EP3328900A1

EP3328900A1 - Novel method for the polymerisation of sugars

Info

Publication number: EP3328900A1
Application number: EP16745708.4A
Authority: EP
Inventors: François JEROME; Karine DEOLIVEIRA VIGIER; Joakim DELAUX; Elodie FOURRE; Jean-Michel TATIBOUËT
Original assignee: Centre National de la Recherche Scientifique CNRS; Universite de Poitiers
Current assignee: Centre National de la Recherche Scientifique CNRS; Universite de Poitiers
Priority date: 2015-07-30
Filing date: 2016-07-28
Publication date: 2018-06-06
Also published as: CN107922511A; FR3039548A1; WO2017017243A1; FR3039548B1; US20180223001A1

Abstract

The invention relates to a method for producing a polysaccharide, comprising a step of polymerising a saccharide monomer by means of non-thermal plasma processing.

Description

NEW PROCESS FOR POLYMERIZING SUGAR

The subject of the present invention is a new process for the polymerization of sugars, making it possible to obtain hyperbranched and / or compact polysaccharides in solid form.

In research to reduce greenhouse gas emissions, the chemical industry faces major scientific and technological barriers to adapt or design new processes and commercialize new products. In order to sustainably reduce the carbon footprint while keeping in mind the imperatives of economic, societal and environmental competitiveness, the chemical industry is actively seeking new technologies.

Plasma is an ionized gas that may or may not be at thermodynamic equilibrium. This technology is widely used especially for surface treatment and the depollution of water or air. Plasma assisted polymerization is commonly used for the deposition of organic polymers on inorganic or organic substrates. However, in all cases, the use of volatile and ionizable monomers is necessary so that the latter can be in the gas phase in the plasma zone. Therefore, single monomers are mainly used among which include furans, acrylonitrile, styrene, acetylene, etc. In addition, in current processes, plasma-produced polymers are graft polymers as they develop on the surface of a solid support.

To date, the preparation of polysaccharides is essentially according to two technologies, namely: acid catalyzed polymerizations or enzymatic processes. However, these processes have many disadvantages such as obtaining secondary products such as furan compounds and humins, which requires the implementation of purification steps. In addition, the enzymatic processes are carried out in water and require an effluent treatment step.

Also, to date, there is a need for a method to avoid the aforementioned disadvantages, and in particular to overcome the purification steps after the polymerization. It is an object of the present invention to provide a rapid process for obtaining a polysaccharide and not including a step of purifying said polysaccharide.

Another object of the present invention is to provide a rapid process with high productivity.

Another object of the present invention is to provide a dry process (ie without solvent), not requiring the use of a catalyst or a solid support.

Thus, the present invention relates to a process for preparing a polysaccharide comprising a non-thermal plasma polymerization step of a saccharide monomer.

The method of the invention therefore consists in polymerizing at least one saccharide monomer by plasma treatment. This polymerization is also called plasma assisted polymerization. The specificity of the process of the invention is therefore the presence of a plasma for polymerizing sugars.

The present invention is based on the use of plasma technology to prepare polysaccharides from saccharide monomer.

According to the process of the invention, the polymerization step is not carried out in the presence of a solid support.

The method of the invention is therefore different from a plasma surface treatment method because it does not consist in placing the saccharide monomer on a support to be treated. The method of the invention makes it possible to dispense with the use of a solid support, which allows a gain in terms of efficiency because the process does not include a step of recovering and purifying the polysaccharide obtained.

A plasma is a partially or totally ionized gas. It consists of electrons and ions, possibly atoms or molecules. There are different types of plasma that can be globally differentiated between thermal plasma and non-thermal plasma.

The thermal plasma is in fact the state of a gas heated to a very high temperature (that is to say above 3000 ° C). At this temperature, the gas is strongly ionized. There is therefore simultaneous presence of free electrons and positively charged species, these different species being in a state of equilibrium, this state persisting as long as the temperature remains the same. In particular, among the thermal plasma technologies, we can mention the technologies "High Frequency" (or "High Frequency" in English) and radio-frequency plasma.

The non-thermal plasma (or cold plasma) or out of equilibrium corresponds to a transient state of ionization of the gas during which there has been formation of free electrons and thus of positively charged species, which will very quickly recombine or react to form again a neutral, non-ionized gas, the gas being mainly at a low or moderate temperature. In general, to create a non-thermal plasma, the gas must be subjected to an intense electric field in order to generate a process of acceleration of the few free electrons still present in the gases and resulting, for example, from the action of cosmic rays. These few electrons, very strongly accelerated by the electric field are then able, by inelastic shocks, to extract electrons from the gas molecules, which in turn will be accelerated. This process is called an electronic avalanche and is the initiation step of the non-thermal plasma. These highly energetic electrons are then able to activate the molecules of the gas, either by transferring some of their energy or even by breaking chemical bonds, thus making these species very reactive and therefore able to react, even if the average conditions gas would not allow it.

The way of applying the electric field will then differentiate the types of non-thermal plasma. To achieve an intense electric field, necessary for the formation of the plasma, it is necessary to apply a significant electric potential difference (often greater than 10 000V) between two electrodes.

It is possible either to generate the electric field between two electrodes of very different shapes (a tip and a plane, for example), or to isolate one or both electrodes by a dielectric material. In the case of electrodes of different geometry, we speak of "corona" plasma, or corona discharge, the plasma only developing around the electrode having the smallest radius of curvature (peak effect) and this plasma can be generated either by a DC voltage or by an AC voltage. In the case of electrodes insulated by a dielectric material, it will be called "dielectric barrier discharge" and the plasma can be generated only by the application of a variable voltage.

From these basic conformations, many different geometries have been declined, both in "corona" plasma and in dielectric barrier discharge. In the case of dielectric barrier discharges, it is also possible to mention the surface plasma which has the particularity of being generated directly to the surface of the dielectric, the electrodes then being applied on either side of this dielectric.

A third way exists, proceeding from both the electric arc and the discharge "corona", called "gliding discharge" or arc blown or "Glidarc" and comes from the observation that during the formation of an electric arc a Non-thermal plasma is briefly formed before the onset of the electric arc at the beginning of the ionization of the gas under the influence of the electric field. The device then consists of literally blowing the ions and electrons by a strong gas flow so as to always remain below the concentration of ions and electrons necessary for the formation of the electric arc. Simultaneously, a particular shape of the facing electrodes whose distance between them is not constant makes it possible to avoid a too high value of the electric field and the risk of formation of the arc. In practice, the discharge is initiated at the point where the electrodes are closest, then develops, pushed by the gas stream into the area where the electrodes progressively diverge.

Finally, it is also possible to achieve a real plasma jet by forming a non-thermal plasma near the orifice of a narrow tube in which a fast gas flow circulates. In this case, the species generated by the plasma are literally projected outside in the form of a sting equivalent to that of a torch and allow, for example, to treat surfaces of materials.

Whatever the type of plasma considered, it can be carried out under reduced pressure or at atmospheric pressure, or even at a higher pressure.

According to a preferred embodiment, the plasma used according to the invention is a non-thermal atmospheric plasma (NTAP).

Preferably, the process of the invention is carried out with a dielectric barrier discharge plasma. According to this embodiment, the energy required for the creation of the cold plasma is obtained by applying a strong electric field between two electrodes generated by the application of a high electrical voltage between these electrodes, either in the form of a pulse of voltage or alternating voltage. The dielectric barrier discharge plasma (DBD) is formed when a dielectric material (glass, quartz, ceramic, alumina ...) is placed between the two electrodes, thus avoiding the transition to the electric arc. The presence of the dielectric material also allows the formation of a more homogeneous plasma, distributed over the entire surface of the electrodes. Preferably, when a dielectric barrier discharge plasma is applied, the saccharide monomer is deposited directly between the electrodes without the presence of an additional solid support.

According to one embodiment, the saccharide monomer is a monosaccharide or a disaccharide.

Preferably, the saccharide monomer is a monosaccharide.

Monosaccharides used according to the invention include glucose, mannose, galactose or xylose.

Among the disaccharides used according to the invention, mention may be made of maltulose, isomaltulose, maltose or turanose.

Preferably, the saccharide monomer is in the form of a powder.

The polysaccharides obtained according to the process of the invention are polymers or copolymers. Indeed, the process of the invention may be a polymerization or copolymerization process.

As indicated above, the process of the invention makes it possible to synthesize polysaccharides which can also be indifferently called "sugars" or "carbohydrates".

According to the invention, the carbohydrates have the general formula C _x (H ₂ 0) _y . They may also be functionalized, in particular with -C0 ₂ H, -CHO, -NR ₂ (R = H, alkyl, aromatic), ether, phosphate or sulfate groups.

The polysaccharides obtained according to the invention are hyperbranched polymers and / or compact or related to dendritic polymers (or dendrimers). They are obtained in solid form.

The process of the invention advantageously makes it possible to obtain the polysaccharide directly and, preferably, does not comprise a subsequent purification step, contrary to the usual methods of the state of the art.

The process advantageously makes it possible to control the degree of polymerization of the polysaccharides obtained. It is therefore possible, for example, to stop the polymerization when it is desired and thus to control the degree of polymerization and the molecular weight. Preferably, the polysaccharides obtained according to the process of the invention have molar masses ranging from 1000 g / mol to 100,000 g / mol. They may have degrees of polymerization (DP) of from 3 to 400 and their hydrodynamic radii may vary from 0.8 to 40 nm.

According to one embodiment, the polymerization step is carried out at a temperature below the melting temperature of the saccharide monomer, which allows the process to be carried out at a temperature at which the saccharide monomer is solid.

Preferably, the polymerization step is carried out at a temperature between 0 ° C and 140 ° C, preferably between 0 ° C and 100 ° C.

Advantageously, the polymerization step of the process of the invention is carried out in the absence of catalyst and solvent.

The polysaccharides obtained according to the invention are solid and white products which do not require a post-treatment stage (such as effluent recycling, purification, decolorization steps, etc.) after polymerization, contrary to the processes of the state of the art.

Preferably, the polymerization step is carried out for a period of less than 30 minutes, preferably of between 5 and 20 minutes.

The method according to the invention may comprise a first step which consists in placing at least one saccharide monomer in a gaseous medium capable of forming a plasma. Preferably, the saccharide monomer is placed between two electrodes, in particular insulated from each other by a dielectric material.

According to one embodiment, the method according to the invention also comprises a step consisting in forming the plasma, in particular by heating the gaseous medium at a very high temperature (thermal plasma) or by subjecting this medium to an intense electric field (non plasma). -thermal). Preferably, the gaseous medium is subjected to an electric field of at least 5.10 ⁵ V / m

According to a preferred embodiment, the method according to the invention comprises the following steps:

placing a saccharide monomer between two electrodes insulated from each other by a dielectric material, and preferably separated by a distance of between 4 mm and 10 mm; the application of an electric field between the two electrodes greater than 5.10 ⁵ V / m to generate a plasma discharge between the two electrodes;

the formation of a polysaccharide by polymerization of said saccharide monomer; and

the possible recovery of the polysaccharide thus formed.

According to one embodiment, the voltage used for the method of the invention is between 8.5 kV and 10.5 kV.

According to the melting temperature of the saccharide monomer, as mentioned above, the process of the invention may further comprise a preliminary step of heating or cooling the reaction medium (corresponding to the space (or reactor) formed by the electrodes ).

EXAMPLES

Example 1 Polymerization of Mannose

The mannose was placed in the solid state between two 25 cm ² copper electrodes arranged in parallel and each insulated from each other by a dielectric (called DBD reactor). In order to maintain the formation of an optimal plasma, the gap between the two electrodes was set at 4 mm. The plasma was created using a bipolar generator at a voltage of 9.5 kV and a frequency of 2.2 KHz. The air flow is 100 mL / min. During the plasma treatment, mannose samples were taken after 10, 15 and 30 min and then analyzed by steric exclusion chromatography (SEC). It has thus been found that mannose is completely consumed after only 15 minutes of plasma treatment and that products of higher molecular weight are formed.

The polymerization of mannose can also be indirectly observed by X-ray diffraction analysis (XRD) and by ¹ H and ¹³ C NMR. Indeed, after plasma treatment, a significant widening of the signals is observed in both types of analyzes what is often the signature of anarchic (or disordered) polymerization.

Interestingly, it can be observed on the MALDI-TOF spectra that the polymerization actually starts after 7 min of plasma treatment. In order to obtain more information on this aspect, the conversion of mannose to Plasma treatment time was studied by SEC. In agreement with the MALDI-TOF analyzes, an induction period of 7 min was observed by SEC after which the mannose is rapidly polymerized in only 3 min. This induction period is related to the increase of the temperature of the plasma reactor (provided by the dissipated energy). In particular, this induction period corresponds to the time required for the reactor to reach 40 ° C. In order to support this hypothesis, the plasma reactor was initially cooled to -23 ° C. In this case, the time required for the reactor to reach 40 ° C. goes from 7 to 15 min which coincides with an extension of the induction period of 7 to 15 min. Similarly, when the reactor is placed at 65 ° C or 75 ° C from the start of treatment, there is no induction period and polymerization begins almost instantaneously. Finally, when the plasma reactor is successively started and then stopped in order to avoid an increase of the temperature above 40 ° C, no polymerization takes place and the mannose remains unconverted. All of these results suggest that the polymerization of mannose begins when the external temperature of the reactor reaches 40 ° C.

Analysis of mannose polymers

The mannose polymers have been analyzed by various techniques. At first, IR and RAMAN spectroscopy was used. No characteristic signal of a C = 0 or C = C group has been demonstrated thus again confirming the stability of the mannose units during the plasma treatment. Solid or liquid NMR analysis ( ¹ H and ¹³ C) confirms this observation and no characteristic peak of a C = O group was observed. These results are surprising considering that the species generated by the plasma are often used for oxidation reactions. In order to obtain additional information, the mannose polymers were analyzed by X-ray photoelectron spectrometry (XPS) which provides information on the chemical composition of a surface in a 10 nm layer. Interestingly, XPS reveals oxidation of the surface of the mannose polymer particles with the presence of 0-C = O moieties with about one -C = 0 for three mannose units. The oxidation of the surface of the mannose particles is also supported by the measurement of the pH (at 10 g / L) which decreases from 6 to 4.2 after plasma treatment in agreement with the production of a small amount of C0 ₂ H group. It should be noted that when the mannose is impregnated with an acetic acid solution so as to lower its pH to 4.2 and then treated at 50 ° C. for 15 min in the solid state, no Polymerization does not suggest that the acidic species formed on the surface of mannose are not responsible for the observed polymerization. Moreover, the mannose conversion rate remains similar, regardless of the initial plasma reactor temperature, suggesting that the activation energy is very low, which is in agreement with a radical mechanism.

In order to collect more information at a molecular level, the mannose polymers were analyzed by GC / MS using commercial standards for assignment of different peaks. More particularly, we focused on the dissincharide fraction in order to determine the different positions of the mannose involved in the polymerization. Disaccharide fraction analysis was performed at 43% conversion of mannose so that the signals could be more accurately quantified. These analyzes reveal that all of the hydroxyl groups are involved in the polymerization of mannose. However, the link between two mannose units is primarily between positions 1 and 6 (71% probability). The selectivity between the α-1, 6 and β-1, 6 bonds is respectively 27% and 44%. It is clear that the polymerization of mannose takes place in a disordered manner which rationalizes the signal widening observed by XRD and NMR.

The mannose polymers were analyzed by SEC / MALS to obtain information on the mass distribution and conformation of the mannose polymers. Elution profiles show at least three different types of populations that differ in their hydrodynamic volume, reflecting a strong polydispersity. These analyzes reveal that the molar masses of the mannose polymer range from 2 × 10 ³ to 9 × 10 ⁶ g / mol with a hydrodynamic radius ranging from 1.2 to 37.2 nm. More generally, the mannose polymers are characterized by an average molecular weight (M _w ) of 95,590 g / mol, an intrinsic viscosity (η) of 7.7 ml / g and a hydrodynamic radius (Rh) of 3.3 nm. Mannose polymers also exhibit high polydispersity (M _w / M _n) of 15 which is, again, in accordance with a disordered polymerization mannose.

The conformation of the mannose polymers was then studied by plotting Rh as a function of M _w . Rh and M _w are bound together and obey equation (1) where Rh and M _w are the hydrodynamic radius and the molar mass respectively, v _h is the hydrodynamic coefficient and K _{h is} a constant.

Rh = K _h M¾. _equate i _{0n (1)}

The hydrodynamic coefficient depends on the general shape of the macromolecules, the temperature and the macromolecule-solvent interactions. A v _h theoretical of 0.33 is obtained for a sphere, for a 0.5-0.6 shaped coil 1 and to a rod. The v _h obtained is 0.43. A linear relationship between Rh and M _w is obtained, meaning that the mannose polymers have similar conformations regardless of the degree of polymerization. A v _h value of 0.43 means that the mannose polymers adopt a conformation close to a sphere, which means that the mannose polymers have compact and / or hyperbranched structures. This statement is supported by the high solubility of mannose polymers in water (500 g / L).

Example 2 Polymerization of Other Mono- and Disaccharides

Three mono- and four disaccharides were tested. Because induction periods vary with carbohydrate, plasma treatment was arbitrarily set at 30 min in all cases. The results are summarized in Table 1 below. Remarkably, the plasma is able to polymerize all the carbohydrates tested. Only the carbohydrates liquefying in the reactor (for example fructose) could not be polymerized but a cooling of the plasma reactor should allow their polymerization. A difference in induction period was observed between the different carbohydrates, which is related to a different activation temperature. When the disaccharides were used, it was observed by MALDI / TOF that the disaccharide unit was the basic unit of the polymer suggesting that the glycosidic linkages are not broken. As observed in the case of mannose, a white powder is obtained in all cases.

The structural parameters of the recovered polymers were determined as before. The average molar mass remains similar in all cases and ranges from 2,000 to 5,500 g / mol with a polydispersity ranging from 2 to 1 1. These values are however lower than those obtained from mannose. This result is not surprising and comes from the fact that the plasma has been optimized for mannose and the parameters applied are certainly not the optimal parameters for each carbohydrate. This is the reason why the M _w and the conversions presented in Table 1 differ from that of mannose. Nevertheless, Table 1 clearly illustrates the plasma potential for the polymerization of carbohydrates under dry conditions. As previously carried out with the mannose polymers, the conformation of the polymers presented in Table 1 was studied by plotting Rh as a function of M _w . Again, a linear correlation was obtained. In particular, a v _h at around 0.40 was obtained (values ranging from 0.37 to 0.44) indicating that the polysaccharides have very close macromolecular structures. As previously mentioned, a v _h of 0.40 indicates a compact and / or hyperbranched organization of polysaccharides. The formation of hyperbranched polysaccharides also confirms a disordered polymerization of carbohydrates. However, it is interesting to note that from isomaltulose and turanose, v _h are lower, suggesting a more compact appearance and / or hyperbranched for polysaccharides corresponding agreement with the mass distribution profile. Table 1. Polymerization of various plasma-induced carbohydrates

glucose galactose xylose

maltulose Isomaltulose maltose

Duration Temp. of

Conv Mw Mn Rh η

DP polymerization induction saccharides

(g / mol) (g / mol) (nm) (ml / g) v _h (min) (° C) (%)

Glucose 15 66 70 5051 909 5.6 33 1, 4 5.0 0.41

Xylose 10 56 90 5368 1 121 5.3 45 1, 4 5.3 0.42

Galactose 20 72 62 3378 302 1 1, 2 28 0.8 3.5 0.44

Maltulose 7 40 92 3723 1746 2.1 26 1, 2 4.2 0.4 Maltose 10 56 91 2325 835 2.8 15 1, 0 4.2 0.42 Isomaltulose 15 64 87 3409 1207 2.8 25 1, 0 3.5 0.38

Turanose 30 80 80 2214 581 3.8 18 0.8 3.2 0.37

Claims

A process for preparing a polysaccharide comprising a step of non-thermal plasma polymerization of a saccharide monomer, said polymerization step not being carried out in the presence of a solid support.

The process according to claim 1, wherein the saccharide monomer is a monosaccharide or a disaccharide.

The process of claim 1 or 2, wherein the saccharide monomer is a monosaccharide.

4. A process according to any one of claims 1 to 3, wherein the polymerization step is carried out at a temperature below the melting temperature of the saccharide monomer.

5. A process according to any one of claims 1 to 4, wherein the polymerization step is carried out at a temperature between 0 ° C and 140 ° C.

6. Process according to any one of claims 1 to 5, wherein the polymerization step is carried out for a period of less than 30 minutes, preferably between 5 and 20 minutes.

7. A process according to any one of claims 1 to 6, wherein the polysaccharide has a molar mass of from 1000 g / mol to 100,000 g / mol.

8. Process according to any one of claims 1 to 7, characterized in that it does not comprise a subsequent purification step.

The method of any one of claims 1 to 8, comprising the steps of:

placing a saccharide monomer between two electrodes insulated from one another by a dielectric material;

the application of an electric field greater than 5.10 ⁵ V / m between the two electrodes to generate a plasma discharge between the two electrodes; and

- The formation of a polysaccharide by polymerization of said saccharide monomer.