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WO2018047928A1 - Procédé de fabrication de lignine résistante à la chaleur - Google Patents

Procédé de fabrication de lignine résistante à la chaleur Download PDF

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Publication number
WO2018047928A1
WO2018047928A1 PCT/JP2017/032385 JP2017032385W WO2018047928A1 WO 2018047928 A1 WO2018047928 A1 WO 2018047928A1 JP 2017032385 W JP2017032385 W JP 2017032385W WO 2018047928 A1 WO2018047928 A1 WO 2018047928A1
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Prior art keywords
lignin
solution
resin
heat
resistant
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English (en)
Japanese (ja)
Inventor
匡貴 岡野
啓人 小山
山尾　忍
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Idemitsu Kosan Co Ltd
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Idemitsu Kosan Co Ltd
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Priority to JP2018538476A priority Critical patent/JP6955498B2/ja
Publication of WO2018047928A1 publication Critical patent/WO2018047928A1/fr
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  • the present invention relates to a heat-resistant lignin.
  • raw materials derived from biomass are attracting attention. For example, particularly remarkable in the production of bioethanol, raw materials that compete with food, such as starch and sugar, are often used as raw materials derived from biomass. For this reason, problems such as an increase in food prices and a decrease in food production have been pointed out. Therefore, at present, a technique for producing raw materials from cellulosic biomass that does not compete with food is attracting attention.
  • Cellulosic biomass that does not compete with food such as palm palm trunks and empty bunches, palm palm fruit fibers and seeds, bagasse (sugar cane (including high biomass and sugar cane)), rice straw, straw, corn cob Stem and leaves / corn residues (corn stover, corn cob, corn hull), sorghum (including sweet sorghum) residues, Jatropha seed coat and shell, cashew shell, wood chip, switchgrass, Elianthus and the like.
  • These cellulosic biomasses contain 20-30% by mass of lignin in addition to cellulose and hemicellulose.
  • lignin has been separated from cellulose and hemicellulose, recovered as black liquor, and mainly used as fuel.
  • a phenol derivative can be produced, and conversion to a chemical or bioplastic can be expected. Therefore, it is desired to extract lignin.
  • Patent Document 1 discloses a lignin derivative obtained by decomposing biomass by stirring it under high temperature and pressure in the presence of a solvent. After the decomposition treatment, a water-insoluble component is extracted with acetone, and the acetone is distilled off to obtain a lignin derivative.
  • Patent Document 2 discloses a lignin polymer comprising a 1,1-diphenylpropane unit grafted with a phenol derivative at the ⁇ -position of a phenylpropane unit of lignin and having an ester moiety in which one or more hydroxyl groups are acylated. To do. Since lignophenol derivatives are recovered as aggregates containing various chemical structures derived from natural lignin, heat treatment is performed by thermal annealing to homogenize molecular weight fractionation and structural diversity.
  • Patent Document 1 the lignin extracted in Patent Document 1 has many components having a molecular weight that is too small, and heat resistance is poor when lignin is used as a resin, and in order to improve workability, a secondary induction is separately performed in a reaction kettle. Therefore, there is a problem that lignin is not suitable for use as it is.
  • Patent Document 2 another phenolic hydroxyl group is bonded to the unreacted benzylic hydroxyl group derived from natural lignin, or the hydroxyl group is acylated and modified, so that thermal annealing is performed at a temperature of 200 ° C. or higher. And the reaction point derived from natural lignin disappears at the same time, and it is inferior in attractiveness as a material.
  • This method also requires secondary derivatization in a separate reaction vessel.
  • An object of the present invention is to provide a lignin having high heat resistance without imparting a functional group having a hydroxyl group or the like (secondary derivatization) for the purpose of improving reactivity while maintaining a structure derived from natural lignin. .
  • the present inventors have found that the above problems can be solved by a production method having the following steps, and have completed the present invention. That is, the present invention provides the following [1] to [10].
  • a raw material lignin solution is mixed with at least one solvent (a) selected from water having a volume of 1 to 50 times that of the raw material lignin solution and a hydrocarbon having a dipole moment of 0.25d or less.
  • the manufacturing method of heat-resistant lignin including the process (I) to do.
  • the raw material lignin solution is a lignin solution obtained by solubilizing lignin from plant biomass in a solvent containing an organic solvent, or a solution obtained by dissolving solid lignin in a solvent containing an organic solvent.
  • Lignin production method (II-1) The organic phase containing the heat-resistant lignin is separated from the solution obtained in the step (I), and the organic phase is concentrated. [5] The heat resistance according to any one of the above [1] to [3], which further requires the following step (II-2) when the solution obtained by the step (I) is a single phase. Lignin production method: (II-2) Solid-liquid separation of the solution. [6] (1) a dynamic viscoelasticity measuring method (DMA method) a glass transition temperature T g is 70 ° C.
  • DMA method dynamic viscoelasticity measuring method
  • the molecular weight is 3200 or more.
  • the ratio of the structural component is 7% or more and 50% or less.
  • the method for producing a heat-resistant lignin in the present embodiment includes at least one selected from a raw lignin solution, water having a capacity of 1 to 50 times that of the raw lignin solution, and a hydrocarbon having a dipole moment of 0.25 d or less. It includes the step (I) of mixing the seed solvent (a).
  • Plant biomass examples include woody biomass and herbaceous biomass.
  • woody biomass examples include conifers such as cedar, cypress, hiba, cherry, eucalyptus, beech and bamboo, and broad-leaved trees.
  • Herbaceous biomass includes palm palm trunks and empty bunches, palm palm fruit fibers and seeds, bagasse (sugar cane and high biomass sugar cane squeezed rice cake), cane top (sugar cane top and leaf), energy cane, rice straw, straw, Corn cob, foliage, residue (corn stover, corn cob, corn hull), sorghum (including sweet sorghum) residue, Jatropha seed shell and shell, cashew shell, switchgrass, Elianthus, high biomass yield crop, energy crop, etc. Is mentioned. Among these, from the viewpoint of availability and compatibility with the production method applied in the present invention, it is preferably a herbaceous biomass, palm palm empty bunch, straw, corn stover, bagasse, cane top, energy cane.
  • bagasse contains about 5 to 30% by mass of lignin.
  • lignin in bagasse contains all of H nucleus, G nucleus, and S nucleus as a basic skeleton.
  • the G nucleus has one methoxy group (—OCH 3 ) in the ortho position of the phenol skeleton, the S nucleus has two methoxy groups in the ortho position, and the H nucleus has It does not have a methoxy group at the ortho position.
  • the lignin derived from woody biomass does not contain H nuclei.
  • the plant biomass can be pulverized. Moreover, any form of a block, a chip
  • a lignin solution (i) obtained by solubilizing lignin from plant biomass in a solvent containing an organic solvent, or a solution (ii) in which solid lignin is dissolved in a solvent containing an organic solvent. can be mentioned.
  • Examples of the solution (i) as the raw material lignin solution include those obtained by solubilizing the lignin contained in the biomass in a solvent containing an organic solvent by separating the plant biomass by an existing method. Yes, it is not particularly limited. For example, a method for treating plant biomass in a mixed solvent of water and an aliphatic alcohol having 4 to 10 carbon atoms described in International Publication No. 2014/142289, or a water treatment described in Japanese Patent No. 5256679. The processing method of the plant-type biomass by can be mentioned.
  • the plant biomass is mixed with the plant biomass and the mixed solvent using a mixed solvent of water and an aliphatic alcohol (a solvent containing an organic solvent).
  • Lignin can be separated by treatment under conditions of specific charge concentration, specific reaction temperature and time.
  • the charging concentration of the plant biomass with respect to the solvent containing the organic solvent is preferably 1% by mass or more and 50% by mass or less, more preferably 3% by mass or more and 20% by mass or less, and further preferably 5% by mass or more and 18% by mass. % Or less.
  • the treatment reaction temperature is preferably 100 ° C. or higher and 350 ° C. or lower, more preferably 150 ° C. or higher and 300 ° C. or lower, and further preferably 170 ° C. or higher and 270 ° C. or lower.
  • the treatment reaction time is 0.1 hour or more and 10 hours or less, preferably 0.2 hour or more and 8 hours or less, more preferably 1 hour or more and 6 hours or less, and further preferably 1 hour or more. 3 hours or less. If it is 0.1 hour or more, the separation of lignin is sufficiently advanced, and if it is within 10 hours, the production of coke due to the decomposition of cellulose and the repolymerization of lignin can be suppressed.
  • any solid lignin can be used, and there is no particular limitation.
  • solid lignin obtained by solubilizing lignin from the above-mentioned plant biomass and then concentrating, solid lignin obtained from black liquor produced in the pulp manufacturing process, in the process of saccharifying plant biomass, cellulose and The remaining residue obtained by hydrolyzing hemicellulose and taking out the sugar can be used.
  • the organic solvent is not particularly limited, and may be any selected from saturated or unsaturated linear alcohols and branched alcohols.
  • ketones such as acetone and methyl ethyl ketone
  • ethers such as tetrahydrofuran, ethylene glycol, and polyethylene glycol may be used.
  • the organic solvent may be used alone or in combination.
  • the solvent containing the organic solvent include a mixed solvent of these organic solvents and, for example, water.
  • the raw lignin solution preferably has a lignin concentration of 1% by mass to 90% by mass in an organic solvent at 25 ° C. If the concentration of lignin at 25 ° C. is less than 1% by mass, the energy efficiency of the heat-resistant lignin production process deteriorates, which is not preferable. When the concentration of lignin at 25 ° C. exceeds 90% by mass, the degree of purification in the subsequent step (I) is inferior, which is not preferable.
  • the concentration of lignin at 25 ° C. is preferably 1% by mass to 70% by mass, more preferably 1% by mass to 50% by mass, still more preferably 2% by mass to 40% by mass, and particularly preferably 4% by mass or more. 30% by mass or less.
  • concentration of the said lignin means the density
  • Step (I) In step (I) in the present embodiment, at least selected from the raw lignin solution, water having a volume of 1 to 50 times the volume of the raw lignin solution, and a hydrocarbon having a dipole moment of 0.25 d or less. Mix with one solvent (a).
  • the said process (I) corresponds to the process of refine
  • a heat-resistant lignin having excellent heat resistance can be obtained.
  • water that can be used include tap water, industrial water, ion exchange water, and distilled water.
  • the hydrocarbon having a dipole moment of 0.25 d or less is preferably a saturated chain hydrocarbon, an unsaturated chain hydrocarbon, a saturated cyclic hydrocarbon or an unsaturated cyclic hydrocarbon having 5 to 8 carbon atoms. .
  • the “dipole moment” is a value calculated by Winstar MOPAC AMI (MOP6W70).
  • MOP6W70 Winstar MOPAC AMI
  • An example of a compound that can be used as such a hydrocarbon is shown below together with its dipole moment value.
  • the dipole moment of the hydrocarbon is preferably 0.23 d or less, more preferably 0.20 d or less.
  • the amount of at least one solvent (a) selected from hydrocarbons having a dipole moment of 0.25 d or less when mixed with the raw material lignin solution is included in the raw material lignin solution when the volume is less than 1 time
  • the light components that are produced cannot be removed sufficiently.
  • the amount of the solvent (a) exceeds 50 times by volume, the target heat-resistant lignin cannot be efficiently recovered due to an increase in waste water, an increase in the amount of hydrocarbon used, and the like.
  • the amount of the solvent (a) means the total amount of water and the plurality of types of hydrocarbon solvents.
  • the amount of the solvent (a) to be mixed with the raw lignin solution is a volume with respect to the raw lignin solution, preferably 1 to 40 times, more preferably 1 to 30 times, and even more preferably 2 to 20 times. 2 times or less, particularly preferably 2 times or more and 15 times or less.
  • the mixing method is not particularly limited as long as the lignin-resin-containing solution and the solvent (a) can be uniformly mixed.
  • the equipment used for mixing includes, for example, edge runners, stirring mixers, roll mills, cone mills, flat stone mills, speed line mills, ball mills, bead mills, sand grind mills, pearl mills, attritors, vertical mixers, kneaders, and high-speed agitators. Machine (dissolver).
  • the lignin in a raw material lignin solution can be refine
  • purified and heat-resistant lignin can be obtained.
  • light components contained in the raw lignin solution can be removed. Examples of the light component include phenols such as vanillin and sugar hyperdegradation products such as furfural, but are not particularly limited.
  • the solution temperature in the above step (I) in which the raw material lignin solution is mixed with water and at least one solvent (a) selected from hydrocarbons having a dipole moment of 0.25 d or less depends on the stability of the solution, the lignin In view of solubility in the solution, etc., it is preferably 0 ° C. or higher and 100 ° C. or lower.
  • the solution temperature is more preferably 10 ° C. or higher and 90 ° C. or lower, further preferably 20 ° C. or higher and 80 ° C. or lower, and particularly preferably 25 ° C. or higher and 70 ° C. or lower.
  • step (I) when the raw lignin solution is mixed with water and at least one solvent (a) selected from hydrocarbons having a dipole moment of 0.25 d or less, stirring is performed as necessary. You may go. In the case of stirring, static separation may be further performed as necessary.
  • the standing time is usually 1 minute or more and 120 minutes or less. If the standing time is 1 minute or longer, the heat-resistant lignin and other light components can be sufficiently separated. Moreover, 120 minutes is sufficient as the upper limit of the standing time.
  • the standing time is preferably 5 minutes to 100 minutes, more preferably 10 minutes to 60 minutes, and still more preferably 15 minutes to 30 minutes.
  • Step (II-1) or (II-2) it is preferable to perform the following step (II-1) or (II-2) depending on whether the solution obtained in step (I) has two phases or one phase.
  • the solution obtained by the step (I) has two phases, it is preferable to continue the step (II-1) after the step (I).
  • the step (II-1) the phase containing the heat-resistant lignin obtained in the step (I) is separated from the two phases, the separated phase is concentrated, and the obtained solid content is dried.
  • the solution obtained by the step (I) is separated into two phases of an aqueous phase and an organic phase, or an aqueous phase and an organic phase and a hydrocarbon phase having a dipole moment of 0.25d or less. Since the desired heat-resistant lignin is dissolved on the organic phase side, in step (II-1), the organic phase side is separated, and after the organic phase side is concentrated, the obtained solid content is dried.
  • the “organic phase side” means that when a single phase is formed by a hydrocarbon phase having a dipole moment of 0.25 d or less and an organic phase containing a heat-resistant lignin, it is separated from an aqueous phase. It means a single phase containing the organic phase.
  • the “organic phase side” means the organic phase.
  • the solution obtained by the step (I) is divided into two phases of a hydrocarbon phase having a dipole moment of 0.25 d or less and an organic phase (an organic phase other than the hydrocarbon)
  • the organic phase is separated, the organic phase is concentrated, and the obtained solid content is dried.
  • an organic phase (side) is isolate
  • step (II-2) When the solution obtained by the step (I) is a single phase, that is, when the heat-resistant lignin is precipitated as a solid, it is preferable to continue the step (II-2).
  • step (II-2) the solution is subjected to solid-liquid separation, and the obtained solid is dried.
  • the solution obtained in step (I) is a two-phase solution, light components can be removed from the raw material lignin solution by performing liquid separation in step (II-1).
  • the solution obtained by the step (I) is a single phase, the light component can be removed from the raw material lignin solution by solid-liquid separation of the solid precipitated due to the difference in solubility.
  • the heat-resistant lignin obtained by the production method of the present embodiment described above has the following physical properties: (1) in a dynamic viscoelasticity measurement (DMA method) a glass transition temperature T g is 70 ° C. or higher by, (2) The number average molecular weight is 600 or more, and (3) 5% thermogravimetric decrease starting temperature is 210 ° C. or more in simultaneous differential heat and thermogravimetric measurement (TG-DTA measurement).
  • DMA method dynamic viscoelasticity measurement
  • T g glass transition temperature
  • the number average molecular weight is 600 or more
  • thermogravimetric decrease starting temperature is 210 ° C. or more in simultaneous differential heat and thermogravimetric measurement (TG-DTA measurement).
  • the glass transition temperature T g by dynamic viscoelasticity measurement (DMA) method is not less 70 ° C. or more, preferably 75 ° C. or higher, more preferably 80 ° C. or higher, further Preferably it is 85 degreeC or more.
  • DMA dynamic viscoelasticity measurement
  • the number average molecular weight (Mn) of the heat-resistant lignin obtained by the production method of the present embodiment is 600 or more.
  • Such a number average molecular weight is obtained by measurement by gel permeation chromatography (GPC) using polystyrene as a conversion standard.
  • the lignin having a low molecular weight can be cut, so that the degree of purification of lignin is increased and lignin having excellent heat resistance can be obtained.
  • the number average molecular weight of the heat-resistant lignin is preferably 630 or more, more preferably 650 or more.
  • thermogravimetric decrease start temperature in the TG-DTA measurement of the heat-resistant lignin is 210 ° C. or higher, it can be seen that the heat-resistant lignin has high heat resistance.
  • the 5% thermogravimetric decrease starting temperature is more preferably 230 ° C or higher.
  • the heat-resistant lignin obtained by the production method of the present embodiment preferably further satisfies the following requirements (4) and (5).
  • (4) In an integral molecular weight distribution curve obtained by gel permeation chromatograph (GPC) using polystyrene as a conversion standard, the proportion of components having a molecular weight of 320 or less is 15% or less, and (5) polystyrene is a conversion standard.
  • the proportion of components having a molecular weight of 3200 or more is 7% to 50%.
  • the molecular weight of lignin is obtained by measurement by gel permeation chromatography (GPC) using polystyrene as a conversion standard.
  • the component whose molecular weight of polystyrene conversion is 320 or less, and the component whose molecular weight of polystyrene conversion is 3200 or more were calculated
  • the ratio of the constituent component having a molecular weight of 320 or less is 15% or less.
  • the proportion of components having a molecular weight of 320 or less is 15% or less, there are few monocyclic phenols (light components) having a small molecular weight.
  • the proportion of components having a molecular weight of 320 or less is preferably 11% or less, more preferably 8% or less, and even more preferably 5% or less.
  • the proportion of components having a molecular weight of 3200 or more determined from an integral molecular weight distribution curve determined by GPC is 7% or more and 50% or less. When the proportion of the constituent component having a molecular weight of 3200 or more is less than 7%, the heat resistance is inferior, which is not preferable.
  • the ratio of the structural component whose molecular weight is 3200 or more exceeds 50%, since the moldability is inferior, it is not preferable.
  • the proportion of components having a molecular weight of 3200 or more is preferably 10% or more and 50% or less, more preferably 10% or more and 30% or less.
  • the heat-resistant lignin obtained by the production method of the present embodiment can be soluble in an organic solvent and a mixed solvent of an organic solvent and water.
  • the organic solvent is not particularly limited, and examples thereof include alcohols such as methanol, ethanol and butanol, ethers such as dimethyl ether, diethyl ether and tetrahydrofuran, and ketone compounds such as acetone. In particular, it has high solubility in tetrahydrofuran and acetone (and a mixed solvent with water) and is completely soluble at room temperature.
  • the amount of 1-butanol reacted with the lignin of the heat-resistant lignin obtained by the production method of the present embodiment is preferably 10 wt% or less, more preferably 5 wt% or less, still more preferably 2.5 wt% or less, and particularly preferably 1 wt%. It is as follows. If the amount exceeds 10 wt%, if a considerable amount of lignin cannot be added to 1-butanol, the cost for 1-butanol loss increases, which is not preferable in terms of reducing economic efficiency. Although a lower limit is not specifically limited, Usually, it is 0.1 wt% or more.
  • the amount of 1-butanol reacted with lignin can be measured, for example, by the following method.
  • the lignin obtained by replacing 1-butanol used in the production method of this embodiment with 1-butanol-d 10 was analyzed using 2 H-NMR, thereby reacting with lignin.
  • the amount of butanol can be calculated.
  • 3- (trimethylsilyl) -1-propanesulfonic acid-d 6 sodium salt is added to lignin as an internal standard, and 2 H-NMR measurement is performed.
  • the heat-resistant lignin obtained by the production method according to the present embodiment can be used alone in application fields where phenol resins have been used so far. It is also possible to produce a resin composition by blending the heat-resistant lignin according to this embodiment with another phenol resin. Moreover, since the heat-resistant lignin obtained by the manufacturing method according to the present embodiment has a small amount of sulfur compounds and other light components, it can be converted into an epoxy-modified product by a known reaction for introducing an epoxy group. The epoxy-modified heat-resistant lignin can be applied to fields of use where epoxy resins have been used.
  • the heat-resistant lignin obtained by the production method according to the present embodiment can be used as an additive for thermoplastic resins.
  • the heat-resistant lignin can also be applied as a base resin raw material of a phenol resin or an epoxy resin, an epoxy resin additive (curing agent), a thermoplastic resin additive, or the like. This is due to the characteristic that heat-resistant lignin has a phenolic structural unit.
  • the heat-resistant lignin according to this embodiment can be used in combination with a curing agent such as an acid anhydride known to those skilled in the art.
  • the heat-resistant lignin obtained in the present embodiment has few light components (low molecular weight components), and therefore can be used as a base resin raw material and additive.
  • a conventionally known method can be used for use as the base resin material.
  • a resin composition in which a known crosslinking agent typified by lignin and hexamethylenetetramine is blended can be mentioned. You may mix
  • conventionally known methods such as those described in JP 2014-15579 A and International Publication No. 2016/104634 can be used. You may mix
  • the resin composition containing lignin can include two embodiments. Details will be described below.
  • the resin composition according to the first embodiment includes the heat-resistant lignin described above.
  • a resin component such as a thermoplastic resin or a thermosetting resin may be included.
  • the method for producing the resin composition in the present embodiment is not particularly limited, and the resin composition can be obtained by appropriately mixing the above-described heat-resistant lignin and other resin components. Components other than heat-resistant lignin will be described below.
  • thermoplastic resin that can be blended in the resin composition according to the present embodiment is an amorphous thermoplastic resin having a glass transition temperature of 200 ° C. or lower, or a crystalline thermoplastic resin having a melting point of 200 ° C. or lower. Is preferred.
  • thermoplastic resin examples include polycarbonate resin, styrene resin, polystyrene elastomer, polyethylene resin, polypropylene resin, polyacrylic resin (polymethyl methacrylate resin, etc.), polyvinyl chloride resin, cellulose acetate resin, polyamide resin, Low melting point polyester resins (PET, PBT, etc.) represented by polyesters of combinations of terephthalic acid and ethylene glycol, terephthalic acid and 1,4-butanediol, polylactic acid and / or copolymers containing polylactic acid, acrylonitrile-butadiene -Styrene resin (ABS resin), polyphenylene oxide resin (PPO), polyketone resin, polysulfone resin, polyphenylene sulfide resin (PPS), fluororesin, silicon resin, polyimide resin, polybenzimi Tetrazole resins, polyamide elastomers, and copolymers thereof with other monomers.
  • thermosetting resin which can be mix
  • a phenol resin a novolak-type phenol resin and a resol-type phenol resin can be mentioned, These may be used independently or may be used together.
  • other general thermosetting resins such as an epoxy resin, a polyurethane resin, a melamine resin, a urea resin, an unsaturated polyester resin, a silicone resin, and an alkyd resin can also be used.
  • lignin it has a phenolic hydroxyl group, can react with lignin, and can also be used as a diluent for lignin. Therefore, among the thermosetting resins, it is preferable to use a phenol resin. .
  • thermosetting resin which can be mix
  • the compound having a functional group capable of reacting with lignin include (e) a compound that causes an electrophilic substitution reaction with a phenol compound, (f) a compound having an epoxy group, and (g) a compound having an isocyanate group.
  • thermosetting resins (e) to (g) may be blended together with the above-described phenolic resin in consideration of physical properties such as processability of the resin composition, strength of the molded product, and heat resistance. Since lignin has a phenolic structural unit, it can be applied as a base resin raw material such as phenol resin and epoxy resin, an additive (curing agent) of epoxy resin, and the like.
  • (E) Compound that causes an electrophilic substitution reaction with a phenol compound
  • the compound that causes an electrophilic substitution reaction with a phenol compound include formaldehyde, a formaldehyde-donating curing agent compound, or a formaldehyde equivalent compound.
  • formaldehyde a formaldehyde-donating curing agent compound
  • formaldehyde equivalent compound a formaldehyde equivalent compound.
  • hexamethylenetetramine, hexaformaldehyde, and paraformaldehyde can be used.
  • (F) Compound having an epoxy group
  • the compound having an epoxy group belongs to a category referred to as a so-called epoxy resin.
  • examples include 2,2-bis (4-hydroxyphenyl) propane (referred to as bisphenol A), bis (2-hydroxyphenyl) methane (referred to as bisphenol F), 4,4′-dihydroxydiphenyl sulfone.
  • a curing accelerator can be appropriately added depending on the purpose of promoting the curing reaction.
  • Specific examples include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5,4,0).
  • Tertiary amines such as undecene-7, phosphines such as triphenylphosphine, quaternary ammonium salts such as tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, triphenylbenzyl
  • quaternary phosphonium salts such as phosphonium salts, triphenylethylphosphonium salts, and tetrabutylphosphonium salts, and metal compounds such as tin octylate.
  • the counter ion of the quaternary phosphonium salt include halogen, organic acid ion, hydroxide ion and the like, and organic acid ion and hydroxide ion are particularly preferable.
  • (G) Compound having an isocyanate group
  • examples of the compound having an isocyanate group include polyisocyanates, or compounds obtained by reacting polyisocyanates and polyols.
  • Polyisocyanates include aromatic polyisocyanates such as tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), polymeric MDI (MDI-CR), carbodiimide-modified MDI (liquid MDI), and norbornane diisocyanate (NBDI).
  • Aliphatic polyisocyanates such as isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 4,4′-methylene-bis (cyclohexyl isocyanate) (hydrogenated MDI), xylylene diisocyanate (XDI), and blocked isocyanates.
  • IPDI isophorone diisocyanate
  • HDI hexamethylene diisocyanate
  • MDI 4,4′-methylene-bis (cyclohexyl isocyanate)
  • XDI xylylene diisocyanate
  • blocked isocyanates Can be mentioned.
  • tolylene diisocyanate (TDI) and 4,4′-diphenylmethane diisocyanate (MDI) are preferably used.
  • a curing accelerator can be appropriately added to the resin composition according to the present embodiment according to the purpose of promoting the curing reaction.
  • the curing accelerator include zirconium and aluminum organometallic catalysts, dibutyltin laurate, DBU phenol salts, octylates, amines, imidazoles, and the like.
  • zirconium and aluminum organometallic catalysts include zirconium and aluminum organometallic catalysts, dibutyltin laurate, DBU phenol salts, octylates, amines, imidazoles, and the like.
  • aluminum sec-butyrate, aluminum ethyl acetoacetate diisopropylate, zirconium tributoxyacetylacetonate, zirconium tetraacetylacetonate and the like are particularly preferable.
  • the resin composition according to this embodiment may contain a resin such as a urea resin, a melamine resin, a silicone resin, an unsaturated polyester resin, an alkyd resin, and a polyurethane resin.
  • a resin such as a urea resin, a melamine resin, a silicone resin, an unsaturated polyester resin, an alkyd resin, and a polyurethane resin.
  • the resin composition according to the present embodiment may include a filler.
  • the filler may be an inorganic filler or an organic filler.
  • the inorganic filler for example, silica powder such as spherical or crushed fused silica, crystalline silica, alumina powder, glass powder, glass fiber, glass flake, mica, talc, calcium carbonate, alumina, hydrated alumina, nitriding Examples thereof include boron, aluminum nitride, silicon nitride, silicon carbide, titanium nitride, zinc oxide, tungsten carbide, and magnesium oxide.
  • the organic filler examples include carbon fiber, aramid fiber, paper powder, cellulose fiber, cellulose powder, rice husk powder, fruit shell / nut powder, chitin powder, and starch.
  • the inorganic filler and the organic filler may be contained singly or in combination, and the content is determined according to the purpose. When the inorganic filler and / or the organic filler is contained, it is desirable that the content of the inorganic filler and / or the organic filler is an appropriate amount in order to obtain good physical properties and moldability.
  • thermoplastic resins include resins in which polar groups are introduced by adding maleic anhydride, epoxy, or the like to thermoplastic resins, such as maleic anhydride-modified polyethylene resins, maleic anhydride-modified polypropylene resins, and various commercially available phases. A solubilizer may be used in combination.
  • the surfactant examples include linear fatty acids such as stearic acid, palmitic acid, and oleic acid, and branched / cyclic fatty acids with rosins, but are not particularly limited thereto.
  • additives that can be blended include a flexibilizer, a heat stabilizer, an ultraviolet absorber, a flame retardant, an antistatic agent, an antifoaming agent, a thixotropic agent, a release agent, and an antioxidant.
  • a molded product can be obtained from the resin composition containing the heat-resistant lignin.
  • the method for molding into a predetermined shape is not particularly limited as long as the resin composition can be molded.
  • examples of the method for molding into a predetermined shape include a compression molding method, an injection molding method, a transfer molding method, an intermediate molding method, and an FRP molding method.
  • examples of the method for molding into a predetermined shape include an extrusion molding method and an injection molding method.
  • Examples of molded products include cured resin compositions containing heat-resistant lignin and cross-linking agents, and various fillers and industrially obtained general phenol resins as needed. Examples thereof include those cured after being molded into a predetermined shape, those molded after being cured, and those obtained by molding a resin composition obtained by mixing heat-resistant lignin with a thermoplastic resin. Molded articles of such resin compositions include: heat insulating materials for housing, electronic parts, resin for flack sand, resin for coated sand, resin for impregnation, resin for lamination, resin for FRP molding, automobile parts, reinforcement of automobile tires It can be used for materials, OA equipment, machines, information communication equipment, industrial materials and the like.
  • the resin composition in the second embodiment includes the following steps: Adding a resin to the raw material lignin solution to obtain a lignin-resin-containing solution (IA); At least one solvent selected from the above lignin-resin-containing solution and a hydrocarbon having a volume of 1 to 50 times that of the lignin-resin-containing solution and having a dipole moment of 0.25 d or less.
  • a lignin solution (i) obtained by solubilizing lignin from plant biomass in a solvent containing an organic solvent, or a solution (ii) in which solid lignin is dissolved in a solvent containing an organic solvent can be mentioned. Details, preferred embodiments, and the like are the same.
  • the amount of the resin in the step (IA) is usually preferably 10 to 2000 with respect to 100 parts by mass of the lignin solid content of the raw material lignin solution. Parts by mass, more preferably 20 to 1000 parts by mass, and still more preferably 50 to 500 parts by mass.
  • the resin used in the step (IA) is not particularly limited as long as it is a resin that dissolves in the raw material lignin solution, and may be a thermosetting resin or a thermoplastic resin.
  • a resin component it is as above-mentioned, and the preferable thing about each resin component is also the same.
  • a thermosetting resin In view of a molding method for molding a molded product suitable for a lignin-containing resin composition, it is more preferable to use a thermosetting resin.
  • a phenol resin such as the above-described novolac phenol resin or resol phenol resin can be used.
  • other general thermosetting resins and thermoplastic resins described above can also be used.
  • lignin Like lignin, it has a phenolic hydroxyl group, can react with lignin, and can also be used as a diluent for lignin. Therefore, among these resins, phenol resins are preferred, and novolak phenol resins and resoles are used. More preferred is at least one phenol resin selected from the group consisting of phenolic phenol resins.
  • the lignin-containing resin composition Light components derived from the raw lignin solution cannot be sufficiently removed.
  • the amount of the solvent (a ′) exceeds 50 times by volume, the target heat-resistant lignin cannot be efficiently recovered due to an increase in waste water, an increase in the amount of hydrocarbon used, and the like.
  • the amount of the solvent (a ′) means the total amount of water and the plurality of types of hydrocarbon solvents.
  • At least one solvent (a ′) selected from water and hydrocarbons having a dipole moment of 0.25 d or less used in step (IB) is the same as the solvent (a) described above.
  • the amount of the solvent (a ′) relative to the lignin-resin-containing solution is preferably 1 to 40 times, more preferably 1 to 30 times, further preferably 2 to 20 times, and particularly preferably 2 times. It is not less than 15 times and not more than 15.
  • the solution temperature in the step (IB) of mixing the lignin-resin-containing solution with at least one solvent (a ′) selected from the group consisting of water and a hydrocarbon having a dipole moment of 0.25 d or less is the stability of the solution.
  • solubility of lignin in the solution, etc. it is preferably 0 ° C. or higher and 100 ° C. or lower.
  • the solution temperature is more preferably 10 ° C. or higher and 90 ° C. or lower, further preferably 20 ° C. or higher and 80 ° C. or lower, and particularly preferably 25 ° C. or higher and 70 ° C. or lower.
  • the mixing method is not particularly limited as long as the lignin-resin-containing solution and the solvent (a ′) can be mixed uniformly.
  • the equipment used for mixing includes, for example, edge runners, stirring mixers, roll mills, cone mills, flat stone mills, speed line mills, ball mills, bead mills, sand grind mills, pearl mills, attritors, vertical mixers, kneaders, and high-speed agitators. Machine (dissolver).
  • step (IB) when mixing the lignin-resin containing solution with water and at least one solvent (a ′) selected from hydrocarbons having a dipole moment of 0.25 d or less, Stirring may be performed. In the case of stirring, static separation may be further performed as necessary.
  • the standing time is usually 1 minute or more and 120 minutes or less. If the standing time is 1 minute or longer, other light components derived from the raw material lignin solution can be sufficiently separated from the lignin-containing resin composition. Moreover, 120 minutes is sufficient as the upper limit of the standing time.
  • the standing time is preferably 5 minutes to 100 minutes, more preferably 10 minutes to 60 minutes, and still more preferably 15 minutes to 30 minutes.
  • the light component By passing through the step (IB), the light component can be separated from the lignin contained in the lignin-resin-containing solution.
  • the light component include phenols such as vanillin and sugar hyperdegradation products such as furfural, but are not particularly limited.
  • step (IIA) or (IIB) it is preferable to perform the following step (IIA) or (IIB) depending on whether the mixed solution obtained in step (IB) has two phases or one phase.
  • the solution obtained by the step (IB) has two phases, it is preferable to continue the step (IIA).
  • the step (IIA) the phase containing the heat-resistant lignin obtained in the step (IB) is separated from the two phases, and the separated phase is concentrated, and then the obtained solid content is dried.
  • the solution obtained by the step (IB) is divided into two phases of an aqueous phase and an organic phase, or an aqueous phase and an organic phase and a hydrocarbon phase having a dipole moment of 0.25d or less.
  • the organic phase side is separated, and after the organic phase side is concentrated, the obtained solid content is dried.
  • the “organic phase side” means that when a single phase is formed by a hydrocarbon phase having a dipole moment of 0.25 d or less and an organic phase containing a heat-resistant lignin, it is separated from an aqueous phase. It means a single phase containing the organic phase.
  • the “organic phase side” means the organic phase.
  • the solution obtained in the step (IB) is separated into two phases of a hydrocarbon phase having a dipole moment of 0.25 d or less and an organic phase (an organic phase other than the hydrocarbon)
  • the organic phase is separated, the organic phase is concentrated, and the obtained solid is dried.
  • an organic phase (side) is isolate
  • step (IIB) When the solution obtained by the step (IB) is one phase, that is, when the target lignin-containing resin composition is precipitated as a solid, it is preferable to continue the step (IIB).
  • step (IIB) the solution is subjected to solid-liquid separation, and the obtained solid is dried.
  • the solution obtained in the step (IB) is a two-phase solution, the light component can be removed from the lignin-containing resin composition by performing liquid separation in the step (IIA).
  • the solution obtained by the step (IB) is a single phase, the light component can be removed from the lignin-containing resin composition by solid-liquid separation of the solid precipitated due to the difference in solubility.
  • the lignin reactive compound, curing accelerator, inorganic filler, organic filler and other additives that can be used in the method for producing a lignin-containing resin composition according to the second embodiment of the present invention are the It is the same as that which can be used in the lignin containing resin composition concerning one embodiment.
  • the above lignin reactive compound or the like may be added together with the resin in the step (IA), or the above lignin reactive compound or the like is added between the step (IA) and the step (IB) described later. A process may be provided.
  • the above lignin-reactive compound or the like may be added after the step (IIA) or the step (IIB).
  • the molded product using the lignin-containing resin composition according to the second embodiment, the molding method and its use are the same as those of the lignin-containing resin composition according to the first embodiment, and are as described above.
  • the mass of the mixed solvent consisting of water and butanol was 300 g.
  • the charged concentration of bagasse was 10% by mass with respect to the mixed solvent.
  • the temperature was raised to 200 ° C., and a decomposition reaction was performed at a reaction temperature of 200 ° C. for 2 hours.
  • the reaction time was the elapsed time after reaching 200 ° C.
  • the temperature was measured with a thermocouple.
  • the internal pressure during the reaction was 1.9 MPa.
  • the SUS batch-type apparatus was cooled to near room temperature, and then the entire contents were taken out and filtered to separate the biomass residue and the liquid phase. Further, the aqueous phase and 1-butanol phase of the filtrate were subjected to liquid / liquid separation with a separatory funnel. The separated 1-butanol phase was used as a raw lignin solution.
  • the solid content (lignin) concentration was determined by separately concentrating the butanol phase and found to be 50 g / L-butanol phase.
  • the mass of the mixed solvent consisting of water and butanol was 300 g.
  • the charged concentration of bagasse was 10% by mass with respect to the mixed solvent.
  • the temperature was raised to 200 ° C., and a decomposition reaction was performed at 200 ° C. for 2 hours.
  • the reaction time was the elapsed time after reaching 200 ° C.
  • the temperature was measured with a thermocouple.
  • the internal pressure during the reaction was 1.9 MPa.
  • the SUS batch-type device was cooled to near room temperature, and then the entire contents were taken out and filtered to separate the biomass residue and the liquid phase. Further, the aqueous phase and 1-butanol phase of the filtrate were subjected to liquid / liquid separation with a separatory funnel. The separated butanol phase was concentrated and vacuum dried at 125 ° C. to obtain 6.5 g of a solid (lignin).
  • Example 1 14 mL of the raw material lignin solution (water + butanol phase) obtained in Production Example 1 (the concentration of lignin is 6 mass%, 0.7 g of lignin is dissolved in a mixed solvent of 14 mL of butanol + water) is added with 178 mL of ion-exchanged water. added. The amount of water was 12.7 times that of the raw lignin solution.
  • the resulting mixed solution was stirred at 25 ° C. for 15 minutes.
  • the liquid phase after stirring was one phase.
  • the solid was separated by filtration, and the obtained solid was dried at 125 ° C.
  • the molecular weight, the thermogravimetric decrease starting temperature, and the glass transition point were determined for the solid matter. The results are shown in Table 2.
  • Example 2 10 mL of ion-exchanged water was added to 10 mL of the lignin solution obtained in Production Example 1 (the concentration of lignin was 6 wt%, 0.5 g of lignin was dissolved in a mixed solvent of 10 mL of butanol + water). The amount of water was 1 time with respect to the raw material lignin solution.
  • the mixed solution was stirred at 50 ° C. for 15 minutes.
  • the liquid phase after stirring was two phases.
  • the liquid phase was filtered, and no solid remained on the filter paper.
  • the aqueous phase and the butanol phase were separated, the butanol phase was concentrated, and the resulting solid was dried at 125 ° C.
  • the molecular weight, the thermogravimetric decrease starting temperature, and the glass transition point were determined for the solid matter. The results are shown in Table 2.
  • Example 3 The same operation as in Example 2 was performed except that the amount of ion-exchanged water was 20 mL. The amount of water was twice that of the raw lignin solution. The results are shown in Table 2.
  • Example 4 The same operation as in Example 2 was performed except that the amount of ion-exchanged water was 70 mL. The amount of water was 7 times that of the raw lignin solution. The results are shown in Table 2.
  • Example 5 The same operation as in Example 2 was performed except that the amount of ion-exchanged water was 20 mL and the mixture was stirred at 70 ° C. The amount of water was twice that of the raw lignin solution. The results are shown in Table 2.
  • Example 6 The same operation as in Example 2 was performed except that the amount of ion-exchanged water was 70 mL and the mixture was stirred at 70 ° C. The amount of water was 7 times that of the raw lignin solution. The results are shown in Table 2.
  • Example 7 The same operation as Example 1 was performed except stirring at 70 degreeC. The amount of water was 13 times that of the raw lignin solution. The results are shown in Table 3.
  • Example 8 1 g of the solid obtained in Production Example 2 was completely dissolved in 30 mL of acetone. The concentration of lignin in the solution was 4% by mass. To this acetone solution was added 30 mL of ion-exchanged water (1 time with respect to the raw lignin solution). The mixed solution was stirred at 25 ° C. for 15 minutes, and the liquid phase after stirring was one phase. The solid was separated by filtration, and the obtained solid was dried at 125 ° C. The molecular weight, the thermogravimetric decrease starting temperature, and the glass transition point were determined for the solid matter. The results are shown in Table 3. Example 9 The same operation as in Example 8 was performed except that the amount of ion-exchanged water was changed to 60 mL.
  • Example 10 The same operation as in Example 8 was performed except that the amount of ion-exchanged water was 90 mL. The amount of water was three times that of the raw lignin solution. The results are shown in Table 3.
  • Example 11 140 mL of heptane was added to 14 mL of the lignin solution (water + butanol phase) obtained in Production Example 1 (the concentration of lignin was 6 mass%, 0.7 g of lignin was dissolved in a mixed solvent of 14 mL of butanol + water). The amount of heptane was 10 times that of the raw lignin solution.
  • Example 12 1 g of the solid obtained in Production Example 2 was completely dissolved in 30 mL of acetone. The concentration of lignin in the solution was 4% by mass. 30 mL of heptane (1 time with respect to the raw material lignin solution) was added to this acetone solution. The mixed solution was stirred at 25 ° C. for 15 minutes, and the liquid phase after stirring was one phase. The solid was separated by filtration, and the obtained solid was dried at 125 ° C. The molecular weight, the thermogravimetric decrease starting temperature, and the glass transition point were determined for the solid. The results are shown in Table 3.
  • Td5 Thermal weight reduction start temperature
  • Td5 The 5% thermogravimetric decrease starting temperature (Td5) was measured with EXSTAR6000 TG / DTA6200 manufactured by Seiko Instruments Inc. About 10 mg of a sample was weighed in a Pt pan, and measured at a temperature rising rate of 10 ° C./min, measurement atmosphere: air 200 mL / min, and a temperature of 35 ° C. to 800 ° C. to obtain a temperature at which the weight decreased by 5%.
  • Tg Glass transition temperature
  • Tg The glass transition temperature (T g ) was measured by a solid viscoelastic method (DMA method).
  • a lignin molded plate obtained in each example and comparative example was prepared, and a 5 mm ⁇ 30 mm ⁇ 1 mm sample was cut out from the molded plate.
  • DMA8000 manufactured by PerkinElmer Japan Co., Ltd.
  • measurement was performed under the conditions of a temperature increase temperature of 2 ° C./min and 1 Hz until reaching the minimum elastic modulus at 0 ° C. to 300 ° C.
  • the obtained tan ⁇ peak temperature was defined as the glass transition temperature (T g ). 4).
  • Phenolic hydroxyl group (OH group) equivalent The phenolic hydroxyl group equivalent was determined with reference to the method described in Energy Fuel 2010, 24, 2723.
  • lignin of this example has high heat resistance, it is not necessary to perform secondary modification such as secondary derivatization. Moreover, since it has the phenolic hydroxyl group equivalent derived from natural lignin as it is, it turns out that it can be used suitably also as a material.

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Abstract

L'invention concerne un procédé de fabrication de lignine résistante à la chaleur qui inclut une étape (I) au cours de laquelle une solution de lignine matière première, et au moins une sorte de solvant (a) choisie parmi une eau et un hydrocarbure de moment dipolaire inférieur ou égal à 0,25d qui équivalent en termes de volume 1 fois ou plus à 50 fois ou moins la solution de lignine matière première.
PCT/JP2017/032385 2016-09-09 2017-09-07 Procédé de fabrication de lignine résistante à la chaleur Ceased WO2018047928A1 (fr)

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JP7785152B2 (ja) 2024-11-20 2025-12-12 日鉄エンジニアリング株式会社 有機溶媒可溶性リグニンの回収システム及び回収方法

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WO2016043218A1 (fr) * 2014-09-17 2016-03-24 出光興産株式会社 Composition de résine thermodurcissable
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WO2014142289A1 (fr) * 2013-03-15 2014-09-18 出光興産株式会社 Procédé pour la fabrication de produit de décomposition de lignine
WO2016043218A1 (fr) * 2014-09-17 2016-03-24 出光興産株式会社 Composition de résine thermodurcissable
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Publication number Priority date Publication date Assignee Title
WO2021049359A1 (fr) * 2019-09-10 2021-03-18 日鉄エンジニアリング株式会社 Système de récupération et procédé de récupération de lignine soluble dans un solvant organique
JP2021042289A (ja) * 2019-09-10 2021-03-18 日鉄エンジニアリング株式会社 有機溶媒可溶性リグニンの回収システム及び回収方法
JP7343337B2 (ja) 2019-09-10 2023-09-12 日鉄エンジニアリング株式会社 有機溶媒可溶性リグニンの回収システム及び回収方法
JP2023175712A (ja) * 2019-09-10 2023-12-12 日鉄エンジニアリング株式会社 有機溶媒可溶性リグニンの回収システム及び回収方法
JP7599531B2 (ja) 2019-09-10 2024-12-13 日鉄エンジニアリング株式会社 有機溶媒可溶性リグニンの回収システム及び回収方法
JP2025022927A (ja) * 2019-09-10 2025-02-14 日鉄エンジニアリング株式会社 有機溶媒可溶性リグニンの回収システム及び回収方法
JP7785152B2 (ja) 2024-11-20 2025-12-12 日鉄エンジニアリング株式会社 有機溶媒可溶性リグニンの回収システム及び回収方法

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