WO2016062578A1 - Procédé de préparation de polylysines - Google Patents

Procédé de préparation de polylysines Download PDF

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Publication number
WO2016062578A1
WO2016062578A1 PCT/EP2015/073606 EP2015073606W WO2016062578A1 WO 2016062578 A1 WO2016062578 A1 WO 2016062578A1 EP 2015073606 W EP2015073606 W EP 2015073606W WO 2016062578 A1 WO2016062578 A1 WO 2016062578A1
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polylysine
water
lysine
mixture
range
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PCT/EP2015/073606
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English (en)
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Olivier FLEISCHEL
Radoslaw Kierat
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/10—Alpha-amino-carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/04—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/48—Polymers modified by chemical after-treatment

Definitions

  • a process for preparing polylysines The present invention relates to a process for preparing polylysines and to polylysines obtainable by the process.
  • Polymers in particular branched polymers, can be prepared by what is called the AB2 route.
  • An AB2 molecule is a term used to refer to a trifunctional monomer containing one reactive group A (e.g., lysine carboxyl group) and two reactive groups B (e.g., lysine amino groups). Where these groups A and B are reactive with one another, branched polymers can be produced by intermolecular reaction.
  • Polylysines can, for example, be synthesized by direct thermal addition polymerization of L-lysines.
  • the thermal addition polymerization of lysine has been carried out in the absence of solvent.
  • Harada (Bull. Chem. Soc. Japan 1959, 32, 1007-1008) heated DL- lysine (0.01 mol) for 2 hours to temperatures in the range from 180 °C to 210 °C.
  • the obtained lysine polymer was water-soluble, contained gel-like material but was non- diffusable through cellophane tubing. No molecular weight is reported. At 150 °C to 170 °C free DL-lysine was converted to its liquid lactam.
  • WO 2007/0601 19 describes the condensation of L-lysine hydrochloride in the presence of sodium hydroxide, water (10 % by weight based on the L-lysine hydrochloride) and the catalyst dibutyltin dilaurate. The mixture was heated with stirring to an internal temperature of 150 °C. After a reaction time of 5 hours, water was distilled off under reduced pressure (200 mbar), and after the major amount of water was removed the temperature was slowly raised to 180 °C and the pressure was reduced to 10 mbar. After 8 hours 240 g of water distillate had been collected. The weight-average molecular weight of the obtained polymer was 15 000 g/mol, the polydispersity was 5.0. Use of the catalyst requires additional effort in terms of starting material and for removing the catalyst from the obtained polylysine. Moreover, the use of lysine hydrochloride as starting material is undesirable due to the risk of corrosion.
  • Hennon et al. (Biochimie 1971 , 53, 215-223) describe the preparation of a brown resin starting from an aqueous solution of lysine (50 %). The solution was concentrated by evaporation at 105 °C to 1 10 °C and then kept at 165 °C to 170 °C while it was agitated by directing a weak preheated nitrogen stream through it. The brown resin was obtained after 8 hours at 165 to 170 °C. A polylysine fraction that could be dialysed (40 % of the total polymer formed) and a polylysine fraction that could not be dialysed (60 % of the total polymer formed) were extracted from the resin.
  • the mass of the fraction that could not be dialyzed was 1.79 g starting from 5 g of lysine. Accordingly, the mass of the fraction that could be dialysed must have been 1.19 g.
  • the overall mass of the polylysine obtained was thus less than 60 % of the mass of the lysine starting material, which shows that the process is inefficient in terms of product yield.
  • Ho et al. describe the synthesis of polylysine by thermally heating an aqueous lysine solution for two days at 160 °C.
  • the obtained polylysine has a degree of branching between 0.50 and 0.54. when using microwave assisted heating at 200 °C, the obtained polylysine has a degree of branching between 0.30 and 0.32.
  • the molecular weight M n could be controlled in a range of 5000-12,000 g/mol.
  • US 2013/0123148 discloses the preparation of polylysine by heating an aqueous lysine solution in the presence of catalytical amounts of dibutyltindilaurate. According to the examples, the obtained polylysine has a degree of branching above 0.30.
  • the problem underlying the present invention was to provide a simple process suitable for large scale production of polylysine with improved yield.
  • a further problem was to provide a process for producing a polylysine having a high degree of biodegradability.
  • a further problem was to provide a process for producing a polylysine with a low degree of branching (crosslinkages).
  • step (b) keeping the reaction mixture of step (a) at a temperature in a range from 135 to 165 °C at a pressure below atmospheric pressure, wherein water is removed from the mixture, and any temperature increase is ⁇ 30 °C in 60 minutes.
  • the temperature ranges refer to the internal temperature of the reaction mixture in a reaction vessel, not to the temperature of an external heat source used for heating the reaction vessel.
  • Customary technical aqueous lysine solutions can be used in the process according to the invention and no catalyst is required.
  • the mixture is in a liquid state, e.g., a melt of polylysine, not a resin.
  • the material fed into the reaction mixture, nor the reaction itself is in a solid state at any time which means that no solid materials need to be transported, fed into the process, mixed in the reaction vessel, or be taken from the reaction vessel at the end of the process. Further, there is no need of isolating any catalysts from the obtained polylysine.
  • the water content of the molten polylysine can, for example, be in the range from 0 to 30 % by weight, prefera- bly 0 to 20 % by weight, more preferably 0 to 10 % by weight, most preferably 0 to 5 % by weight.
  • the molten polylysine can easily be removed from the reaction vessel in which the process according to the invention is carried out.
  • the polylysine obtained at the end of the second step may for example be cooled to solidify it.
  • the polylysine obtained at the end of the second step is directed from the reaction vessel into a cooling unit where its temperature is decreased such that it solidifies.
  • Any apparatus in which heat can be removed from the polylysine is suitable as a cooling unit.
  • the cooling unit may, for example, be an open container that can be cooled.
  • a solvent e.g. water, can be added to dilute the polylysine obtained at the end of the second step.
  • the diluted polylysine can then, for example, be easily removed from the reaction vessel.
  • the boiling aqueous reaction mixture of the process according to the invention is obtained by heating an aqueous starting mixture comprising lysine and water in a weight ratio of 1 : 10 to 3: 1 . It is also possible to first heat water and then add the lysine in one or more portions. Preferably, the starting mixture is heated at atmospheric pressure in order to provide the boiling aqueous reaction mixture.
  • the aqueous starting mixture comprises water and lysine.
  • other constituents may be present, for example, residual constituents from the preparation of the lysine.
  • the content of any constituent other than lysine and water is generally low.
  • the mass of all constituents other than water or lysine in the starting mixture is, for example at most 10 %, preferably at most 5 %, further preferably at most 3 %, and most preferably at most 1 % by weight of the lysine contained in the starting mixture.
  • the aqueous starting mixture is preferably an aqueous solution of lysine in water.
  • the weight ratio of lysine to water in the aqueous starting mixture is therefore at least 1 :10, for example at least 1 :5, preferably at least 1 :3, and most preferably at least 1 :1 .5.
  • the aqueous starting mixture is an aqueous solution of lysine in water, wherein the weight ratio of lysine to water is 1 :1 .5 to 3:1 , preferably 1 :1 .5 to 1 .5:1 .
  • the lysine comprised by the aqueous starting mixture can be L-lysine, D-lysine, or any mixture of L-lysine and D-lysine, e.g. a racemic mixture.
  • the aqueous starting mixture can, for example, be an aqueous solution of L-lysine in water that contains 50 % by weight of L-lysine and 50 % by weight of water; e.g., ADM Liquid L-Lysine, Product Code: 035101 sold by Archer Daniels Midland, Sewon L- Lysine ® 50% liquid feed sold by Paik Kwang, or BestAminoTM L-Lysine liquid feed grade sold by CJ CheilJedang.
  • Polylysine is formed from lysine in a polycondensation reaction in which water is released when an amino group of one lysine molecule and a carboxyl group of another lysine molecule react with each other to form an amide bond under production of water.
  • the removal of water from the reaction mixture favors polylysine formation.
  • the temperature increase of the mixture is ⁇ 30 °C in 60 minutes throughout the whole process. This means that the temperature of the reaction mixture is controlled such that its temperature does not increase by more than 30 °C in any 60 minutes from the beginning of the first step to the end of the second step.
  • the temperature increase of the mixture is ⁇ 25 °C in 60 minutes and preferably ⁇ 20 °C in 60 minutes, throughout the whole process.
  • the temperature increase of the mixture is in general at least 10 °C and preferably at least 15 °C in 60 minutes.
  • the temperature increase is in the range of from 10 to 25 °C or from 10 to 20 °C in 60 minutes.
  • the temperature increase is in the range of from 15 to 25 °C or from 15 to 20 °C in 60 minutes.
  • the tempera- ture of the reaction mixture is increased continuously.
  • the process according to the invention requires that water is removed from the reaction mixture. Any means suitable for removing water may be applied in order to remove water from the reaction mixture. Water is preferably evaporated from the mixture. The water is most preferably removed from the mixture by distillation.
  • the formation of foams is efficiently suppressed when the evaporation is carried out continuously. It is thus favorable to continuously remove water from the mixture in both steps, most pref- erably throughout both steps, of the process according to the invention by evaporation, e.g., by distillation.
  • the amount of water removed in 60 minutes is ⁇ 30 %, preferably ⁇ 20 %, further preferably ⁇ 10 %, more preferably ⁇ 5 % of the total amount of water to be removed from the reaction medium.
  • the pressure in the first step is preferably in the range from about 0.8 bar to about 1 .2 bar, for example at atmospheric pressure.
  • the process according to the invention requires a pressure below atmospheric pressure in the second step.
  • the pressure reduction facilitates the evaporation of water and thus accelerates the polycondensation reaction.
  • the pressure is, for example, reduced in the second step to a pressure in the range from about 0.1 to about 500 mbar, preferably about 1 to about 450 mbar, further preferably about 10 to about 400 mbar, more preferably about 50 to about 350 mbar, and most preferably about 100 to about 300 mbar. It is particularly preferable to reduce the pressure in the second step to about 200 mbar.
  • the removal of water may, for example, be continued in the process according to the invention until the water content in the reaction mixture is 0 to 30 % by weight, preferably 0 to 20 % by weight, more preferably 0 to 10 % by weight, most preferably 0 to 5 % by weight. It is thus particularly advisable to remove water from the reaction mixture in both steps when the reaction mixture is dilute, e.g. at a weight ratio of lysine to water of 1 :10 to 1 :1. It is sufficient to limit the removal of water from the reaction mixture to a part of the process when less water has to be removed from the reaction mixture, i.e. when the starting mixture is more concentrated, e.g. at a weight ratio of lysine to water of 1 :1 to 3:1 .
  • the initial aqueous polylysine solution is heated to boiling.
  • the boiling aqueous reaction mixture is then heated in the first step within about 2 to about 8 hours, for example within about 4 to about 8 hours, to a temperature in the range from about 135 to about 165 °C, and in the second step the reac- tion mixture of the first step is kept in a range from about 135 to about 165 °C.
  • the reaction mixture is generally kept for 1 to 5 hours at a temperature from about 135 to about 165 °C.
  • the heating time in the first and second step together generally is about 4.5 hours to about 1 1 hours, preferably about 5 to about 10.5 hours, most preferably about 5.5 to about 10 hours.
  • the reaction mixture is thus, for example, for at most about 6 hours, preferably for at most about 5 hours, most preferably for at most about 4 hours kept at a temperature of about 160 °C or more.
  • This upper limit refers to the whole process, i.e. the sum of all time intervals throughout the first and second step, at which the temperature of the reaction mixture is 160 °C or more, amounts to at most 6 hours, preferably at most 5 hours, most preferably at most 4 hours.
  • the reaction mixture of the first step is kept in a range from about 135 to about 165 °C, for example about 140 °C to about 165 °C, preferably about 145 to about 165 °C.
  • the process is carried out without a catalyst.
  • the process can be carried out continuously or, preferably, batchwise.
  • the process is preferably carried out in what is called a one-pot mode, in which the lysine is included in its entirety in the initial charge and the polycondensation reaction is carried out in a reactor with backmixing.
  • reaction regimes in a multistage reactor system, a stirred-tank cascade, or in a tube reactor.
  • the polylysine obtainable by the process according to the invention is preferably a branched polylysine, e.g., a non-crosslinked branched polylysine.
  • the invention also relates to a branched polylysine, e.g., a non-crosslinked branched polylysine, obtainable by the process according to the invention.
  • the polylysine obtainable by the process according to the invention is preferably a branched polylysine, e.g., a non-crosslinked branched polylysine. It preferably has a weight-average molecular weight in the range from about 1000 Da to about 10000 Da, preferably from about 1500 Da to about 4000 Da, most preferably from about 2000 Da to about 3000 Da. It may, for example, have a degree of branching of from 20 % to 30 %, preferably of from 21 % to 28 %, most preferably from 21 % to 25 %.
  • polydispersity of at most 3.6, preferably at most 3.0, in particular 1 .2 to 3.6, 1 .3 to 3.0 or in particular ⁇ 2, for example 1.2 to 1 .99 or 1 .3 to 1 .98.
  • the most preferred polylysines have a polydispersity in the range from 1.2 to 1 .8.
  • Weight-average and number-average molecular weights are determined by gel permeation chromatography (SEC, size exclusion chromatography) as described in greater detail in the examples section.
  • the amine number of the polylysine is preferably from 365 to 500 mg KOH/g, more preferably from 390 to 480 mg KOH/g, most preferably from 390 to 480 mg KOH/g.
  • the amine number is preferably measured by the potentiometric titration method explained below.
  • non-crosslinked in the context of the present invention that the gel content of a polylysine sample, i.e., the polylysine fraction which is insoluble when stored at room temperature (23 °C) under water for 24 hours, divided by the total mass of the sample is not more than 20%, preferably not more than 10%, and more preferably not more than 5%.
  • the process according to the invention may further comprise a chemical modification of the polylysine to obtain a chemically modified polylysine.
  • the accessible amino groups have been at least partly further modified, i.e., reacted with reagents which alter the properties of the polylysine thus modified. Examples of these properties include solubility, dispersibility, hydrophilicity, hydrophobicity, and rheology.
  • the chemical modification can, for example, be a functionalization.
  • the functionalization of the polylysine can be achieved for example by addition of molecules without amino groups or carboxyl groups but comprising acid groups, isocyanate groups, keto groups or aldehyde groups, or activated double bonds, examples being molecules comprising acrylic double bonds.
  • polypeptides comprising acid groups by reaction with acrylic acid or maleic acid and derivatives thereof, esters for example, with subsequent hydrolysis, if appropriate.
  • polylysine into polylysine polyols by reaction with alkylene oxides, such as ethylene oxide, propylene oxide or butylene oxide, for example.
  • alkylene oxides such as ethylene oxide, propylene oxide or butylene oxide, for example.
  • a further possibility for the functionalization of the amino groups in polylysine lies in the at least partial reaction of the amino groups with lactones and/or lactams, to form polyester chains with a terminal hydroxyl group which start out from these amino groups.
  • lactams are ⁇ -caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam, N-methylcapro- lactam, and N-methylpyrrolidone.
  • Exemplary lactones are ⁇ -caprolactone, ⁇ -valero- lactone, and ⁇ -butyrolactone.
  • a further possibility of chemically modifying the polylysine lies in the reaction of the polypeptides with polyalkylene oxides which are terminated by amino groups or acid groups and have a functionality of one, two or more, preferably polyethylene oxides, polypropylene oxides or polyethylene-propylene oxides.
  • Salts of the polylysine can be formed with protic acids or by quaternization of the amino functions with alkylating reagents, such as methyl halides, alkyl tosylates or dialkyl sulfates.
  • the salt formation can also be carried out by mixing or reacting the amino groups of the polylysine stoichiometrically or substoichiometrically with acidic components or salts thereof that have long-chain linear or branched alkyl radicals, cycloalkyi radicals substituted if appropriate, or aryl radicals substituted if appropriate, and which are commonly known as soaps or surfactants.
  • Acidic components of this kind may preferably contain at least one, with particular preference precisely one, carboxyl, sulfonic acid, sulfate or phosphonic acid group.
  • the polylysine may for example be reacted with alkyl- or alkenylcarboxylic acids, such as, for example, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, hexa- decanoic acid, stearic acid, oleic acid, linoleic acid, linolenic acid or their Li, Na, K, Cs, Ca or ammonium salts, with alkylsulfonic acids, examples being octanesulfonic acid, dodecanesulfonic acid, stearylsulfonic acid or oleylsulfonic acid, or their Li, Na, K, Cs, Ca or ammonium salts, with camphorsulfonic acid, cyclododecylsulfonic acid, p- toluenesulfonic acid, benzenesulfonic acid, 4-hexylbenzenesulfonate, 4-
  • the alkyl, cycloalkyi or aryl radicals may in this case have up to 20 carbon atoms, preferably 6 to 20, more preferably 7 to 20.
  • polylysine In order to achieve nonionic hydrophilization it is possible to react the polylysine with aliphatic or aromatic isocyanates that additionally comprise polyethylene glycol chains.
  • polylysine can also be modified with hydrophobic and hydrophilic agents simultaneously-for example, with long-chain aliphatic carboxylic acids, alcohols, amines or isocyanates which have a functionality of one, two or more, and at the same time with alcohols, amines, acids or isocyanates which contain polyethylene glycol chains and have a functionality of one, two or more.
  • the polylysines of the invention are obtained in a high yield. Furthermore, the polyly- sines of the invention exhibit the following advantages: high degree of biodegradability in terms of OECD Guideline for Testing of Chemicals 301 B (soft water) and 306 (sea water).
  • the polylysines are classified as inherently biodegradable under enhanced test conditions in soft water (biodegradability of >60% after 60 days). For the polylysines of the invention a biodegradability of 80 to 90% was observed. low degree of branching (low molecular weight and low polydispersity).
  • the polylysine and/or the chemically modified polymer obtained by chemical modification of the polylysine may be used as adhesion promoters and thixotropic agents, solu- bilizers, phase transfer reagents for water-insoluble chemicals, phase transfer reagents for water-soluble chemicals, surface modifiers, and components in the production of printing inks, paints, coatings, adhesives, sealants, corrosion control products, casting elastomers, and foams.
  • a 50 % aqueous lysine source was heated to the boiling point and then by increasing the temperature of the external heat source as specified in Table 1 in column 'T(ext)" while water was distilled off.
  • the pressure was then decreased to 200 mbar in examples 1 , 3 to 5 and 7 to 14 using a vacuum pump, while the external heat source was maintained at 180 °C.
  • Amine number [mg KOH/g] (given for 100% pure polylysine)
  • the DB in the examples of the invention was in the range of from 0.21 to 0.25.
  • Mw and M n were determined by size exclusion chromatography under the following conditions:
  • Solvent 0.1 % (w/w) trifluoroacetate, 0.1 M NaCI in distilled water
  • the biodegradability of the polylysine of example 12 was determined as described in the OECD Guideline for Testing of Chemicals 301 B (soft water) using activated sludge from the municipal waste water treatment plant Mannheim, Germany. The results were as follows:
  • Biodegradability in soft water 88 % CO2/TI-1CO2 after 60 days (quantitative determination of the formed carbon dioxide by comparison with the calculated maximum theoretical carbon dioxide production). As the microorganisms oxidize only a part of the test substance and incorporate the rest into biomass, a biodegradation level of 88 % reflects excellent biodegradability. The biodegradation curve for the tested polylysine is shown in figure 1.
  • the biodegradability of the polylysine of example 10 was determined as described in the OECD Guideline for Testing of Chemicals 306 (soft water) using the closed bottle method. The results were as follows:
  • Biodegradability in sea water (closed bottle method): 21 % after 28 days.

Abstract

La présente invention concerne un procédé de préparation d'une polylysine, comprenant les étapes consistant (a) à chauffer un mélange aqueux de réaction en ébullition comprenant de la lysine et de l'eau dans un rapport pondéral de 1:10 à 3:1, en 2 à 8 heures, à une température située dans la plage allant de 135 à 165 °C, et (b) à maintenir le mélange de réaction de l'étape (a) à une température située dans la plage allant de 135 à 165 °C à une pression inférieure à la pression atmosphérique, l'eau étant éliminée du mélange, et toute augmentation de température étant ≤ 30 °C en 60 minutes. Le procédé est simple et approprié pour une production à grande échelle de la polylysine avec un rendement amélioré.
PCT/EP2015/073606 2014-10-21 2015-10-13 Procédé de préparation de polylysines WO2016062578A1 (fr)

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WO2018206239A1 (fr) * 2017-05-12 2018-11-15 Basf Se Dérivé de polylysine et son utilisation dans des compositions à base de solides
WO2019175041A1 (fr) 2018-03-15 2019-09-19 Basf Se Composition appropriée pour des soins capillaires
WO2019233795A1 (fr) 2018-06-06 2019-12-12 Basf Se Polyamidoamines alcoxylées utilisées comme agents dispersants
WO2020094823A1 (fr) * 2018-11-09 2020-05-14 Basf Se Dérivés de poly-lysine pour augmenter l'efficacité de formulations agrochimiques
WO2021004845A1 (fr) 2019-07-08 2021-01-14 Basf Se Copolymère à ramification lysine
WO2021004759A1 (fr) 2019-07-08 2021-01-14 Basf Se Composition, son utilisation et procédé de gravure sélective d'un matériau silicium-germanium
WO2021151828A1 (fr) 2020-01-30 2021-08-05 Basf Se Utilisation d'une polylysine pour augmentation de la brillance des cheveux
WO2021239622A1 (fr) 2020-05-27 2021-12-02 Basf Se Polymères ramifiés à base d'acides aminés pour le renforcement capillaire
WO2021254824A1 (fr) 2020-06-18 2021-12-23 Basf Se Compositions et leur utilisation
WO2022096518A1 (fr) 2020-11-05 2022-05-12 Covestro (Netherlands) B.V. Compositions appropriées pour améliorer les propriétés de flexion d'objets contenant des fibres végétales
CN114621431A (zh) * 2022-01-20 2022-06-14 浙江大学 具有低多分散性指数的超支化聚赖氨酸粉末及其生产方法
WO2022136612A1 (fr) 2020-12-23 2022-06-30 Basf Se Composition de liant comprenant des poly(aminoacide)s pour des articles composites à base de fibres
WO2022136613A1 (fr) 2020-12-23 2022-06-30 Basf Se Composition de liant comprenant une ou plusieurs polyamines ainsi que de la 1,3-dihydroxyacétone, du glycolaldéhyde et/ou du glycéraldéhyde pour des articles composites
WO2022136614A1 (fr) 2020-12-23 2022-06-30 Basf Se Composition de liant comprenant une ou des polyamines et de l'hydroxyacétone pour articles composites
CN114990055A (zh) * 2022-05-30 2022-09-02 浙江大学 一种含有支化结构抗菌肽的新型细胞培养基及其制备方法
WO2024008938A1 (fr) 2022-07-08 2024-01-11 Covestro (Netherlands) B.V. Compositions pour panneaux de fibres présentant des propriétés améliorées lors d'un durcissement rapide à basse température
WO2024008939A1 (fr) 2022-07-08 2024-01-11 Covestro (Netherlands) B.V. Compositions pour panneaux de fibres présentant des propriétés améliorées lors d'un durcissement rapide à basse température
WO2024008940A1 (fr) 2022-07-08 2024-01-11 Covestro (Netherlands) B.V. Compositions pour panneaux de fibres présentant des propriétés améliorées lors d'un durcissement rapide à basse température
WO2024038153A1 (fr) 2022-08-19 2024-02-22 Covestro (Netherlands) B.V. Compositions pour panneaux de fibres présentant des propriétés améliorées lors d'un durcissement rapide à basse température
WO2024038152A1 (fr) 2022-08-19 2024-02-22 Covestro (Netherlands) B.V. Compositions pour plaques de fibres présentant des propriétés améliorées lors d'un durcissement rapide à basse température

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