EP1446662A2 - Procede et substance de determination du degre de decomposition de polymeres comportant des groupes d'amides d'acides de pontage et/ou des groupes chimiquement similaires - Google Patents

Procede et substance de determination du degre de decomposition de polymeres comportant des groupes d'amides d'acides de pontage et/ou des groupes chimiquement similaires

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Publication number
EP1446662A2
EP1446662A2 EP02774702A EP02774702A EP1446662A2 EP 1446662 A2 EP1446662 A2 EP 1446662A2 EP 02774702 A EP02774702 A EP 02774702A EP 02774702 A EP02774702 A EP 02774702A EP 1446662 A2 EP1446662 A2 EP 1446662A2
Authority
EP
European Patent Office
Prior art keywords
polyamide
groups
indicator
substance
degree
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP02774702A
Other languages
German (de)
English (en)
Inventor
Peter Eisner
Andreas MÄURER
Fritz Brandl
Michael Meuner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV filed Critical Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Publication of EP1446662A2 publication Critical patent/EP1446662A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography

Definitions

  • the invention relates to an indicator of the extent of the splitting of bonds in bridging acid amide groups and chemically analogous to these reacting groups, in particular of peptide bonds in organic, preferably native organic materials after treatment of these materials in chemical and / or physical, for example thermal or hydrolytic processes , and a method of determining the extent of this cleavage using this indicator.
  • Organic materials e.g. native organic polymers from amino acids such as native proteins, enzymes and peptides, as well as synthetically produced substances containing amide (peptide) bonds such as polyamino acids or technically modified natural products are subjected to different thermal, chemical and / or physical treatment processes or combinations of these in technology. This is done in pursuit of different goals, but what they have in common is that the properties of the polymers are irreversibly changed, e.g.
  • Waste management objectives are also possible.
  • Native organic substances containing acid amide groups e.g. slaughterhouse waste, animal carcasses, food residues, microbially active sludges, etc.
  • TTI temperature-time indicators
  • the degree of reaction conversion can be determined on the basis of a known temperature and time load. Such indicators can be helpful for chemical reactions under defined conditions or for checking the cold chain of frozen products. In complex mixtures such as In food products, biogenic waste, slaughter waste, animal carcasses or microbially active sludges, no useful data can be obtained on the completeness of the desired reaction due to the multi-layered composition with TTI.
  • TTI for determining the degree of cleavage in the materials mentioned above is its limitation to the parameters of temperature and time. This does not take into account the influence of the matrix. It must be assumed, however, that catalytic influences also act in such complex substance mixtures, which can drastically distort the course of the reaction compared to laboratory conditions.
  • the pH value plays an important role in aqueous systems for the progress of hydrolysis reactions. Since inhomogeneous distribution of complex buffer equilibria can occur, especially in biological materials, a local pH control is also hardly able to make exact predictions about the status of the bonds in the treated polymers.
  • TTI in the described form can also not make any statements about real waste engineering processes for which e.g. is interested in how likely it is that a defined percentage of a substance to be rendered harmless has actually been rendered harmless. Uncertainties can arise here from uneven flow conditions in the reactor, through variation of particle size and composition of the waste, different thermal conductivities of the waste components, formation of agglomerates or moisture "nests" in the process, changes in chemical boundary conditions (e.g. pH value) and others Parameter. The temperature-time history is then not sufficient for an assessment of the process engineering influence.
  • Indicators which could make statements about the extent of the cleavage of CN or other bonds of the acid amide groups of native or synthetic polymers from amino acids in the applications described or other complex substance mixtures are not known. In particular can Cleavage reactions of peptide bonds, which occur specifically and in a defined manner under hydrolysis conditions or thermal action, are not depicted or modeled with indicators according to the prior art. Here, too, assessments can only be made in a direct analytical way.
  • the object of the present invention is therefore to find an indicator reaction and a substance which can be used for it, with the aid of which the degree of reaction or degradation of natural or synthetic polymers which contain bridging acid amide groups and / or groups which react chemically in an analogous manner, according to chemical, thermal and / or physical Action can be reproduced, for example the degree of reaction or degradation of peptides or proteins.
  • This reaction and this substance should make it possible to describe the degree of reaction and / or degradation that materials with bridging acid amide groups and / or chemically related groups, in particular materials with peptide bonds, exhibit when they have been exposed to certain process conditions.
  • the term "bridging" is intended to express that the acid amide and related groups in question are not terminal groups, for example CONH 2 or the like, but rather groups which link molecular components in a polymerizing manner.
  • the degree of reaction or degradation is independent of which cleavage reaction (s) actually take place under the prevailing conditions, e.g. whether C-N bonds are hydrolyzed or whether - e.g. in thermal processes - oxidation reactions with other decomposition patterns or other reactions occur.
  • polyamide is to be understood as meaning compounds which consist of two or more repeating structural units which are bridged / linked via an acid amide bond.
  • the polyamide used can be dimers or oligomers containing more than two monomer units or polymers with a higher, higher or even very high number of monomer units.
  • the compounds used can be used as Solid substances or, if they have this physical physical state, can be used as liquid substances.
  • solutions, dispersions or emulsions of polyamides can be used.
  • the polyamides can be pure substances or polyamide mixtures or can also be in a mixture or combination with other substances, depending on the requirements or the requirements that result from the material to be examined.
  • polyamide is also sometimes referred to with the abbreviation PA.
  • the substance can either be exposed to the process conditions mentioned separately from the material to be examined, but it is preferably added to it.
  • Figure 1 shows the elementary composition of the monomeric building blocks caprolactam and leucine and the polymers PA-6, casein and whey protein (data from Belitz, Grosch: Fundamentals of food chemistry, 1992)
  • FIG. 2 shows the change in the average molar mass of bovine serum albumin (RSA) and polyamide-6 (PA-6) in the course of acidic hydrolysis (6% HCl, 95 ° C.)
  • FIG. 3 shows the change in the concentration of the caprolactam oligomers in polyamide-6 (PA-6) in the course of the thermal treatment (230 ° C.). The concentrations are given relative to the final concentration of the dimer (cf. FIG. 4).
  • FIG. 4 shows the change in the concentration of the caprolactam dimer in polyamide-6 (PA-6) in the course of the thermal treatment (230 ° C.). The concentrations are given relative to the final concentration
  • polyamides under different chemical / physical conditions with regard to kinetics and degree of degradation are very similar to native polymers made from amino acids (peptides, proteins), and that they are still present in traces (order of magnitude ⁇ 100ppb) in the reaction residue are detectable. If it is not an "exotic" variant, polyamides are also very inexpensive and can therefore also be used economically in larger quantities. Such substances are therefore particularly suitable for use as an indicator material for mapping processes and to be used to evaluate the effectiveness of technical systems (especially in the area of waste management).
  • Polyamide and its degradation products also have the advantage that they can only have a toxic effect in very high concentrations.
  • An indicator based on PA can also be used e.g. used in food processes to check product safety.
  • reaction processes can be modeled and the effectiveness of technical processes can be checked.
  • PA-6 in addition to the presence of peptide bonds in the macromolecule, also has a great similarity in its elemental composition with proteins and amino acids (see FIG. 1). This makes this synthetic substance highly suitable as a model for describing the behavior of acid amide bridges in chemical, physical and / or thermal reactions.
  • acid amide bridges Under the influence of chemical, physical or thermal processes, acid amide bridges, their chemical analogs and, in particular, native and synthetic polymers containing peptide bonds, react, for example those from amino acids, to form reaction products and molecular fragments. Under certain circumstances, the reaction products can in turn combine to form new compounds. Turnover and reaction kinetics in such substances are largely dominated by reactions on the acid amide bridges or the like, for example on peptide bonds.
  • the reaction to be investigated thermal cleavage, hydrolysis, ...) added polyamide, especially synthetic polyamide, or the reaction conditions of these reactions to be investigated are simulated in parallel to the actual reaction with such a polyamide as a substrate.
  • the polyamide serves as an indicator of chain breaks at any point in the acid amide groups or their analogues or at their bonds to neighboring groups in the polymer.
  • An indicator based on polyamide has the following advantages:
  • Polyamide oligomers or monomers and / or their secondary products have a low detection limit. In one embodiment of the invention, these compounds can therefore be detected directly in a favorable manner, it being sufficient to investigate a compound as the lead substance.
  • the polyamide to be used as an indicator is a defined, preferably pure or essentially pure substance or compound from which decomposition products are produced under the process conditions used, at least one of which is known or can be easily measured.
  • Synthetic polyamides are particularly suitable, especially homopolyamides of the aminocarboxylic acid type and of the diamine dicarboxylic acid type.
  • An example of this is polyamide 6, which is composed of caprolactam units or ⁇ -aminocaproic acid.
  • PA 66 nylon
  • nylon is a polymer of hexamethylene- ⁇ , ⁇ -diamine and adipic acid. If a commercially available synthetic polymer is used, there is a further advantage that the cost of the indicator is low.
  • the defined connection which is as pure as possible, can be present, for example, in the form of granules, particles or solid balls or balls with a defined particle size or particle size distribution or as a film which preferably has a defined thickness.
  • the size of the particles can be selected from very wide ranges, for example from a few ⁇ m to the centimeter range and preferably between approximately 10 ⁇ m to 10 mm, more preferably between approximately 100 ⁇ m and 1 mm, while foils are suitably a few ⁇ m up to several mm, preferably 10 ⁇ m to 1000 ⁇ m thick.
  • polyamides instead of commercially available synthetic polymers, polyamides are used which are made up of rarer, unusual or previously unknown monomers.
  • these monomers do not occur in our natural environment and / or are not or only sparingly present in the material cycle of our civilization, for example polymers of aliphatic dicarboxylic acids and diamines with chain lengths of preferably C 3 to C 15 , insofar as they are are not used in technical processes such as nylon production, synthetic polyamino acids such as polyglycine, polyalanine or dendrimers based on polyamides, which may also be made up of corresponding non-natural D-amino acids.
  • Such polyamides have a property profile tailored to the requirement as an indicator material; Their advantage is that the probability of finding their degradation products as products of the process to be examined (so-called cross-contamination by common, common polyamides) is very low. They can therefore be added to the material to be examined in a favorable manner; Since their breakdown products are easily definable, they can then be detected in the product mixture using very sensitive methods such as gas chromatography, and conversions due to the presence of these breakdown products also being dispensed with in the material to be examined. In particular, they are also suitable for use in the investigation of waste streams.
  • solutions made from oligomeric building blocks of a polyamide are used as indicators.
  • a polyamide e.g. a commercially available polyamide, extracted with water.
  • the extraction conditions can vary widely, e.g. Water or ethanol can be used as the extractant at different temperatures and with different extraction times.
  • An aqueous extraction is preferably selected, which can take place, for example, at 40-90 ° C. and with residence times between 4 and 48 hours.
  • the soluble components of the polyamide pass into the liquid phase.
  • such a solution can have a characteristic composition of monomer, dimer, trimer and possibly other, water-soluble oligomers.
  • the change in this composition during a chemical, thermal or physical treatment is an easy to analyze parameter that allows a specific statement about the existing process conditions.
  • Polyamide is suitable as an indicator of the extent of the hydrolytic cleavage of peptide bonds in polymers made from amino acids (example 1).
  • the previously described analogy between RSA and PA-6 under acidic hydrolysis conditions shows that it is possible to correlate the behavior of peptide bonds e.g. in proteins and those in PA.
  • the indicator can then be added to the process medium and, depending on its thermal / physical / chemical load over time (e.g. by changing its molecular weight distribution or by activating a dye in a polyamide shell), provides information about the real treatment conditions in the Process. On the basis of statistical evaluations of the indicator results, a statement on the degree of treatment of the target product is made possible.
  • PA can be used as an indicator for mapping hydrolysis processes e.g. in the production of gelatin and wort or in processes of protein hydrolysis for food ingredients and technical products, but also for the mapping of thermal pressure hydrolysis in the area of waste management.
  • the temperature-time load during the thermal decomposition of organic polymeric materials containing acid amide groups can also be determined with the aid of the indicator. It is known from studies in Great Britain that amino acids can be detected in the residues of thermal processes (e.g. in coal-fired plants), in the input of which protein-containing animal meal was added (http://www.environment-agency.gov.uk/business/ ippc / 107824 / bse_risks /). This proves that the thermal conversion of the proteins in technical combustion plants does not take place completely in CO 2 , water and nitrogen oxides. The concentration of the free amino acids (monomers) and the dimer and oligomer pattern of the amino acids provide information about how far the conversion of the proteinaceous material has gone.
  • PA-6 is therefore suitable as a temperature-time indicator for materials containing acid amide groups.
  • the mapping of thermal decomposition processes can be used for the detection of central chain breaks in organic materials. This is particularly relevant for the secure inactivation of infectious materials, such as prions in infected waste.
  • the procedure for experimentally adapting the indicator to the selected “product” (eg prion) and for mathematically evaluating the data obtained is carried out analogously to hydrolysis.
  • the limit for the mapping of chemical, physical or thermal reactions is the proof of the effectiveness of technical systems.
  • the indicator is primarily required that he use a yes-or-no statement to describe whether e.g. In the area of waste management, the target value is not reached and whether the technical system largely eliminates the added substances.
  • a defined limit concentration of indicator polymer, monomer, dimer or oligomer can be established.
  • the simplest limit is the requirement that none of the compounds mentioned can be detected.
  • An example of this is the incineration of waste containing protein, to which a PA indicator has been added. When the thermal oxidation process in the system under investigation has been completed, no PA or PA monomer should be detectable in the combustion residues such as slag and ash.
  • PA Under the thermal-oxidative conditions in waste incineration plants, PA should be completely mineralized. In reality, however, the combustion can be incomplete due to a short residence time (e.g. diarrhea due to incineration rust), lack of oxygen, moisture, compacting or similar effects. This lack of effectiveness of the system can be clearly demonstrated by analytical detection of monomers, oligomers and / or other defined fragments of the PA in the combustion residues down to the trace area. The effectiveness of technical systems is therefore very easy to determine and compare with other systems.
  • sample preparation techniques such as those used for. B. be used in environmental and contaminant analysis for the investigation of fly ash, slags and similar materials. This allows isolation and possibly concentration from complex matrices in the trace area.
  • the molecular weight distribution (synonymous with the chain length distribution) is an important parameter of polymeric materials.
  • Gel permeation chromatography GPC; also known as size exclusion chromatography (SEC)
  • SEC size exclusion chromatography
  • a prerequisite is a sufficient amount of sample with a complete mass balance, which suggests use in closed systems (e.g. PA in an inert hollow body made of steel or the like).
  • the indicator effect of polyamide can also be used indirectly.
  • the kinetic data of depolymerization in different environments can be used to indicate the dissolution of the polymer with the release of an enclosed indicator substance according to the prior art.
  • Defined degradation processes can be set according to the morphology of the polymer material or the surface structure in order to be able to deal with different process conditions.
  • the defined polyamide can be used in combination with a marker substance.
  • a marker substance in this embodiment, it is generally not a degradation product of the polyamide that is measured, but rather the marker substance or a property of this substance.
  • the marker substance can be selected from a large number of possible substances, such as, for example, dyes, which can absorb in different spectral ranges (UV / VIS, NIR, IR) or fluoresce, reactive dyes that react with components of the matrix when released, radioactive substances, chiral substances, salts of rare elements as well as salts or other compounds that release physical properties (e.g. conductivity, dielectric constant , ...) of the surrounding material.
  • the marker substance is chemically, physically or mechanically coupled to the polyamide.
  • the marker substance is e.g. adsorptively (e.g. via Van der Waals bonds) bound to the polyamide.
  • a chemical bond is available, for example by covalently coupling reactive groups of the marker molecules to a correspondingly derivatized polyamide.
  • the conditions are to be chosen so that the cleavage of the acid amide groups in the polyamide leads to a quantitatively comparable release of the marker substance.
  • the quantity of marker substance found quantitatively thus enables direct conclusions to be drawn about the quantity of the cleaved acid amide bonds.
  • the marker substance can be homogeneous or, where it appears advantageous, inhomogeneous in the polyamide.
  • the marker substance is hidden / encapsulated in the polyamide and is released by the degradation of the polyamide. Accordingly, the marker substance can be inserted enclosed in the particles of a granulate or in (micro) capsules with a defined particle size distribution (in the case of microcapsules, for example, in the range of about 10 ⁇ m diameter or less) or in a film with a defined thickness. If marker substance can be detected after the process to be examined has been completed, the extent of the cleavage of the acid amide bridges or chemically comparable structures in the materials to be tested can be concluded in such a way that a minimum value for the degree of cleavage can be given.
  • auxiliary substances in a thermolabile shell which is required for modeling or adapting chemical reaction conditions in different matrices.
  • an acid which is enclosed in meltable polyethylene capsules in a (larger) capsule made of PA.
  • the polyamide can be fixed on an inert carrier material or connected to it. For example, it can be applied to the surface of diatomaceous earth, alumina, silica gel or silicate particles.
  • the indicator substance of the present invention is to be kept separate from the material containing acid amide groups while being exposed to the process conditions of the material to be investigated, it is possible in a special embodiment of the invention to introduce it into an inert and dense hollow body which e.g. can consist of steel and in which a defined humidity and defined pH values and heat transfer coefficients can be set.
  • This configuration is e.g. Suitable for thermal processes in which, despite the separation, reliably identical conditions must and can be maintained.
  • the substance is introduced into a hollow body with a semipermeable wall (e.g. made of ceramic), through which a pressure, moisture and / or pH balance between the environment and the interior of the hollow body takes place.
  • the polyamide can be incorporated into a matrix made of a water-swellable polymer, preferably polyacrylate.
  • a defined humidity prevails or can be set in the matrix.
  • Example 1 PA-6 as an indicator of protein hydrolysis
  • Bovine serum albumin with an average molecular weight of approximately 68 kD and a 15 ⁇ m thick polyamide 6 film with an average molecular weight of approximately 58 kD were hydrolyzed under identical conditions (6% HCl, 95 ° C.) in an aqueous medium.
  • the changes in the mean molar masses over time were determined for RSA using HPLC and for PA-6 using GPC.
  • the course of the examination over time is shown in FIG. Taking into account the differences in the analytical Measuring method shows a high degree of similarity.
  • the similarity in the behavior of PA-6 to the investigated protein distinguishes PA in order to be used as an indicator material for changes in the peptide bonds in the hydrolysis of proteins.
  • PA-6 is also an ideal indicator for the thermal stress of substances containing acid amide groups and especially for substances with peptide bonds.

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Molecular Biology (AREA)
  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Biophysics (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Polyamides (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)

Abstract

La présente invention concerne un indicateur destiné à déterminer le degré de division de groupes d'amides d'acides de pontage et/ou de groupes réagissant de façon chimiquement similaire dans un matériau ayant contenu de tels groupes et ayant été soumis à des conditions entraînant une division au moins partielle de ces groupes. L'indicateur selon l'invention est caractérisé en ce qu'il contient ou est composé d'une substance contenant des polyamides. L'invention concerne également des possibilités d'utilisation dudit indicateur. L'invention concerne par ailleurs un procédé destiné à déterminer le degré de division de groupes d'amides d'acides de pontage et/ou de groupes réagissant de façon chimiquement similaire dans un matériau contenant de tels groupes et devant être soumis à des conditions entraînant une division au moins partielle de ces groupes.
EP02774702A 2001-10-19 2002-10-11 Procede et substance de determination du degre de decomposition de polymeres comportant des groupes d'amides d'acides de pontage et/ou des groupes chimiquement similaires Withdrawn EP1446662A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE2001152110 DE10152110A1 (de) 2001-10-19 2001-10-19 Verfahren und Substanz zum Überprüfen des Abbaugrades von Polymeren mit verbrückenden Säureamidgruppen und/oder chemisch ähnlichen Gruppen
DE10152110 2001-10-19
PCT/EP2002/011412 WO2003036292A2 (fr) 2001-10-19 2002-10-11 Procede et substance de determination du degre de decomposition de polymeres comportant des groupes d'amides d'acides de pontage et/ou des groupes chimiquement similaires

Publications (1)

Publication Number Publication Date
EP1446662A2 true EP1446662A2 (fr) 2004-08-18

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EP02774702A Withdrawn EP1446662A2 (fr) 2001-10-19 2002-10-11 Procede et substance de determination du degre de decomposition de polymeres comportant des groupes d'amides d'acides de pontage et/ou des groupes chimiquement similaires

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EP (1) EP1446662A2 (fr)
DE (1) DE10152110A1 (fr)
WO (1) WO2003036292A2 (fr)

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Publication number Priority date Publication date Assignee Title
CN113365608A (zh) * 2018-12-14 2021-09-07 诺维信公司 用于筛选酶或微生物的基于纳米粒子的方法

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FR2028928A7 (fr) * 1969-01-23 1970-10-16 Basf Ag
DE1927271A1 (de) * 1969-05-29 1970-12-03 Badische Anilin & Soda Fabrk A Verfahren zum kontinuierlichen Einarbeiten von Glasfasern in thermoplastische Kunststoffe in engem Schmelzbereich
US4208186A (en) * 1978-08-30 1980-06-17 Allied Chemical Corporation Process for monitoring time-temperature histories of perishables utilizing inactive form of diacetylene
DE3707369A1 (de) * 1987-03-07 1988-09-15 Hoechst Ag Biologisch abbaubare polymere fuer depotzubereitungen mit kontrollierter wirkstoffabgabe
US5057434A (en) * 1989-08-29 1991-10-15 Lifelines Technology, Inc. Multifunctional time-temperature indicator
DE4301809A1 (de) * 1993-01-23 1994-07-28 Huels Chemische Werke Ag Verfahren zur Einarbeitung von Weichmachern in Polyamide
NL1011637C2 (nl) * 1999-03-22 2000-09-27 Dsm Nv Werkwijze voor de bereiding van polyamide perskorrels.
NZ518835A (en) * 1999-10-11 2003-10-31 Timetemp As Full history time-temperature indicator system

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See references of WO03036292A3 *

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WO2003036292A3 (fr) 2003-09-12
DE10152110A1 (de) 2003-05-15

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