and left freely foamed at 23 ° C and then post-cured at room temperature for 48 h.
  • the process characteristics of the foaming and the properties of the prepared foam are summarized in Table 2.
  • the prepared block of foam was cut to cubes of 10x10x10 mm, which were used as porous carriers of microbial biomass according to Example 13.
  • Table 2 Characteristics of foaming and porous polyurethane foams obtained ti - cream time of polyurethane foam growth; t2 - gel time of the polyurethane foam; t 3 - end-of- rise time of polyurethane foam growth; U - tack-free time of the polyurethane foam surface; p density of polyurethane foam; OV% open cell content of polyurethane foam.
  • Example 11 Microorganisms used for enzyme production
  • Tested bacterial species Pseudomonas gessardi, Bacillus cereus and Aeribacillus pallidus ) were stored in a freezer at -80 °C (Liebherr CP 4023) in a solution of 25% glycerol in microtubes. Prior to being tested, all bacterial cultures were aseptically (in a flowbox) innoculated in a Petri’s dish comprising growth medium (DEV agar). DEV agar contents, as given by the producer, are listed in Table 3. The innoculated Petri’s dishes were placed into a desiccator, wherein cultivation occured at room temperature. Table 3: DEV agar contents
  • Microscopy was performed using Olympus BX40 microscope, and the pictures were taken using a camera Canon EOS 700D.
  • Example 13 Microbial biofilm cultivation on the biodegradable polyurethane foam Microbial biofilm cultivation was performed in 250 mL Erlenmayer flasks, each cultivation was repeated twice. Each microorganism tested was cultivated in the presence and absence of the particular substrate (glucose, peptone, ethanol). Four pieces of the biodegradable polyurethane foam according to the present invention were placed into each cultivation flask. The microbial culture was then grown using the particular substrate. Optical density of individual samples of 1 piece of foam and 1 mL of the substrate were measured.
  • Bacterial Standard Medium was used as growth medium, having the following composition: 6.8 [g.U 1 ] KH2PO4, 8.6 [g.U 1 ] K2HPO4, 4 [g.U 1 ] (NH ) 2 S04, 0.68 [g.U 1 ] MgCk.6H20, 200 [pL.L 1 ] trace elements.
  • BSM medium was prepared by dissolving the above amounts of K2HPO4 (99%, PENTA, batch number 280308) and KH2PO4 (99%, Lach-Ner, batch number PP/2010/06505) in 1 L of distilled water.
  • biodegradable polyurethane foams After 5 hours, sterile biodegradable polyurethane foams according to the present invention were placed into the indicidual suspensions (the biodegradable polyurethane foams were sterilised at 110 °C in a drying chamber Zalimp, KBC G16/250, Tru). Actual substrate concentration (HPLC) and optical density were measured. The suspensions were further shaken at 30 °C and 120 rpm (laboratory shaker) and further samples were taken after 2, 3, 4, and 5 hours of cultivation. The biodegradable polyurethane foam-based material was then colored using Gram stain, and the samples were analysed using microscopy (Olympus BX40 microscope, zoom 40x). The area covered by a particular biofilm was then calculated for each sample.
  • Optical density was measured using spectrophotometer (Biochrom, Libra S22, wavelength 600 nm) to analyze actual growth of the bacterial culture within the particular suspension. Correlation with the biofilm growth was observed.
  • Biofilm growth was analyzed using photos of biodegradable polyurethane foam (synthesized in Comparative example 2) taken from the culture suspension after 2, 3, 4, and 5 hours, using NIS- elements AR 3.0 program.
  • Fig. 1 depicts photos of biofilms of Pseudomonas sp., Bacillus cereus and Aeribacillus pallidus, cultivated on the biodegradable polyurethane foam from Comparative example 2, with glucose substrate after 2 and 5 hours. Other cultivations using other biodegradable polyurethane foams according to the present invention (as substrates) had similar biofilm formation.
  • Example 14 Examples of production cultivations and determination of enzymatic activity Cultivation conditions:
  • sterile BSM 50 ml of sterile BSM was added into sterile Erlenmayer flask with 0.5 g of the biodegradable polyurethane foam according to the present invention (comprising 5 % (w/w) chitin (Example 8B), 5 % (w/w) B-starch (Example 7), and 2.5 % (w/w) maltodextrin (Example 3)) and a commercial foam as a control.
  • Cell suspension was added to each flask such that the resulting optical density was about 0.1.
  • 10 samples were prepared (3 samples of each biodegradable foam and 1 control). Ethanol was added to the control sample and to two of the three samples of each foam according to the present invention.
  • Example 15 Chitinase production by bacteria immobilized on the biodegradable polyurethane foam from Example 8 A porous biodegradable polyurethane foam was synthesised according to Example 8, having the composition as listed in Table 8. Table 9 details results of the chitinase production.
  • Table 8 Composition of biodegradable polyurethane foams A bacteria strain Pseudomonas gessardii CCM 8663 was immobilized onto the biodegradable polyurethane foams according to previous Examples 13 and 14.
  • the immobilized bacteria were cultivated in BSM media. To this was optionally added glucose (1 % solution) or ethanol (1 % solution). The biomass growth was observed, and it was shown that even in a low carbon environment (i.e. only BSM), bacterial growth occured. Moreover, significant growth was observed in samples with added glucose.
  • the foam with 5 % chitin was used for measuring the area covered by the bacteria after 24 hours at 20, 25 and 30 °C. Coverage was good for all experiments (> 70 %) but the highest for the reaction performed at 25 °C (92 %). This value was influenced by the amount of inoculum used. Although all amounts between 0.5 and 2 % (v/v) were good

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Abstract

La présente invention concerne un procédé de synthèse d'une mousse de polyuréthane biodégradable, comprenant les étapes suivantes : i) mélange d'au moins un isocyanate aliphatique portant au moins deux groupes isocyanate avec au moins un saccharide en rapport pondéral de 1:1 à 30:1 pour former un précurseur saccharide-isocyanate ; ii) homogénéisation du précurseur saccharide-isocyanate de l'étape i) avec 20 à 70 % (w/w) d'au moins un polyester-éther-polyol aliphatique biodégradable ayant une masse moléculaire dans la plage de 0 à 10 000 g/mol et un indice d'hydroxyle de 10 à 100 mg de KOH/g, 1 à 5 % (w/w) d'eau, et 1 à 10 % (w/w) d'au moins un agent d'expansion autre que l'eau, lié au poids total du mélange résultant ; iii) moussage du mélange homogénéisé de l'étape ii) à la température de 20 à 100 °C, conduisant à la mousse de polyuréthane biodégradable comprenant un saccharide incorporé. L'invention concerne en outre une mousse de polyuréthane biodégradable pouvant être obtenue par ce procédé, un matériau à base de mousse de polyuréthane biodégradable pour la production d'enzyme de clivage de saccharide et son utilisation.
PCT/CZ2021/050007 2020-01-22 2021-01-21 Mousse de polyuréthane biodégradable, matériau à base de mousse de polyuréthane biodégradable pour la production d'enzyme de clivage de saccharide, procédé de synthèse et utilisation de celui-ci WO2021148064A1 (fr)

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CZ202032A CZ308954B6 (cs) 2020-01-22 2020-01-22 Biodegradovatelná polyuretanová pěna, materiál na bázi biodegradabilní polyuretanové pěny pro produkci enzymů štepících sacharidy, způsob jejich přípravy a jejich použití
CZPV2020-32 2020-01-22

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WO2024135690A1 (fr) * 2022-12-21 2024-06-27 株式会社イノアックコーポレーション Mousse de polyuréthane et composition pour produire la mousse de polyuréthane

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