WO2014062129A1 - Modification régiosélective d'une hémicellulose de xyloglucane de films barrières en biopolymère à haute performance - Google Patents

Modification régiosélective d'une hémicellulose de xyloglucane de films barrières en biopolymère à haute performance Download PDF

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WO2014062129A1
WO2014062129A1 PCT/SE2013/051222 SE2013051222W WO2014062129A1 WO 2014062129 A1 WO2014062129 A1 WO 2014062129A1 SE 2013051222 W SE2013051222 W SE 2013051222W WO 2014062129 A1 WO2014062129 A1 WO 2014062129A1
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hemicellulose
modified
oxidized
reduced
groups
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PCT/SE2013/051222
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Joby Jose KOCHUMALAYIL
Lars Berglund
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Kth Holding Ab
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D105/00—Coating compositions based on polysaccharides or on their derivatives, not provided for in groups C09D101/00 or C09D103/00
    • C09D105/14—Hemicellulose; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0057—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Xylans, i.e. xylosaccharide, e.g. arabinoxylan, arabinofuronan, pentosans; (beta-1,3)(beta-1,4)-D-Xylans, e.g. rhodymenans; Hemicellulose; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/14—Hemicellulose; Derivatives thereof

Definitions

  • the present invention relates to a modified xyloglucan and a method of preparing said xyloglucan.
  • the invention further relates to the use of said modified xyloglucan.
  • the packaging industry is a major consumer of the global plastic production.
  • plastic films are used due to favorable cost, mechanical performance, gas barrier function towards oxygen, moisture and aroma, and compatibility with other structural components (Buchner, Weisser, Vogelpohl, Baner, Brandsch & Piringer, 2000; Halek, 1988).
  • Oxygen barrier performance is sometimes the most critical parameter. Aluminium is often used as the oxygen barrier (Lange & Wyser, 2003; Leterrier, 2003).
  • synthetic polymers such as polyvinyl alcohol (PVOH), ethylene vinyl alcohol copolymer (EVOH), polyvinylidene chloride (PVDC) have successfully replaced some aluminium-based packaging solutions.
  • XG has very low oxygen permeability of the order of 0.5 - 2.0 cc ⁇ m-2 d- i kPa- i at 23 °C and 50 %RH.
  • the chemical structure of XG is described by several authors (Gidley et al., 1991; Urakawa, Mimura & Kajiwara, 2002), where XG has a cellulose backbone with ⁇ -(1 ⁇ 4)- linked D-glucopyranoses. Up to 75 % of glucose residues are being substituted at 0-6 with a-D-Xylose and part of these xylose residues are further substituted by ⁇ -D-Galactopyranose.
  • the basic repeating unit of xyloglucan comprises four oligosaccharides which differ in the number and linkages of galactose residues. They are conveniently represented as XXXG, XLXG, XXLG, and XLLG in the molar ratio: 1:0.42:2.08:6.20 (Urakawa, Mimura & Kajiwara, 2002), where X denotes xylose; L, galactose; and G, glucose at the reducing end of the oligomer (Fry et al., 1993; York, van Halbeek, Darvill & Albersheim, 1990). These oligomers are represented in Figure SI in supporting information, SI.
  • the XG chains are self-aggregated in water solutions forming highly viscous solutions (Lang & Kajiwara, 1993; Picout, Ross-Murphy, Errington & Harding, 2003). Though the polymer has shown excellent oxygen barrier performance of the order of
  • Tg glass transition temperature
  • Sorbitol was reported to be a suitable plasticizer for XG with a Tg decrease of more than 100 °C with 40 wt% sorbitol addition
  • a hemicellulose is chemically modified in order to reduce the Tg.
  • the chemical modification uses periodate oxidation of vicinal hydroxyl groups present on XG to form dialdehyde products with ring cleavage and subsequent reduction to dialcohols.
  • the schematic of the oxidation and reduction reaction of a representative sugar moiety is presented in Figure 1.
  • the galactose and part of xylose rings have three consecutive -OH groups which upon periodate oxidation can consume two moles of periodate ions resulting in dialdehyde and a formic acid molecule (Bhagavan, 2002).
  • the present invention relates to a modified hemicellulose comprising a main chain and sugar monomer side chains and wherein at least 70% of the sugar monomers are oxidized and reduced.
  • the modified hemicellulose according to the present invention may comprise at least one of the sugar monomers xylose, galactose and mannose groups and wherein at least 70% of the xylose, galactose or mannose groups are oxidized and reduced.
  • the modified hemicellulose according to the present invention comprises galactose groups and wherein at least 70% of said galactose groups are oxidized and reduced.
  • the modified hemicellulose according to the present invention comprises xylose groups and wherein at least 70% of said xylose groups are oxidized and reduced.
  • the modified hemicellulose according to the present invention comprises mannose groups and wherein at least 70% of said mannose groups are oxidized and reduced.
  • the modified hemicellulose according to the present invention comprises xylose and galactose groups and wherein at least 70% of the xylose groups are oxidized and reduced and at least 70% of the galactose groups are oxidized and reduced.
  • the present invention relates to a method of preparing the modified hemicellulose according to the present invention comprising the steps of: a. Providing hemicellulose; b. Providing an oxidizing agent; c. Providing an reducing agent: d. Mixing the hemicellulose and the oxidizing agent in order to obtain an oxidized hemicellulose; e. Optionally isolating the oxidized hemicellulose; f. Optionally washing and rinsing the isolated oxidized hemicellulose; g. Mixing the oxidized hemicellulose with the reducing agent; and h. Isolating the oxidized-reduced hemicellulose.
  • the present invention relates to a film comprising the modified hemicellulose according to the present invention.
  • the present invention relates to a modified hemicellulose obtainable by the method described above.
  • the present invention relates to a protective barrier comprising the film described above.
  • the present invention relates to an oxygen barrier comprising the film described above.
  • the present invention relates to a liquid barrier comprising the film described above
  • the present invention relates to a food container comprising the film described above. In another aspect the present invention relates to a beverage container comprising the film described above.
  • the present invention relates to the use of the modified hemicellulose according to the present invention when producing a protective barrier, an oxygen barrier, liquid barrier, food container or a beverage container.
  • Figure 1 Periodate oxidation and subsequent reduction of pyranose rings with vicinal diol groups
  • Figure 2. FTIR spectra of modified xyloglucan substrates in comparison with native XG.
  • the modified XG samples are designated dXG30, dXG60 and dXG120, the numbers denote time in minutes for periodate treatment.
  • Figure 4 Schematic of modified XG structures with different oxidation times in minutes. Designations dXG30, dXG60 and dXG120, refer to time in minutes for periodate treatment.
  • Figure 5. (A) Typical tensile stress-strain curves for xyloglucan films conditioned at room temperature and 50 %RH
  • FIG. 1 Storage modulus (E ) and tan ⁇ at 1 Hz as a function of temperature for XG and modified XG with different oxidation times. Designations dXG30, dXG60 and dXG120, refer to time in minutes for periodate treatment.
  • Figure 7. Thermogravimetric analysis (A) and first derivative thermogram (B) results for native xyloglucan and modified xyloglucans. Designations dXG30, dXG60 and dXG120, refer to time in minutes for periodate treatment.
  • Figure 8 Four basic repeating units of oligosaccharides present in tamarind seed xyloglucan
  • Figure 9 The modified XGOs obtained from enzymatic hydrolysis of the modified XG samples by periodate oxidation as depicted in MALDI-TOF MS in Figure 2.
  • the exact mass (EM) includes the mass of counter ion Na + from MALDI - TOF.
  • Hemicelluloses are embedded in the cell walls of plants, sometimes in chains that form a 'ground' - they bind with pectin to cellulose to form a network of cross-linked fibres.
  • the hemicellulose comprises a main chain and sugar monomer side chains.
  • glucose hemicellulose may contain one or more sugar monomer side chains such as xylose, mannose, galactose, rhamnose and arabinose groups.
  • Hemicelluloses include xylan, glucuronoxylan, arabinoxylan, glucomannan, and xyloglucan.
  • Xyloglucan is an interesting polysaccharide biopolymer of high molar mass obtained for example from tamarind seed waste, with excellent mechanical and gas barrier performance.
  • xyloglucan Only xyloglucan (XG) has a cellulose backbone among all known hemicelluloses.
  • an oxidation time less than 2 hours with an equimolar amount of periodate is preferably used for the complete oxidation of sugars present in XG.
  • the reaction can further be controlled by addition of smaller amount of periodate (corresponding to the side group sugars, sugar monomer side chains) and keeping it for longer time.
  • the Tg of the resulting material was reduced by more than 100°C as the pendant sugar rings were transformed. More importantly, the oxygen permeability was improved at 50 %RH, primarily due to reduced moisture adsorption compared with native XG. Moreover, at 30 minutes oxidation time the resulting material showed a superior combination of mechanical properties and oxygen barrier performance compared with petroleum-based polymers used in current industrial applications.
  • the present study provides data on the changes in chemical structure due to the modification scheme, and shows correlations between these structural changes and reductions in Tg, modulus and yield strength.
  • the achievement of regioselective modification with preserved cellulose backbone is highly significant, since this leads to favorable physical properties.
  • Prior art have failed to present a method of similar structural changes without effecting the polymer backbone.
  • Morooka et al. disclose an oxidation reduction treatment which results in ring cleavage of the polymer backbone.
  • the present polymers are a new form of cellulose derivative where the XG origin means that the use of strong solvents can be avoided.
  • the modified hemicellulose according to the present invention comprises sugar monomer side chains of which at least 70% have been oxidized and reduced. In one embodiment 80% of the sugar monomers are oxidized and reduced. These sugar monomers may be galactose, xylose or mannose groups, or a combination thereof. In one embodiment the modified hemicellulose according to the present invention may comprise at least 70% oxidized and reduced xylose and galactose groups. In one embodiment at least 85% of the sugar monomers have been oxidized and reduced. In one embodiment the modified hemicellulose may comprise at least 80 %, or at least 85%, or at least 90% or at least 95% oxidized and reduced xylose and galactose groups. In one embodiment the modified hemicellulose comprises at least 95% oxidized and reduced galactose and at least 85% oxidized and reduced xylose.
  • the modified hemicellulose has a high molecular weight despite the modification and it may have a molecular weight of at least 0.31 MDa, or at least 0.57 MDa, or at least 0.77 MDa.
  • the films from the hemicellose according to the present invention exhibit exceptional mechanical properties.
  • the strain to failure is at least 10 %, or at least 30 %, or at least 33 % preferably at least 40 %.
  • the toughness of the modified hemicellulose is very high and even if a decrease in tensile strength is seen it is still at least 17 MPa. In one embodiment it is at least 20 MPa, or at least 30 MPa. In one embodiment it is less than 40 MPa.
  • the elastic modulus is at least 291 MPa, or at least 333 MPa, or at least 800 MPa, or at least 1084 MPa. In one embodiment it is less than 2000 MPa. All measurements are performed at 23°C and 50% RH using an Instron 5944 with A 50 N load cell.
  • the hemicellulose of the present invention exhibit a Tg that is more than 100°C lower than the native hemicellulose.
  • the Tg of the hemicellulose is not higher than 180°C, preferably not higher than 170°C, or not higher than 167°C.
  • the Tg is from 145°C to 170°C.
  • the modified hemicellulose has a higher thermal stability than the native hemicellulose.
  • Oxygen permeability is an important property especially in the packing industry. Therefore the low oxygen permeability of the films from the modified hemicellulose of the present invention is an advantage.
  • the oxygen permeability is not more than 0.170 ( ⁇ m/tnAdaylkPa- 1 (dry, 23°C). In one embodiment the oxygen permeability is not more than 152 cc ⁇ m/ [m 2 .day]kPa- 1 , or not more than 150 cc ⁇ m/ [m 2 .day]kPa- 1 , or not more than 140 cc ⁇ m/ [m 2 .day]kPa- 1 (dry, 23°C). The oxygen permeability was improved in comparison with native hemicellulose at 50% RH.
  • the oxygen permeability in 50% RH and 23°C for the modified hemicellulose is less than 5 cc ⁇ m/ [m 2 -day] kPa, or less than 4 cc ⁇ m/ [m 2 -day] kPa, or less than 3 cc ⁇ m/ [m 2 -day] kPa, or less than 2 cc ⁇ m/[m 2 -day] kPa, or less than 1 cc ⁇ m/ [m 2 -day] kPa.
  • the hemicellulos is modified through an oxidation and reduction process where the hemicellulose is first oxidized using an oxidizing agent, for example a periodate, a peroxide, nitrate, a permanganate, halogens, nitrous oxide, silver oxide, osmium tetraoxide or ozone, preferably sodium periodate.
  • the oxidation step may be performed during at least 10 minutes, or at least 20 minutes, or at least 30 minutes, or at least 60 minutes, or at least 120 minutes. In one embodiment the oxidation step is performed during 10 to 30 minutes.
  • the oxidation is preferably performed in an aqueous medium using an equimolar or near equimolar amount of the oxidizing agent.
  • the oxidized hemicellulose may be precipated or isolated using any suitable technique.
  • the isolated hemicellulose may then be washed and rinsed, preferably using an alcohol such as methanol, and preferably dried.
  • the dried oxidized hemicellulose may in one embodiment be grounded prior to the reduction step.
  • the reduction is preferably also performed in an aqueous solution using a reduction agent such as a sulfite, lithium aluminum hydride, diborane, sodium amalgam, sodium borohydride, hydrazine, formic acid, ascorbic acid, phosphites, carbon monoxide and carbon, preferably sodium borohydride.
  • the oxidized-reduced hemicellulose was then isolated preferably through precipitation.
  • a film made of an oxidized and reduced hemicellulose may also be used in coating or lamination applications.
  • the film is transparent or at least essentially transparent.
  • the film has a tensile strength less than 40 MPa, an elongation above 10 %, and an elastic modulus below 2000 MPa.
  • the present invention may be used as a film which may be used to coat cardboard, paper for example.
  • the film may be used as a protective barrier in order to reduce or eliminate oxygen permeability or moisture uptake or leakage.
  • the film may be arranged or laminated on the inside and/ or the outside of a food container or a beverage container for example.
  • the film may be applied in one or more layers in order to further lower the oxygen permeability for example.
  • the film may further be used as a packing material to cover or wrap a product.
  • Xyloglucan (XG) from tamarind seed kernel powder was acquired from Innovassynth technologies Ltd., India and further purified by removing the proteinous material by centrifuging a 0.5 wt% XG solution in water. The solution was then freeze dried to obtain pure XG for further experiments. 2 g of purified XG is dissolved in 100 ml water by heating at 60 °C for lhr under continuous magnetic stirring. The oxidation and reduction steps were carried out in accordance with an earlier protocol reported for cellulose (Morooka, Norimoto & Yamada, 1989).
  • modified XG samples and native XG sample were dissolved in 40 ml distilled water at 50 °C for lhr under magnetic stirring.
  • the resulting solutions were degassed under vacuum and the solutions were then spread over Teflon-coated Petri dishes and placed on an oven shelf at 35 ° C.
  • the dried films were peeled- off, and conditioned at 23 °C, 50 %RH for two days.
  • FTIR Fourier Transform Infrared Spectroscopy
  • the buffer (0.1M NaN0 3 + 0.05M NH 4 OAc) at pH 4.5 was used as the eluent at a flow rate of 1 mL/min.
  • Analyte detection and quantification were performed by a 410 differential refractometer (Waters Corp.). Pullulan polysaccharide standards (Polymer Laboratories) were used to calibrate the system over the Mw range 180- 1660000.
  • MALDI-TOF-MS Matrix-assisted laser desorption/ ionization time-of-flight mass spectrometry (MALDI-TOF-MS) was performed on Ultraflex MALDI-TOF workstation (Bruker Daltonics, Bremen, Germany) equipped with a nitrogen laser (337 nm) and operated in positive reflector mode. About 2 mg of enzyme digested samples were dissolved in 1ml of MilliQ water and 3 ⁇ , of sample solution was mixed with 6 ⁇ , of matrix (5 mg of 2,5-dihydroxy benzoic acid in 0.5 ml acetone) and spread over a MALDI-TOF plate (Bruker Daltonics) and air-dried. The ions were accelerated with a laser power of 21 kV.
  • Tensile properties The mechanical properties of conditioned films were measured using an Instron 5944 tensile testing machine in tensile mode with a 50 N load cell. The specimens were thin rectangular strips (30 ⁇ X 5 mm) and the gauge length was 40 mm. The stress-strain curves of specimen samples were recorded at room temperature and 50 % RH at a strain rate of 10 % min 1 . Young's modulus (E) was determined from the slope of the low strain region in the vicinity of 0.05% strain. Yield stress was calculated as the intersection of the tangent of the initial elastic region and the following plastic region.
  • the moisture content (M) at a particular RH level was calculated on a dry (or total weight) basis, as indicated by the formula below:
  • Wd J where M is the moisture content (%) of material, W w is the weight of the sample in the DVS cell when the water content has reached steady state condition, and W d is the weight of the dried sample.
  • DMTA Dynamic mechanical analysis
  • Thermo gravimetric Analysis was conducted on a Mettler Toledo TGA/SDTA851 instrument. The samples were heated from 25 °C to 500 °C, using a heating rate of 5 °C/min, in a N2 flow of 50 mL/min.
  • Oxygen Permeability The oxygen transmission rate (OTR) measurements were performed with Oxygen Permeation Analyser (Systech 8001 , Systech Instruments Ltd., UK) at 23 °C using 100 % oxygen as test gas. Tests were done in dry condition and at 50 %RH. The active area of measurement was 5 cm 2 by using a steel mask. Results and discussion
  • the FTIR spectra of native XG, dialdehyde XG, and modified XG samples are shown in Figure 2.
  • XG was rapidly oxidized at room temperature to form dialdehyde XG, which was evidenced by a strong aldehyde absorption peak at 1720 cm 1 .
  • the viscosity of the solution increased significantly during the course of the reaction and stirring was hindered by the gelatinous nature of the solution after 30 min. of reaction.
  • the resulting aldehyde groups were reduced to alcohols by the use of NaBH 4 .
  • the reduction of the aldehyde groups was complete with no characteristic carbonyl absorption peak at 1720 cm 1 in the modified XG samples.
  • the pyranose ring was opened by periodate oxidation and two distinct CH groups were formed in modified XG samples as compared to native XG.
  • the CH stretching frequency at around 2898 cm 1 for native XG was well resolved into two peaks at 2873 and 2930 cm 1 for both dialdehyde XG and modified XGs.
  • the FTIR spectra also tentatively reveals that -OH stretching band at 3300 cm 1 was shifted to higher frequency range for dialdehyde XG, which indicates the fact that part of the carbonyl groups form hemiacetal linkages with -OH groups resulting in a cross-linked structure of the polymer.
  • Table 1 Carbohydrate composition of XG and modified XG samples. Data are reported as mmols of carbohydrates / 100 mg of sample. Designations dXG30, dXG60 and dXG120, refer to time in minutes for periodate treatment.
  • the side galactose and xylose groups are thus favored for oxidation compared to the glucopyranose rings in the main chain.
  • the vicinal -OH groups of the ⁇ -(1 ⁇ 4)- linked D-glucopyranoses main chain is in trans state, which is kinetically less favourable for periodate oxidation than the predominant cis conformations observed in side sugars.
  • the periodate reaction oxidizes regioselectively the side galactose and xylose groups of XG. Longer oxidation time will result in a structure with stiff cellulose chain segment and soft linkages from opened glucose units, similar to segmented block copolymers based on hard and soft segments.
  • xyloglucan oligosaccharides obtained by enzymatic hydrolysis of XG and modified XG samples are presented in Figure 3.
  • the mass peaks at m/Z values of 1409.2, 1247.2 and 1085.2 corresponds to the XGO structures XLLG, XXLG or XLXG and XXXG respectively having molecular weights in the order 1386.5, 1224,4 and 1062.4 Da respectively (see Figure SI in SI). All XGOs were oxidized during periodate treatment with none of the original XGOs present in the final product in all oxidation conditions.
  • the m/Z value of 1063.3 and 1093.3 for XXXG of dXG60 and dXG120 samples points to the fact that oxidation also occurred at one of the four glucose units, which resulted in a increase of the m/Z value by 2 units.
  • no oxidation at glucose groups was detected for the dXG30 sample and the resulting m/Z value was recorded at 1061.2 and 1091.3. This verifies the carbohydrate analysis discussed earlier, where the amount of glucose present remained constant for dXG30 sample, whereas a slight decrease was observed for dXG60 and dXG120 samples (Table 1).
  • the oxidation opens the side groups and this result in a different spatial packing of chains compared with native XG. Also, the intermolecular interactions are influenced as well as molecular mobility. The trend in decreased yield strength with increased oxidation time is strong. Yielding in ductile amorphous polymers tend to be by shear yielding (Kinloch & Young, 1983). Removal of the pendant sugar rings appears to greatly facilitate this process.
  • the molecular weights of all modified XG substrates were fairly high due to the short oxidation time used. In contrast, periodate oxidation of cellulose requires longer time and is always accompanied by severe depolymerization so that the final product has inferior properties compared to commercial polymers(Painter, 1988).
  • the native XG has a Tg of the order of 275 °C.
  • the modification reduces the glass transition temperature of native XG to 167 °C for dXG30, where all galactose and a significant part of the xylose have disappeared in the carbohydrate analysis (Table 1).
  • the Tg is reduced to around 145 °C for dXG60 and dXG120 samples ( Figure 6), where all xylose has disappeared in carbohydrate analysis (Table 1).
  • These reductions in Tg are very significant from a thermal processing point of view.
  • the decrease in Tg is a consequence of the opening of pendant sugar rings. It results in perturbations in the spatial packing of modified XG chains, changes in intermolecular interactions and increased molecular mobility.
  • the thermal stability of modified XGs was studied with TGA and the result together with the derivative thermogram is presented in Figure 7.
  • the native XG has very high thermal stability compared to other hemicelluloses(Bergstrom, Salmen, Kochumalayil & Berglund, 2011; Yang, Yan, Chen, Lee & Zheng, 2007), whereas the modified XG samples have even higher thermal stability than XG.
  • the thermal degradation of modified XG has shown two stages, the first being the pyrolysis of labile opened side groups with a maximum at about 305 °C whereas the cellulose backbone is degraded in the second stage with a maximum at 320-325 °C. The onset of degradation corresponding to labile side chains occurs at a lower temperature than for native XG.
  • modified XGs were showing thermal stability similar to cellulosic materials where the pyrolysis occurs in 315-400 °C with maximum weight loss at about 350 °C (Alen, Kuoppala & Oesch, 1996; Yang, Yan, Chen, Lee & Zheng, 2007).
  • Oxygen barrier properties This is a very significant property for packaging applications.
  • the permeabilities of modified XGs in comparison with XG are given in Table 3.
  • Oxygen permeability of modified XG is somewhat higher than for native XG in the dry state, whereas it is significantly lower than for commercial barriers in use today, such as PVOH.
  • the oxygen permeability of a material depends on solubility of oxygen in the material and diffusion of the oxygen molecules in the material. This in turn depends on the polarity and free volume of the material (Comyn, 1985; Miller & Krochta, 1997).
  • the chain packing in XG was significantly altered as a result of the opening of side groups. This is reflected in increased oxygen permeability of modified XGs compared to XG.
  • the oxygen barrier property of modified XGs was markedly improved at 50 %RH.
  • modified XGs have reduced moisture uptake compared with XG.
  • Moisture adsorption is detrimental to the oxygen barrier performance of many hydrophilic polymers at high RH since intermolecular interactions between polymer molecules are reduced due to the presence of moisture.
  • the highly advantageous oxygen permeability of XG is improved at 50 %RH for modified XG samples making this novel biopolymer an interesting candidate for packaging applications.
  • the largely preserved cellulose backbone is important as is the reduced moisture adsorption compared with XG.

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Abstract

Des polymères d'origine biologique tels que l'amidon et les hémicelluloses du bois présentent un intérêt pour des applications d'emballage, mais souffrent de limitations des performances dans des conditions humides. Le xyloglucane provenant de déchets industriels de graine de tamarin possède un potentiel, mais son Tg est trop élevé pour des applications de traitement thermique. Une modification régiosélective est par conséquent réalisée en utilisant une approche impliquant une oxydation au periodate suivie d'une réduction. Les structures polymères résultantes sont caractérisées par MALDI-TOF-MS, chromatographie d'exclusion, et analyse FTIR et des glucides. Les films sont coulés à partir d'eau et caractérisés par thermogravimétrie, analyse mécanique dynamique, sorption dynamique de vapeur d'eau, transmission d'oxygène et essais de traction. Les modifications de propriété sont interprétées à partir de modifications structurales. Ces nouveaux polymères présentent des performances nettement supérieures aux polymères à base de pétrole actuels dans l'utilisation industrielle. En outre, cette modification régiosélective peut être soigneusement contrôlée, et conduit à un nouveau type de dérivés de cellulose avec un squelette de cellulose conservé sans nécessiter de solvants nocifs.
PCT/SE2013/051222 2012-10-18 2013-10-18 Modification régiosélective d'une hémicellulose de xyloglucane de films barrières en biopolymère à haute performance WO2014062129A1 (fr)

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WO2017003364A1 (fr) * 2015-06-30 2017-01-05 Kth Holding Ab Barrières contre l'oxygène à base de fibres de cellulose modifiée
CN107082816A (zh) * 2017-05-12 2017-08-22 陕西科技大学 一种苹果渣选择性氧化纤维素衍生物及其制备方法
WO2019081677A1 (fr) * 2017-10-27 2019-05-02 Lantmännen Ek För Procédé pour la préparation d'hémicellulose modifiée
RU2747621C2 (ru) * 2017-01-18 2021-05-11 Ктх Холдинг Аб Формованный из расплава материал с высоким содержанием целлюлозных волокон
CN114369176A (zh) * 2022-01-24 2022-04-19 北京林业大学 一种木聚糖纳米晶及其制备方法

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RU2747621C2 (ru) * 2017-01-18 2021-05-11 Ктх Холдинг Аб Формованный из расплава материал с высоким содержанием целлюлозных волокон
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CN107082816B (zh) * 2017-05-12 2019-11-05 陕西科技大学 一种苹果渣选择性氧化纤维素衍生物及其制备方法
WO2019081677A1 (fr) * 2017-10-27 2019-05-02 Lantmännen Ek För Procédé pour la préparation d'hémicellulose modifiée
CN114369176A (zh) * 2022-01-24 2022-04-19 北京林业大学 一种木聚糖纳米晶及其制备方法

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