WO2020241421A1 - DÉRIVÉ D'α-1,3-GLUCANE ESTÉRIFIÉ, À CHAÎNE RAMIFIÉE - Google Patents

DÉRIVÉ D'α-1,3-GLUCANE ESTÉRIFIÉ, À CHAÎNE RAMIFIÉE Download PDF

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WO2020241421A1
WO2020241421A1 PCT/JP2020/019991 JP2020019991W WO2020241421A1 WO 2020241421 A1 WO2020241421 A1 WO 2020241421A1 JP 2020019991 W JP2020019991 W JP 2020019991W WO 2020241421 A1 WO2020241421 A1 WO 2020241421A1
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molding
glucan
esterified
glucan derivative
group
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PCT/JP2020/019991
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Japanese (ja)
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忠久 岩田
木村　聡
裕哉 深田
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国立大学法人 東京大学
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • 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

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  • the present invention relates to an ⁇ -1,3-glucan derivative introduced with a bi- or tri-branched ester chain.
  • bio-based plastics made from polysaccharides which are one of the natural polymers
  • the natural polysaccharides that have been used so far are cellulose ( ⁇ -1,4-glucan) and starch ( ⁇ -).
  • Plant-derived substances such as 1,4-glucan) and xylan ( ⁇ -1,4-xylan), and microorganisms such as curdlan ( ⁇ -1,3-glucan) and dextran ( ⁇ -1,6-glucan).
  • Such a polymer derived from a natural polysaccharide has greatly different physical properties as a polymer depending on the type of the derived sugar unit, the binding site, and the anomer.
  • ⁇ -1,3-glucan which is a polymer in which glucose is polymerized and bonded by an ⁇ -1,3-glycosidic bond
  • ⁇ -1,3-glucan exists as a structural polysaccharide on the cell wall of fungi and yeast, and is also produced by streptococci, which are oral streptococci.
  • the present inventors cloned the GtfJ gene, which is an ⁇ -1,3-glucan synthase derived from sucrose, and used the recombinant GtfJ enzyme obtained by utilizing the Escherichia coli expression system to linearize from sucrose. It has been reported that ⁇ -1,3-glucan can be synthesized (Patent Document 1). Furthermore, the present inventors have also found that by substituting the OH group in ⁇ -1,3-glucan with a linear saturated carboxylic acid, solubility and thermoplasticity in an organic solvent can be imparted. (Non-Patent Document 1). However, no synthetic example of a derivative in which a branched chain ester is introduced into an OH group in ⁇ -1,3-glucan has been reported, and elucidation of its thermal properties and mechanical properties is required.
  • the present inventors have surprisingly found that the ⁇ -1,3-glucan derivative introduced with a bifurcated or trifurcated ester chain is a conventional linear chain.
  • the film molded from the branched chain esterified ⁇ -1,3-glucan derivative has excellent physical properties such as thermal properties different from those of the derivative into which the ester chain has been introduced, and is excellent in heat resistance and thermoformability. It has been found that it has insulating properties and is suitable as an engineering plastic. Based on these new findings, the present invention has been completed.
  • each R is an acyl group having 4 to 20 carbon atoms having a bifurcated or trifurcated alkyl chain, which may be the same or different, and n is 100 to 20,000.) ;
  • ⁇ 3> The esterified ⁇ -1,3-glucan derivative according to ⁇ 1> or ⁇ 2> above, wherein the melting point is 250 to 340 ° C.
  • the glass transition temperature is in the range of 100 to 210 ° C.; ⁇ 4> The esterified ⁇ -1,3-glucan derivative according to ⁇ 3> above, wherein the glass transition temperature is 150 ° C. or higher and the difference between the melting point and the glass transition temperature is 110 ° C. or lower; ⁇ 5> The esterified ⁇ -1,3-glucan derivative according to any one of ⁇ 1> to ⁇ 4> above, wherein the viscosity is 50 kPa ⁇ s or less in the region of 200 to 280 ° C.
  • ⁇ 6> The esterified ⁇ -1,3-glucan derivative according to any one of ⁇ 1> to ⁇ 5> above, wherein the viscosity is 50 kPa ⁇ s or less in the region between the glass transition temperature and the melting point; ⁇ 7>
  • the invention ⁇ 9> A structure containing the esterified ⁇ -1,3-glucan derivative according to any one of ⁇ 1> to ⁇ 8>above; ⁇ 10> The structure is injection molding, compression molding, blow molding, inflation molding engel molding, extrusion molding, extrusion laminating molding, rotary molding, calendar molding, vacuum molding, stamping molding, spray-up molding, laminate molding, casting.
  • the structure according to ⁇ 9> above which is formed by a method, injection molding, manual stack molding, low pressure molding, transfer molding, foam molding, blow molding, or T-die method; ⁇ 11>
  • a bio-based plastic film or the like having excellent heat resistance and thermoforming properties and also having excellent mechanical properties. Materials can be provided. More specifically, in the ⁇ -1,3-glucan derivative introduced with the branched ester chain of the present invention, a higher glass transition temperature can be obtained and heat resistance is obtained as compared with the case where a linear ester having the same carbon number is introduced. You will get an improvement. In addition, since it exhibits thermal fluidity at a relatively low temperature, it can provide the effect of having excellent thermoformability in addition to improving thermal properties.
  • the melting point tends to decrease as the number of carbon atoms in the ester chain increases, whereas the branched ester chain of the present invention is used.
  • the introduced ⁇ -1,3-glucan derivative has the property of increasing the melting point by increasing the number of carbon atoms in the branched ester chain.
  • the esterified ⁇ -1,3-glucan derivative of the present invention can achieve both high heat resistance and excellent insulating properties, and is useful as a novel heat-resistant insulator.
  • FIG. 1 is a photograph of various cast films prepared from esterified ⁇ -1,3-glucan derivatives.
  • FIG. 2 is a graph showing UV-Vis spectra (transmittance) obtained for various cast films prepared from esterified ⁇ -1,3-glucan derivatives.
  • FIG. 3 is a graph in which the melting points (Tm) and glass transition temperature (Tg) of various esterified ⁇ -1,3-glucan derivatives are plotted for the number of carbon atoms in the acyl group R of the formula (1).
  • FIG. 4 is a graph showing the temperature dependence of the viscosity obtained by the capillary rheometer for various esterified ⁇ -1,3-glucan derivatives.
  • FIG. 5 is a graph showing the temperature dependence of the dielectric constants obtained for various esterified ⁇ -1,3-glucan derivatives.
  • the branched esterified ⁇ -1,3-glucan derivative according to the present invention has a structure in which glucose units are linearly polymerized by ⁇ -1,3-glycosidic bonds. , It is characterized by having a branched chain ester in the molecule as represented by the following formula (1).
  • the ⁇ -1,3-glucan derivative represented by the formula (1) is composed of an acyl group in which three hydroxyl groups (OH groups) in the glucose unit constituting the polymer have a bifurcated or trifurcated alkyl chain. It has a structure that has been esterified to form an OR group.
  • ⁇ -1,3-Glucan having an OH group (unesterified ⁇ -1,3-glucan) itself does not have thermoplasticity, but by performing such esterification, linear ⁇ -1,3- Thermoplasticity can be developed while retaining the structure of glucan. Therefore, by using the ester derivative, it can be used as a thermoplastic engineering plastic material whose shape can be freely changed by heat.
  • each R is an acyl group having 4 to 20 carbon atoms having a bifurcated or trifurcated alkyl chain, which may be the same or different, and preferably has a bifurcated or trifurcated alkyl chain. It is an acyl group having 4 to 12 carbon atoms.
  • Preferred examples of the acyl group having a bifurcated alkyl chain include, but are limited to, an isobutyryl group, an isovaleryl group, an isohexanoyl group, an isoheptanoyyl group, an isooctanoyl group, an isodecanoyl group, and an isostearoyl group. It's not a thing.
  • acyl group having a tri-branched alkyl chain examples include a pivaloyl group (tert-butylyl group), an acetyl tert-butylyl group, a propyl tert-butylyl group, and a butyryl tert-butylyl group.
  • the degree of substitution (DS) by the acyl group in R is in the range of 2.0 to 3.0, preferably in the range of 2.5 to 3.0.
  • the "degree of substitution” means the average number of hydroxyl groups substituted with the ester per glucose unit. That is, when the degree of substitution is 3, it means that all three Rs in the formula (1) are acyl groups, and all three OH groups in each glucose unit are esterified. If the degree of substitution is 1, one of the three OR groups in the formula (1) is esterified on average, and the remaining two ORs remain hydroxyl groups (that is, R is a hydrogen atom). Is shown.
  • the ester groups obtained by substituting the three OH groups (four OH groups in the terminal glucose unit) existing in each glucose unit of ⁇ -1,3-glucan may be the same or different. .. That is, in the ester group within each glucose unit, each R can be the same or different acyl group. For example, R can be randomly different ester groups, or a plurality of different ester groups can be obtained in a ratio of 2: 1 by controlling the esterification method.
  • N in the above formula (1) is 100 to 20,000, preferably 100 to 10,000.
  • the molecular weight of the esterified ⁇ -1,3-glucan derivative changes depending on the value of n, and the weight average molecular weight (Mw) of the ⁇ -1,3-glucan derivative is preferably 1. is 8 ⁇ 10 5 or more.
  • Such control of the molecular weight can be performed mainly by the type of synthase, reaction temperature, reaction time, use of a surfactant and the like when synthesizing ⁇ -1,3-glucan.
  • the degree of polydispersity (also referred to as PDI; or molecular weight distribution) represented by the ratio Mw / Mn of the weight average molecular weight (Mw) and the number average molecular weight (Mn) is preferably in the range of 2.0 to 3.0. Is.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • HPLC high performance liquid chromatography
  • SEC size exclusion chromatography
  • GPC gel permeation chromatography
  • the esterified ⁇ -1,3-glucan derivative of the present invention is characterized by having a structure in which glucose units are linearly polymerized by ⁇ -1,3-glycosidic bonds.
  • the ⁇ -1,3-glucan derivative has a completely linear structure.
  • “completely linear” means that the glucose unit constituting ⁇ -1,3-glucan does not have a branch other than the ⁇ -1,3-glycosidic bond (branch by glucose and other sugars). means.
  • a higher melting point tends to be obtained by increasing the number of carbon atoms of R in the above formula (1). This is in contrast to the fact that ⁇ -1,3-glucan derivatives introduced with a linear ester tend to have a lower melting point as the alkyl chain length is lengthened, and this is the first finding found in the present invention. Is.
  • the esterified ⁇ -1,3-glucan derivative of the present invention preferably has a glass transition temperature in the range of 100 to 210 ° C, more preferably 150 ° C or higher. Thereby, it is possible to have excellent heat resistance and thermoformability.
  • the esterified ⁇ -1,3-glucan derivative of the present invention can have a glass transition temperature of 150 ° C. or higher and a difference between the melting point and the glass transition temperature of 110 ° C. or lower.
  • the esterified ⁇ -1,3-glucan derivative of the present invention has a viscosity at a temperature (generally 350 ° C.) or lower at which decomposition of the ⁇ -1,3-glucan polymer occurs from the viewpoint of excellent thermoformability. It is preferable that it decreases and shows fluidity.
  • the esterified ⁇ -1,3-glucan derivative of the present invention has a viscosity of 50 kPa ⁇ s or less at any point in the region of 200 to 280 ° C.
  • the esterified ⁇ -1,3-glucan derivative of the present invention has a viscosity of 50 kPa ⁇ s or less at any point in the region between the glass transition temperature and the melting point.
  • the esterified ⁇ -1,3-glucan derivative of the present invention can have high insulating properties in addition to the above-mentioned excellent heat resistance. That is, the esterified ⁇ -1,3-glucan derivative of the present invention has a relative permittivity of 5.0 or less, preferably in the range of 2.0 to 4.5, and more preferably 2.5 to 3. It has a relative permittivity in the range of 0.8. Although not necessarily limited to this, in a particularly preferable embodiment, the esterified ⁇ -1,3-glucan derivative of the present invention has a glass transition temperature in the range of 100 to 210 ° C. and a relative permittivity. It can be in the range of 2.5 to 3.8.
  • the esterified ⁇ -1,3-glucan derivative of the present invention is an ⁇ -1,3-glucan having an OH group (unesterified ⁇ -1,3-glucan) using an esterification method known in the art.
  • the OH group of ⁇ -1,3-glucan can be converted to an ester group by reacting with a carboxylic acid anhydride having a desired branched alkyl chain in the presence of a base.
  • the OH group of ⁇ -1,3-glucan can be converted to an ester group by reacting with an organic acid having a desired branched alkyl chain and an acid anhydride in the presence of an acid catalyst.
  • the unesterified ⁇ -1,3-glucan as a raw material can be synthesized from sucrose using a known ⁇ -1,3-glucan synthase.
  • the ⁇ -1,3-glucan synthase is an enzyme capable of polymerizing glucose with an ⁇ -1,3-glycosidic bond while degrading sucrose, and is generally a glucan sucrase or glucosyl transferase (“Gtf” or “GtfJ”). ”) Also called.
  • an enzyme derived from Streptococcus salivarius disclosed in JP-A-2018-102249 can be used as such an ⁇ -1,3-glucan synthase.
  • the enzyme can be obtained by cloning the ⁇ -1,3-glucan synthase gene of caries bacterium, incorporating it into a plasmid vector such as Escherichia coli, and expressing it as a host.
  • the esterified ⁇ -1,3-glucan derivative of the present invention has both high heat resistance and excellent mechanical properties, a structure such as a film can be suitably produced by using the esterified ⁇ -1,3-glucan derivative.
  • the structure containing the esterified ⁇ -1,3-glucan derivative of the present invention can be molded by a method known in the art, for example, injection molding, compression molding, blow molding, inflation molding Engel molding. , Extrusion molding, extrusion laminating molding, rotary molding, calendar molding, vacuum molding, stamping molding, spray-up molding, laminate molding, casting method, injection molding, manual stack molding, low pressure molding, transfer molding, foam molding, blow molding, Alternatively, it can be molded by a method such as the T-die method.
  • the structure of the present invention is a film.
  • a method for producing a film from an esterified ⁇ -1,3-glucan derivative a method known in the art can be used.
  • a solution in which the ester derivative is dissolved in an appropriate organic solvent is applied.
  • the organic solvent include methylene chloride (dimethane), methanol, chloroform, tetrachloroethane, formic acid, acetic acid, bromoform, pyridine, dioxane, ethanol, acetone, alcohols, and aromatic compounds such as toluene, ethyl acetate and acetic acid.
  • Esters such as propyl, ethers such as tetrahydrofuran, methyl cellosolve, and ethylene glycol monomethyl ether, or combinations thereof can be used.
  • the film can also be molded by using a method such as spin coating or spraying.
  • the film can also be applied to the surface of the material by a hot melt method to bond the materials together.
  • the structure formed by the esterified ⁇ -1,3-glucan derivative of the present invention has excellent transparency.
  • a film having a thickness of about 0.05 to 0.2 mm can have a maximum transmittance of 60% or more.
  • the film of the present invention has an advantage of having transparency even in the ultraviolet region, and preferably has a transmittance of 40% or more at 300 nm.
  • the structure formed by the esterified ⁇ -1,3-glucan derivative of the present invention is It can preferably have a tensile strength of 10 MPa or more. In addition, it can have a breaking elongation of 5% or more and a Young's modulus of 0.10 GPa or more.
  • the mechanical properties can be controlled by adjusting the carbon number of R in the ester moiety. These physical properties can be measured by a method known in the art.
  • esterified ⁇ -1,3-glucan derivative of the present invention has high heat resistance and excellent thermoformability as described above, it can be applied to various plastic materials other than films. Furthermore, since the esterified ⁇ -1,3-glucan derivative of the present invention can also have high insulating properties, it can also be used as a heat-resistant insulator.
  • the unesterified ⁇ -1,3-glucan was synthesized by adding a recombinant glucosyl transferase (GtfJ enzyme) produced in Escherichia coli to a pH-adjusted sucrose solution in accordance with the disclosure of JP-A-2018-102249. ..
  • the obtained ⁇ -1,3-glucan was collected by filtration, washed with water, freeze-dried, and further dried in a vacuum dryer set at 105 ° C. for 3.5 hours.
  • ⁇ -1,3-glucan was esterified with various carboxylic acids.
  • 90 ml of acetic acid and 120 ml of trifluoroacetic anhydride (TFAA) were placed in an eggplant flask and stirred in an oil bath at 50 ° C for 5 minutes to mix.
  • Dry 3.0 g of ⁇ -1,3-glucan was added to the obtained mixed solution, and the mixture was stirred at 50 ° C. for 1 hour.
  • the recovered precipitate was dissolved in 100 ml of chloroform, reprecipitated in methanol, and recovered by filtration.
  • ester derivatives obtained by reacting with acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, isobutyric acid, isovaleric acid, isohexanoic acid, isoheptanic acid, and pivalic acid were used as ⁇ -1,3-glucan-Ac and ⁇ , respectively.
  • -1,3-glucan-Pr ⁇ -1,3-glucan-Bu, ⁇ -1,3-glucan-Va, ⁇ -1,3-glucan-Hex, ⁇ -1,3-glucan-iBu, ⁇ Notated as -1,3-glucan-iVa, ⁇ -1,3-glucan-iHex, ⁇ -1,3-glucan-iHep, ⁇ -1,3-glucan-Pi.
  • the molecular weight (Mw), polydispersity (Mw / Mn), and substitution degree (DS) calculated by GPC measurement for the synthesized esterified ⁇ -1,3-glucan derivative are shown in Table 2 below.
  • a film was prepared from the esterified ⁇ -1,3-glucan derivative obtained in Example 1 by a solvent casting method. 0.2 g of esterified ⁇ -1,3-glucan derivative was dissolved in 2 ml of dichloromethane and poured into a Teflon petri dish about 5.4 cm in diameter. The linear ester derivative was allowed to stand at room temperature for 3 days, and the branched ester derivative was allowed to stand on a hot plate at 40 ° C. for 1 hour to completely volatilize the solvent. As shown in FIG. 1, the obtained film was highly transparent in the entire visible light region.
  • the UV-Vis spectra obtained for various cast films are shown in FIG. Table 3 shows the film thickness and the maximum light transmittance in the visible light range (450-760 nm).
  • the esterified ⁇ -1,3-glucan derivative had relatively high transparency and showed the same transparency as polyethylene terephthalate and polyethylene.
  • polyethylene terephthalate has an aromatic ring, so that the transmittance is remarkably lowered, but it was found that the esterified ⁇ -1,3-glucan derivative also has a high transmittance in the ultraviolet region.
  • Thermogravimetric analysis (TGA) TGA-50 (Shimadzu Corporation) was used for the measurement.
  • the sample weight was about 2 mg.
  • the measurement was performed at a temperature range of 30 ° C-500 ° C, a heating rate of 20 ° C / min, and a nitrogen flow rate of 50 ml / s.
  • TGA Thermogravimetric analysis
  • Table 4 shows the temperatures (Td.5%, Td.50%) when the sample weight loss rate calculated from the TGA thermograms obtained for the esterified ⁇ -1,3-glucan derivative was 5% and 50%. Shown in.
  • ⁇ -1,3-glucan-Hex improved the thermal decomposition temperature by about 50 ° C
  • other ⁇ -1,3-glucan ester derivatives improved by about 90 ° C. This result is considered to indicate that the production of levoglucosan was suppressed and the thermal decomposition temperature was improved by substituting the hydroxyl group of ⁇ -1,3-glucan with an ester group.
  • DSC8500 (PerkinElmer) was used for differential scanning calorimetry. A cast film was used as the sample, and the weight was about 3 mg. After each sample was held at an isothermal temperature for 10 or 20 minutes, the melting point was evaluated in the heating process (1st run) from -30 ° C to 380 ° C. The heating rate was 20 ° C / min.
  • Holding temperature is 260 ° C for ⁇ -1,3-glucan-Ac, 250 ° C for ⁇ -1,3-glucan-Pr, ⁇ -1,3-glucan-Bu and ⁇ -1,3-glucan-Va
  • ⁇ -1,3-glucan-Hex is 200 ° C
  • ⁇ -1,3-glucan-iBu is 240 ° C
  • ⁇ -1,3-glucan-iVa and ⁇ -1,3-glucan -iHex and ⁇ -1,3-glucan-iHep were set to 280 ° C.
  • the melting point of ⁇ -1,3-glucan-Pi could be observed without heat treatment, it was not heat-treated. The measurement was carried out in a nitrogen atmosphere, and an empty aluminum pan was used as a control substance.
  • D-VA200S (IT measurement control) was used for dynamic viscoelasticity measurement.
  • a cast film with a thickness of 0.6 mm-1.0 mm was cut into a sample with a length of 7 mm and a width of 5 mm.
  • the conditions were shear mode, the temperature range was 30 ° C-380 ° C, the rate of temperature rise was 2 ° C / min, and the measurement frequency was 10 Hz.
  • Tm melting points
  • Tg glass transition points
  • the branched esterified ⁇ -1,3-glucan derivatives of the present invention ⁇ -1,3-glucan-iBu and ⁇ -1,3-glucan-Pi, have a high glass transition point exceeding 200 ° C. It was found that the temperature and the difference between the melting point and the glass transition point were within 100 ° C. It was also found that in the branched esterified ⁇ -1,3-glucan derivative of the present invention, the melting point tends to increase as the number of carbon atoms in the side chain increases. It was also found that the glass transition point decreases as the number of carbon atoms in the side chain increases, but stops decreasing at some point.
  • the increase in melting point due to the increase in side chain length is a specific behavior for a polysaccharide ester derivative. It is considered that the crystals are more densely constructed as the cause of the increase in the melting point. However, it is considered that the value of the exothermic enthalpy ⁇ H derived from the melting point decreases as the side chain becomes longer, and the crystallinity decreases. The decrease in the glass transition point is considered to be due to the decrease in the intermolecular cohesive force in the amorphous region.
  • the ⁇ -1,3-glucan derivative introduced with the linear ester tends to have a contrasting tendency that the melting point decreases as the side chain becomes longer. It was also found that the glass transition point tends to decrease almost linearly as the side chain becomes longer. It is considered that this is because the introduction of a long side chain increases the distance between the main chains and reduces the intermolecular cohesive force.
  • the branched esterified ⁇ -1,3-glucan derivative of the present invention showed a higher melting point than the linear ester derivative having a side chain having the same carbon number.
  • the branched esterified ⁇ -1,3-glucan derivative of the present invention showed a higher value than the linear ester derivative having a side chain having the same carbon number.
  • ⁇ -1,3-glucan-iBu has Tm of 257 ° C and Tg of 206 ° C
  • ⁇ -1,3-glucan-Pi has Tm of 307 ° C and Tg of 202 ° C.
  • the melt viscosity was measured with a capillary rheometer. CFT-500EX (Shimadzu Corporation) was used for the measurement. Samples include ⁇ -1,3-glucan-Ac, ⁇ -1,3-glucan-Pr, ⁇ -1,3-glucan-Bu, ⁇ -1,3-glucan-iBu, ⁇ -1,3-glucan Pellets of -iVa and ⁇ -1,3-glucan-Pi powder were used. In addition, polypropylene (PP) and polylactic acid (PLLA), which are known to have good thermoformability, were used as comparison targets. The sample mass was 1.5 g. The measurement start temperature was set near the glass transition point of each sample. After heating at the starting temperature for 300 seconds, the temperature was raised at 5 ° C / min. The measurement was finished when all the samples flowed out. The test force was 10 kgf, the die hole diameter was 1 mm, and the die length was 1 mm.
  • Figure 4 shows the temperature dependence of the viscosities obtained by the capillary rheometer for various esterified ⁇ -1,3-glucan derivatives.
  • the viscosity of ⁇ -1,3-glucan-Pi decreased sharply between the glass transition point and the melting point.
  • the viscosity at this time was lowered to the same level as the viscosity of polypropylene or polylactic acid after the melting point, and it was found that thermoforming between the glass transition point and the melting point was possible.
  • the viscosities of ⁇ -1,3-glucan-Pr and ⁇ -1,3-glucan-iBu decreased sharply after the melting point.
  • the viscosity after the melting point is lowered to the same level as the viscosity after the melting point of polypropylene, polylactic acid, etc., and there is a possibility that thermoforming can be performed.
  • an increase in viscosity was observed between the glass transition point and the melting point in all samples except ⁇ -1,3-glucan-Pi. This is considered to be due to the binding of molecular chains due to crystallization.
  • polysaccharide ester derivatives are concerned about decomposition of ester groups and coloration associated therewith at temperatures exceeding 300 ° C. Addition of antioxidants to prevent these problems and plasticizers to increase fluidity. Attempts have been made to add or introduce long-chain ester groups that themselves serve as plasticizers.
  • the introduction of petroleum-derived additives reduces the degree of biomass, and the introduction of long-chain esters reduces thermal properties. Therefore, like ⁇ -1,3-glucan-Pi introduced with a tribranched ester which is an esterified ⁇ -1,3-glucan derivative of the present invention, thermoforming is performed at a relatively low temperature between the glass transition point and the melting point. If possible, it is very useful because good moldability can be obtained without lowering the degree of biomass and thermal properties, and the above measurement results demonstrate such usefulness.
  • ⁇ -1,3-Glucan-Acetate Ac
  • ⁇ -1,3-Glucan-Hexanoate Hex
  • ⁇ -1,3- synthesized in Example 1 as esterified ⁇ -1,3-glucan derivatives Glucan-Ibutyrate (iBu) and ⁇ -1,3-Glucan-Pivalate (Pi) were used.
  • Test method Automatic equilibrium bridge method (LCR meter method)
  • Test equipment LCR meter HP4284A (manufactured by Agilent Technologies) TO-19 constant temperature bath (manufactured by Ando Electric) SE-70 type solid electrode (manufactured by Ando Electric)
  • Specimen size 5 cm Square electrode: Main electrode diameter 10.5 mm
  • Thickness measurement Micrometer Procedure: A sample was placed on a copper plate, and the main electrode was pressed with a cylindrical metal Al. The temperature was measured by a temperature sensor attached on a copper plate.
  • the relative permittivity of the two types of ⁇ -1,3-Glucan branched ester derivatives is smaller than that of the linear ester derivative ⁇ -1,3-Glucan-Ac. It was similar to ⁇ -1,3-Glucan-Hex.
  • a graph of the temperature dependence of the dielectric constant is shown in FIG.
  • the glass transition point of an aromatic polymer such as Toron (registered trademark), which is generally used as a heat-resistant insulator is 200 ° C. or higher, which is equivalent to or equal to that of an ⁇ -1,3-Glucan branched ester derivative.
  • Toron registered trademark
  • their relative permittivity is about 4, and their insulating properties are inferior to those of ⁇ -1,3-Glucan branched ester derivatives.
  • the dielectric constant of polyethylene and polypropylene is lower than that of ⁇ -1,3-Glucan branched ester derivatives, but their glass transition points are significantly lower than those of ⁇ -1,3-Glucan branched ester derivatives.
  • the ⁇ -1,3-Glucan branched ester derivative was found to be promising as a novel heat-resistant insulator.

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  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

Le problème décrit par la présente invention est de fournir un nouveau dérivé d'α-1,3-glucane dans lequel une chaîne ester ayant une ramification a été introduite. La solution selon l'invention porte sur un dérivé d'α-1,3-glucane estérifié représenté par la formule (1), ayant une structure dans laquelle des unités de glucose sont polymérisées de manière linéaire avec des liaisons α-1,3-glycosidiques. (Dans la formule, les R peuvent être identiques ou différents et représentent des groupes acyle ayant 4 à 20 atomes de carbone ayant une chaîne alkyle ramifiée ou 3-ramifiée, et n est compris entre 100 et 20 000.)
PCT/JP2020/019991 2019-05-24 2020-05-20 DÉRIVÉ D'α-1,3-GLUCANE ESTÉRIFIÉ, À CHAÎNE RAMIFIÉE WO2020241421A1 (fr)

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Citations (3)

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JPH09316133A (ja) * 1996-05-31 1997-12-09 Meito Sangyo Kk デキストランエステル共重合体
WO2018098065A1 (fr) * 2016-11-22 2018-05-31 E.I. Du Pont De Nemours And Company Esters de polyalpha-1,3-glucane et articles fabriqués à partir de ceux-ci
JP2018102249A (ja) * 2016-12-27 2018-07-05 国立大学法人 東京大学 高分子量α−１，３−グルカンの合成方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09316133A (ja) * 1996-05-31 1997-12-09 Meito Sangyo Kk デキストランエステル共重合体
WO2018098065A1 (fr) * 2016-11-22 2018-05-31 E.I. Du Pont De Nemours And Company Esters de polyalpha-1,3-glucane et articles fabriqués à partir de ceux-ci
JP2018102249A (ja) * 2016-12-27 2018-07-05 国立大学法人 東京大学 高分子量α−１，３−グルカンの合成方法

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Title
SAKARIN PUANGLEK ET AL: "Thermal and mechanical properties of tailor-made unbranched α-1,3-glucan esters with various carboxylic acid chain length", CARBOHYDRATE POLYMERS, vol. 169, August 2017 (2017-08-01), pages 245 - 254, XP055766615, DOI: 10.1016/j.carbpol.2017.04.015 *
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