JP2013076067A - Method for producing functional material from lignocellulose-containing material - Google Patents
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- 239000002904 solvent Substances 0.000 claims abstract description 41
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 31
- 238000001914 filtration Methods 0.000 claims abstract description 27
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- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
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- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
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- CUZKCNWZBXLAJX-UHFFFAOYSA-N 2-phenylmethoxyethanol Chemical compound OCCOCC1=CC=CC=C1 CUZKCNWZBXLAJX-UHFFFAOYSA-N 0.000 claims description 4
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 4
- 229960005323 phenoxyethanol Drugs 0.000 claims description 4
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- 229920002678 cellulose Polymers 0.000 abstract description 17
- 239000000203 mixture Substances 0.000 abstract description 6
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- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 4
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
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- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
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- 235000007164 Oryza sativa Nutrition 0.000 description 3
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- WMPOZLHMGVKUEJ-UHFFFAOYSA-N decanedioyl dichloride Chemical compound ClC(=O)CCCCCCCCC(Cl)=O WMPOZLHMGVKUEJ-UHFFFAOYSA-N 0.000 description 3
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
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- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
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- 150000004676 glycans Chemical class 0.000 description 2
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- 230000003472 neutralizing effect Effects 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
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- IBLKWZIFZMJLFL-UHFFFAOYSA-N 1-phenoxypropan-2-ol Chemical compound CC(O)COC1=CC=CC=C1 IBLKWZIFZMJLFL-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
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- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
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- HJUFTIJOISQSKQ-UHFFFAOYSA-N fenoxycarb Chemical compound C1=CC(OCCNC(=O)OCC)=CC=C1OC1=CC=CC=C1 HJUFTIJOISQSKQ-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Saccharide Compounds (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
本発明は、リグノセルロース含有材料からの機能材料の製造方法に関する。 The present invention relates to a method for producing a functional material from a lignocellulose-containing material.
地球温暖化や化石資源枯渇の観点から、近年、製材時に排出される樹皮、おが屑、間伐材等の木質系物質や、稲わら、葦、藻類等の植物資源を有効活用することが検討されている。本発明では、これらを含めてリグノセルロース含有材料と総称する。リグノセルロース含有材料の主成分は、セルロース、ヘミセルロースおよびリグニンであるが、液化することで、これら成分の分離・利用に供することが試みられてきた。リグノセルロース含有材料の液化は、高温高圧下や臨界圧下で行われることが多く、大掛かりな装置が必要であった（例えば、特許文献１、２参照）。また、得られた溶液は粘性が強い場合が多く、水で洗浄することも難しいため、各成分の単離は容易ではなかった。そこで、濃酸およびフェノール誘導体の混合系において、室温で前記成分を分離する方法が検討されている（例えば、特許文献３参照）。この方法は、木粉にフェノール誘導体および７３％硫酸を混合、攪拌して各成分を分解するものであるが、混合液から各成分を分離するには、大量の溶剤を用いた希釈、洗浄、抽出が必要であった。 In recent years, from the viewpoint of global warming and fossil resource depletion, it has been studied to effectively use woody materials such as bark, sawdust, and thinned wood emitted during sawing, and plant resources such as rice straw, straw, and algae. Yes. In the present invention, these are collectively referred to as lignocellulose-containing materials. The main components of the lignocellulose-containing material are cellulose, hemicellulose and lignin. However, attempts have been made to separate and utilize these components by liquefaction. Liquefaction of lignocellulose-containing material is often performed under high temperature and high pressure or critical pressure, and a large-scale apparatus is required (for example, see Patent Documents 1 and 2). Moreover, since the obtained solution is often viscous and difficult to wash with water, isolation of each component has not been easy. Therefore, a method of separating the components at room temperature in a mixed system of concentrated acid and phenol derivative has been studied (for example, see Patent Document 3). In this method, a phenol derivative and 73% sulfuric acid are mixed with wood powder and stirred to decompose each component. To separate each component from the mixed solution, dilution with a large amount of solvent, washing, Extraction was necessary.
従来の方法では、リグノセルロース含有材料を液化することに主眼が置かれており、液化する必要のない成分までが液化されていた。特に、セルロースとリグニンとを、利用しやすい状態で取り出すことができ、なおかつ分離や洗浄の工程が容易な処理方法は開発されていなかった。そこで、本発明は、リグノセルロース含有材料からリグニンおよびセルロース等の機能材料組成物を、様々な用途に利用しやすい状態で得ることのできる製造方法を提供することを目的とする。 Conventional methods focus on liquefying lignocellulose-containing materials, and even components that do not need to be liquefied have been liquefied. In particular, a processing method that can take out cellulose and lignin in an easy-to-use state and that allows easy separation and washing steps has not been developed. Then, an object of this invention is to provide the manufacturing method which can obtain functional material compositions, such as a lignin and a cellulose, from a lignocellulose containing material in the state which is easy to utilize for various uses.
前記目的を達成するために、本発明のリグノセルロース含有材料からの機能材料の製造方法は、溶媒中でリグノセルロース含有材料に酸を添加して酸分解する酸分解工程と、濾過工程とを含む機能材料の製造方法であって、
前記酸分解工程は、芳香族系グリコールエーテル、３−メトキシブタノールおよび４−メトキシブタノールからなる群から選ばれる少なくとも１つを含む溶媒中で、酸としてスルホン酸系の酸を用いて行い、
前記酸の添加量が、絶乾状態のリグノセルロース含有材料１０ｇに対して０．１〜５ｍｍｏｌの範囲内であることを特徴とする。
In order to achieve the above object, the method for producing a functional material from a lignocellulose-containing material according to the present invention includes an acid decomposition step in which an acid is added to the lignocellulose-containing material in a solvent to perform acid decomposition, and a filtration step. A method for producing a functional material,
The acid decomposition step is performed using a sulfonic acid acid as an acid in a solvent containing at least one selected from the group consisting of aromatic glycol ether, 3-methoxybutanol and 4-methoxybutanol,
The amount of the acid added is in the range of 0.1 to 5 mmol with respect to 10 g of the absolutely dry lignocellulose-containing material.
本発明によると、リグノセルロース含有材料から、リグニンおよびセルロース等の機能材料組成物を、様々な用途に利用しやすい状態で得ることができる。また、酸分解工程において添加する酸の量を少量とすることができるので、後工程における処理での水、中和剤および溶剤等の使用量を削減することができる。 According to the present invention, a functional material composition such as lignin and cellulose can be obtained from a lignocellulose-containing material in a state where it can be easily used for various applications. In addition, since the amount of acid added in the acid decomposition step can be reduced, the amount of water, neutralizing agent, solvent, etc. used in the treatment in the subsequent step can be reduced.
本発明のリグノセルロース含有材料からの機能材料の製造方法において、前記溶媒として、エチレングリコールモノフェニルエーテル、エチレングリコールモノベンジルエーテル、３−メトキシブタノールおよび４−メトキシブタノールからなる群から選ばれる少なくとも１つを含む溶媒を用いることが好ましい。 In the method for producing a functional material from the lignocellulose-containing material of the present invention, the solvent is at least one selected from the group consisting of ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, 3-methoxybutanol and 4-methoxybutanol. It is preferable to use a solvent containing.
本発明のリグノセルロース含有材料からの機能材料の製造方法において、前記スルホン酸系の酸として、硫酸およびドデシルベンゼンスルホン酸の少なくとも１つを用いることが好ましい。 In the method for producing a functional material from the lignocellulose-containing material of the present invention, it is preferable to use at least one of sulfuric acid and dodecylbenzenesulfonic acid as the sulfonic acid.
本発明のリグノセルロース含有材料からの機能材料の製造方法において、前記酸分解工程を、１２０〜２００℃の範囲内で行うことが好ましい。 In the method for producing a functional material from the lignocellulose-containing material of the present invention, the acid decomposition step is preferably performed within a range of 120 to 200 ° C.
本発明のリグニン系機能材料は、前記本発明の製造方法によって得られたものである。また、本発明のポリステルは、前記リグニン系機能材料を構成成分とすることを特徴とする。そして、前記本発明のポリエステルは、６０℃から２５０℃の範囲に少なくとも一つの融点を持ち、溶融成型加工可能であることが好ましい。 The lignin-based functional material of the present invention is obtained by the production method of the present invention. The polyester of the present invention is characterized in that the lignin-based functional material is a constituent component. The polyester of the present invention preferably has at least one melting point in the range of 60 ° C. to 250 ° C. and can be melt-molded.
つぎに、本発明について詳細に説明する。ただし、本発明は、以下の記載により制限されない。 Next, the present invention will be described in detail. However, the present invention is not limited by the following description.
図１に、本発明のリグノセルロース含有材料からの機能材料の製造方法のチャート図の一例を示す。まず、溶媒中でリグノセルロース含有材料にスルホン酸系の酸を添加し、酸分解工程を行う。酸分解後の液は、濾過によって、固層と液層とに分離することができる。固層として、主にセルロースを含む成分が得られ、液層（油層）としては、リグニンを多く含む成分が得られる。この液層から溶媒を蒸発させ、濃縮することで、高濃度のリグニンが得られる。濃縮工程によって蒸発させた溶媒は、回収して再利用することが可能である。また、液層の溶媒が、疎水性であれば、濃縮した後に、水を加えて、水による抽出工程を行うと、油層には、主にリグニンが、水層には、酸あるいは分解によって生成した糖などのセルロースの一部やヘミセルロース由来の化合物が抽出される。前記抽出工程によって、油層の水洗浄（酸成分の除去）が可能である。従来は、これら成分の分解や分離が困難であったり、過剰な反応に起因する副生成物の生成等が起こりやすかった。本発明の機能材料の製造方法によると、セルロースやリグニン、ヘミセルロース由来の化合物等の分離が容易であり、かつ、これらの化合物を使用しやすい状態で得ることが可能である。 In FIG. 1, an example of the chart figure of the manufacturing method of the functional material from the lignocellulose containing material of this invention is shown. First, a sulfonic acid acid is added to a lignocellulose-containing material in a solvent, and an acid decomposition step is performed. The acid-decomposed liquid can be separated into a solid layer and a liquid layer by filtration. A component containing mainly cellulose is obtained as the solid layer, and a component containing a large amount of lignin is obtained as the liquid layer (oil layer). By evaporating the solvent from the liquid layer and concentrating it, a high concentration of lignin can be obtained. The solvent evaporated by the concentration step can be recovered and reused. Also, if the solvent in the liquid layer is hydrophobic, it is concentrated and then added with water, followed by an extraction step with water. The oil layer produces mainly lignin, and the aqueous layer is produced by acid or decomposition. A part of cellulose such as sucrose and compounds derived from hemicellulose are extracted. By the extraction step, the oil layer can be washed with water (acid component removal). Conventionally, it has been difficult to decompose or separate these components, or to easily generate by-products due to excessive reaction. According to the method for producing a functional material of the present invention, it is possible to easily separate compounds derived from cellulose, lignin, hemicellulose, and the like, and to obtain these compounds in an easy-to-use state.
本発明のリグノセルロース含有材料からの機能材料の製造方法は、リグノセルロース含有材料に酸を添加して酸分解する酸分解工程を含んでいる。そして、前記酸分解工程を、芳香族系グリコールエーテル、３−メトキシブタノールおよび４−メトキシブタノールからなる群から選ばれる少なくとも１つを含む溶媒中で、酸としてスルホン酸系の酸を用いて行うことを特徴とする。リグノセルロース含有材料としては、木材のバージン材やチップ以外にも、製材時に排出される樹皮、おが屑、木粉、間伐材、および建築廃材などの木質系廃棄物を使用することができる。また、竹、葦、稲わら、もみ殻、麦わら、藻類などの非木材系植物資源も使用することができる。これらの材料は、チップ状、フレーク状、あるいは粉状にすることで好ましく用いられる。 The method for producing a functional material from the lignocellulose-containing material of the present invention includes an acid decomposition step in which an acid is added to the lignocellulose-containing material for acid decomposition. The acid decomposition step is performed using a sulfonic acid acid as an acid in a solvent containing at least one selected from the group consisting of an aromatic glycol ether, 3-methoxybutanol and 4-methoxybutanol. It is characterized by. As the lignocellulose-containing material, woody waste such as bark, sawdust, wood powder, thinned wood, and building waste discharged during lumbering can be used in addition to virgin wood and chips. Non-wood plant resources such as bamboo, straw, rice straw, rice husk, wheat straw, and algae can also be used. These materials are preferably used in the form of chips, flakes, or powders.
本発明で用いられる溶媒のうち、芳香族系グリコールエーテルは、一価または二価のフェノールを原料としたポリオールである。芳香族系グリコールエーテルとしては、エチレングリコールフェニルエーテル、エチレングリコールベンジルエーテル、プロピレングリコールフェニルエーテル等があげられる。芳香族系グリコールエーテルのうち、エチレングリコールモノフェニルエーテルおよびエチレングリコールモノベンジルエーテルが特に好ましく使用できる。 Among the solvents used in the present invention, the aromatic glycol ether is a polyol using a monovalent or divalent phenol as a raw material. Examples of the aromatic glycol ether include ethylene glycol phenyl ether, ethylene glycol benzyl ether, propylene glycol phenyl ether and the like. Of the aromatic glycol ethers, ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether can be particularly preferably used.
前記溶媒は、芳香族系グリコールエーテル、３−メトキシブタノールおよび４−メトキシブタノールからなる群から選ばれる溶媒以外の、他の溶媒を混合して用いることができる。例えば、脂肪族グリコールエーテルやアルコール類を混合した場合でも、スムーズに反応が進む。芳香族系グリコールエーテル、３−メトキシブタノールおよび４−メトキシブタノールからなる群から選ばれる少なくとも１つの溶媒は、溶媒全体に対し、１０〜１００重量％の範囲で含まれることが好ましく、より好ましくは、２０〜１００重量％の範囲である。 The solvent can be used by mixing other solvents other than the solvent selected from the group consisting of aromatic glycol ethers, 3-methoxybutanol and 4-methoxybutanol. For example, even when aliphatic glycol ethers or alcohols are mixed, the reaction proceeds smoothly. At least one solvent selected from the group consisting of an aromatic glycol ether, 3-methoxybutanol and 4-methoxybutanol is preferably contained in a range of 10 to 100% by weight, more preferably, based on the total solvent. It is in the range of 20 to 100% by weight.
前記溶媒は、リグノセルロースへの親和性とリグニンに対する溶解性とが良好であることが好ましい。また、前記溶媒の沸点は、１６０℃以上であることが好ましく、より好ましくは、１６０〜２５０℃の範囲内である。図１の濃縮工程において、前記溶媒の沸点が１６０℃以上のあまり高くない温度であると、蒸発や回収が容易であり、好ましい。前記溶媒として、例えば、エチレングリコールブチルエーテル、メトキシブタノール等の水と任意に混合する溶媒を混合した場合は、濾液（液層）をそのまま濃縮して回収すればよいが、２−エチルヘキシルアルコール等の水と混ざり合わずに共沸する溶媒を混合した場合には、水蒸気蒸留によって回収することも可能である。 The solvent preferably has good affinity for lignocellulose and solubility for lignin. Moreover, it is preferable that the boiling point of the said solvent is 160 degreeC or more, More preferably, it exists in the range of 160-250 degreeC. In the concentration step of FIG. 1, it is preferable that the boiling point of the solvent is not so high as 160 ° C. or more because evaporation and recovery are easy. For example, when a solvent arbitrarily mixed with water such as ethylene glycol butyl ether or methoxybutanol is mixed as the solvent, the filtrate (liquid layer) may be concentrated and recovered as it is, but water such as 2-ethylhexyl alcohol may be recovered. In the case of mixing an azeotropic solvent without being mixed, it can be recovered by steam distillation.
リグノセルロース含有材料と前記溶媒との混合比率は両者が均一に混合できれば特に限定されるものではないが、前記溶媒１００重量部に対してリグノセルロース含有材料を、好ましくは１〜１００重量部、より好ましくは１０〜５０重量部混合する。 The mixing ratio of the lignocellulose-containing material and the solvent is not particularly limited as long as both can be mixed uniformly, but the lignocellulose-containing material is preferably 1 to 100 parts by weight, more preferably 100 parts by weight of the solvent. Preferably, 10 to 50 parts by weight are mixed.
本発明で用いられる酸は、スルホン酸系の酸である。塩酸、燐酸および酢酸等の他の酸を用いた場合には、セルロースとリグニンの分離がうまくいかず、残渣もリグニン含量の多いものとなり、目的物が得られない。スルホン酸系の酸としては、硫酸およびドデシルベンゼンスルホン酸が、好ましく使用できる。前記スルホン酸系の酸の添加量は、絶乾状態のリグノセルロース含有材料１０ｇに対して０．１〜５ｍｍｏｌの範囲内であることが好ましく、０．５〜２ｍｍｏｌの範囲内であることがより好ましい。 The acid used in the present invention is a sulfonic acid acid. When other acids such as hydrochloric acid, phosphoric acid and acetic acid are used, separation of cellulose and lignin is not successful, and the residue also has a high lignin content and the desired product cannot be obtained. As the sulfonic acid acid, sulfuric acid and dodecylbenzenesulfonic acid can be preferably used. The addition amount of the sulfonic acid acid is preferably in the range of 0.1 to 5 mmol, more preferably in the range of 0.5 to 2 mmol, with respect to 10 g of the absolutely dry lignocellulose-containing material. preferable.
酸分解工程においては、リグノセルロース含有材料、スルホン酸系の酸および前記溶媒の含有される混合物を加熱することも好ましい。加熱温度は、使用する前記溶媒の沸点まで上げることが可能であるが、１２０〜２００℃の範囲が好ましく、より好ましくは、１４０〜１６０℃の範囲である。１６０℃以下であれば、汎用の蒸気ボイラーを使用することができ、また、様々な産業で発生する廃熱を利用することも可能となる。前記温度範囲で前記酸分解工程を行うと、水分が系外に排出される。したがって、本発明の製造方法では、リグノセルロース含有材料を粉砕して、そのまま使用することが可能であり、原料となる木粉等の材料の含水率を減少させるための乾燥工程等を必要としない点で好ましい。 In the acid decomposition step, it is also preferable to heat the mixture containing the lignocellulose-containing material, the sulfonic acid acid and the solvent. The heating temperature can be raised to the boiling point of the solvent used, but is preferably in the range of 120 to 200 ° C, more preferably in the range of 140 to 160 ° C. If it is 160 degrees C or less, a general purpose steam boiler can be used and the waste heat which generate | occur | produces in various industries can also be utilized. When the acid decomposition step is performed in the temperature range, moisture is discharged out of the system. Therefore, in the production method of the present invention, the lignocellulose-containing material can be pulverized and used as it is, and a drying step or the like for reducing the moisture content of the raw material such as wood flour is not required. This is preferable.
なお、従来においても木質系物質を液化する検討がなされてきたが、得られた溶液にはリグニンあるいはセルロース系多糖がすべて溶解するため、これらの成分を単離することは容易ではなかった。さらに、余剰の酸を水で抽出しようとしても、水と均一に混和させることが難しいほど粘稠になってしまっていた。本発明の製造方法によって得られるリグニン等の機能材料は、流動性に優れた状態で得ることが可能であり、前述のとおり、酸の除去や分離・濃縮等の操作が容易にできる。 In the past, studies have been made to liquefy woody substances. However, since all lignin or cellulosic polysaccharides are dissolved in the obtained solution, it is not easy to isolate these components. Furthermore, even if it tried to extract an excess acid with water, it became so viscous that it was difficult to mix with water uniformly. A functional material such as lignin obtained by the production method of the present invention can be obtained in a state excellent in fluidity, and as described above, operations such as acid removal, separation and concentration can be easily performed.
本発明の製造方法によると、分子量が１００以上６００未満の範囲と低分子量のリグニンも得られる。前記低分子量のリグニンは、各種の溶媒に可溶な芳香族原料である。前記リグニンは、水酸基を多く含んでおり、これを原料として機能性ポリマー、特にポリエステルを好適に合成することができる。ただし、合成できる機能性ポリマーはポリエステルに限るものではなく、前記リグニンの含有する水酸基と反応可能な官能基（イソシアネート基、エポキシ基等）を有する化合物を用いることで、ポリウレタン、エポキシ樹脂等の合成も可能である。 According to the production method of the present invention, a low molecular weight lignin having a molecular weight in the range of 100 or more and less than 600 can also be obtained. The low molecular weight lignin is an aromatic raw material that is soluble in various solvents. The lignin contains a large amount of hydroxyl groups, and functional polymers, particularly polyesters can be suitably synthesized using this as a raw material. However, the functional polymer that can be synthesized is not limited to polyester, but by using a compound having a functional group (isocyanate group, epoxy group, etc.) that can react with the hydroxyl group contained in the lignin, synthesis of polyurethane, epoxy resin, etc. Is also possible.
前記本発明の製造方法で得られるリグニンを構成成分とすることで、６０〜２５０℃の範囲に少なくとも一つの融点を有するポリエステルを得ることができる。このようなポリエステルは、溶融成形加工が可能であり、特に、前記ポリエステルが液晶ポリマーであると、強度に異方性を持たせることが可能となる。 By using lignin obtained by the production method of the present invention as a constituent component, a polyester having at least one melting point in the range of 60 to 250 ° C. can be obtained. Such a polyester can be melt-molded. In particular, if the polyester is a liquid crystal polymer, the strength can be made anisotropic.
つぎに、本発明の実施例について比較例と併せて説明する。なお、本発明は、下記の実施例および比較例によってなんら限定ないし制限されない。また、各実施例および各比較例における各種特性および物性の測定および評価は、下記の方法により実施した。 Next, examples of the present invention will be described together with comparative examples. The present invention is not limited or restricted by the following examples and comparative examples. In addition, various properties and physical properties in each example and each comparative example were measured and evaluated by the following methods.
（ＧＰＣ分析）
ＧＰＣ分析は試料の濃度が０．１ｗｔ％となるようにテトラヒドロフラン（ＴＨＦ）で希釈し、下記の条件で行った。
ＧＰＣ （株）島津製作所製
本体 ＣＢＭ−２０Ａ
ＵＶ ＳＲＤ−２０Ａ（検出波長２５４ｎｍ）
ＲＩ ＲＩＤ−１０Ａ
摂取量 約０．１ｍｌ 流量 １．０ｍｌ／１ｍｉｎ 溶媒ＴＨＦ
カラム温度 ４０℃
(GPC analysis)
GPC analysis was performed under the following conditions after diluting with tetrahydrofuran (THF) so that the concentration of the sample was 0.1 wt%.
Main body CBM-20A manufactured by Shimadzu Corporation, GPC
UV SRD-20A (detection wavelength 254 nm)
RI RID-10A
Intake approx. 0.1ml Flow rate 1.0ml / 1min Solvent THF
Column temperature 40 ° C
（硬度）
ＪＩＳ Ｋ ５６００−５−４（１９９９）による鉛筆硬度を測定した。鉛筆は、三菱鉛筆株式会社製「ｕｎｉ」（商品名）を用いた。
(hardness)
The pencil hardness according to JIS K 5600-5-4 (1999) was measured. As the pencil, “uni” (trade name) manufactured by Mitsubishi Pencil Co., Ltd. was used.
（耐溶剤性評価）
２ポンドハンマーの凸部にガーゼを１６枚重ねて固定し、メチルエチルケトン（ＭＥＫ）でよく湿らせた後、塗装試験片の上を往復させた。前記塗料の塗膜がはがれた時の回数を耐溶剤性とした。
(Solvent resistance evaluation)
Sixteen pieces of gauze were fixed on the convex part of a 2-pound hammer and fixed with methyl ethyl ketone (MEK), and then reciprocated on the coated test piece. The number of times the paint film was peeled off was defined as solvent resistance.
（碁盤目密着）
ＪＩＳ Ｋ ５６００−５−６（１９９９）に準じて、密着性を評価した。塗膜にカッターで１ｍｍ×１ｍｍのマス目を碁盤目状に１００個形成し、その部分に粘着テープ（ニチバン株式会社製セロテープ（登録商標））を貼着した後、急速に剥離し、塗膜の剥離状態を目視観察にて評価した。
(Cross board close contact)
The adhesion was evaluated according to JIS K 5600-5-6 (1999). 100 squares of 1 mm x 1 mm are formed on the coating film in a grid pattern, and adhesive tape (cello tape (registered trademark) manufactured by Nichiban Co., Ltd.) is applied to the part, and then the film is peeled off rapidly. The peeled state was evaluated by visual observation.
（濾過性評価）
酸分解工程後の反応液を、ヌッチェを用いて、直径７０ｍｍの円形濾紙（Ｎｏ．２ ＡＤＶＡＮＴＥＣ社製）を使用して濾過した際の濾過性を、以下の基準で評価した。
判定基準
Ｇ ：濾過に要した時間が１０分以内。
ＮＧ：濾過に要した時間が１０分を超える、あるいは、濾過による分離が不可能。
(Filterability evaluation)
The filterability when the reaction solution after the acid decomposition step was filtered using a circular filter paper (No. 2 ADVANTEC) having a diameter of 70 mm using a Nutsche was evaluated according to the following criteria.
Criteria G: Time required for filtration is within 10 minutes.
NG: Time required for filtration exceeds 10 minutes, or separation by filtration is impossible.
［実施例１］
（酸分解工程）
木粉（杉、富山県西部森林組合 おが粉）１１．３６ｇ（含水率１２％ 絶乾状態で１０ｇ）、エチレングリコールモノフェニルエーテル（日本乳化剤株式会社製、商品名「フェニル グリコール（ＰｈＧ）」、沸点２４４．７℃）９０ｇ、９５％硫酸０．０８ｇ（０．８ｍｍｏｌ）をフラスコに計量し、１５０℃で４時間攪拌した。このとき系に含まれている水分（木粉起因のものと思われる）はディーンスタークフラスコなどの器具を用いることで系外へ留去される。
[Example 1]
(Acid decomposition process)
Wood flour (cedar, Toyama Prefecture Forestry Association sawdust) 11.36 g (water content 12%, 10 g in absolutely dry state), ethylene glycol monophenyl ether (manufactured by Nippon Emulsifier Co., Ltd., trade name “Phenyl Glycol (PhG)”) , Boiling point 244.7 ° C.) 90 g and 95% sulfuric acid 0.08 g (0.8 mmol) were weighed in a flask and stirred at 150 ° C. for 4 hours. At this time, water contained in the system (which seems to be caused by wood flour) is distilled out of the system by using an instrument such as a Dean Stark flask.
（濾過工程）
前記混合物を常温まで冷却し、ヌッチェを用いて濾過した。濾過には、直径７０ｍｍの円形濾紙（Ｎｏ．２ ＡＤＶＡＮＴＥＣ社製）を使用した。濾過に要した時間は１０分以内で、スムーズな濾別が可能だった。フラスコはプロピレングリコールメチルエーテル１００ｇをもちいて洗浄し残渣上に濾過した。濾過残渣は、メチルエチルケトン（ＭＥＫ）で洗浄した後、風乾後１３０℃で２時間乾燥させた。得られた濾過残渣は、白っぽい綿状であり、３．６ｇであった。また濾液は、ＵＶ検出によるＧＰＣ分析により、数平均分子量１４２１、重量平均分子量３１０８をピークとする成分を多く含み、透明感のある黒っぽい粘稠な液体だった。
(Filtering process)
The mixture was cooled to room temperature and filtered using a Nutsche. For filtration, a circular filter paper (No. 2 ADVANTEC) having a diameter of 70 mm was used. The time required for the filtration was within 10 minutes, and a smooth separation was possible. The flask was washed with 100 g of propylene glycol methyl ether and filtered over the residue. The filtration residue was washed with methyl ethyl ketone (MEK), air-dried and then dried at 130 ° C. for 2 hours. The obtained filtration residue was whitish cotton-like and was 3.6 g. Further, the filtrate was a blackish viscous liquid having a clear feeling and containing many components having a peak of number average molecular weight 1421 and weight average molecular weight 3108 by GPC analysis by UV detection.
（酸不溶性リグニンの分離工程）
前記乾燥後の濾過残渣１ｇに対し、７２％硫酸を１６．４ｇ加え、３０℃で１時間混練した。硫酸と混練した濾過残渣を、水２７７ｇとともに、５００ｍＬの耐圧瓶に移した。この耐圧瓶を滅菌機に入れ、１３０℃で１時間のレトルト処理を行った。この処理で、残渣中のセルロースはほぼ溶解する。その後、耐圧瓶を常温まで冷却し、ヌッチェを用いて濾過した。濾過には、直径７０ｍｍの円形濾紙（Ｎｏ．２ ＡＤＶＡＮＴＥＣ社製）を使用した。不溶解成分（酸不溶性リグニン）は、４．３質量％であった。
(Separation process of acid-insoluble lignin)
16.4 g of 72% sulfuric acid was added to 1 g of the filtered residue after drying and kneaded at 30 ° C. for 1 hour. The filtration residue kneaded with sulfuric acid was transferred to a 500 mL pressure bottle together with 277 g of water. The pressure bottle was placed in a sterilizer and retorted at 130 ° C. for 1 hour. By this treatment, the cellulose in the residue is almost dissolved. Thereafter, the pressure bottle was cooled to room temperature and filtered using a Nutsche. For filtration, a circular filter paper (No. 2 ADVANTEC) having a diameter of 70 mm was used. The insoluble component (acid-insoluble lignin) was 4.3% by mass.
（赤外吸収スペクトル分析）
前記濾過工程で濾別された濾過残渣について、赤外吸収スペクトル分析を行った。赤外吸収スペクトル分析は、日本分光株式会社製 ＦＴ／ＩＲ４１００を用い、一点ＡＴＲ法にて測定した。対照サンプルとして、高純度のセルロースを含むパルプ素材からなる産業用ワイパーである「キムワイプ」Ｓ−２００（商品名、日本製紙クレシア株式会社製）を用いた。結果を図２に示す。得られた濾過残渣のスペクトル（図２（ａ））は、「キムワイプ」のスペクトル（図２（ｂ））と略同一であり、得られた濾過残渣は、純度の高いセルロースを含むことがわかった。
(Infrared absorption spectrum analysis)
Infrared absorption spectrum analysis was performed about the filtration residue separated by the said filtration process. Infrared absorption spectrum analysis was measured by a one-point ATR method using FT / IR4100 manufactured by JASCO Corporation. As a control sample, “Kimwipe” S-200 (trade name, manufactured by Nippon Paper Crecia Co., Ltd.), which is an industrial wiper made of a pulp material containing high-purity cellulose, was used. The results are shown in FIG. The spectrum of the obtained filtration residue (FIG. 2 (a)) is almost the same as the spectrum of “Kimwipe” (FIG. 2 (b)), and the obtained filtration residue contains high-purity cellulose. It was.
（濾液（液層））
得られた濾液について、ＧＰＣ分析を行った結果を図３に示す。溶出時間４４分付近までのＵＶ吸収強度が大きい画分がリグニンである。それ以降のＲＩ強度が大きい画分について、酵素法によるグルコース検出キット（和光純薬工業株式会社製、グルコースＣＩＩ−テストワコー）を用いて測定したところ、グルコースが検出され、低分子化されたセルロース系多糖が含まれていることがわかった。液層には、リグニン、リグノセルロースおよびセルロース由来のグルコースが含まれていることが特定できた。液層は、リグノセルロースとして使用したり、燃料として活用することもできる。リグニンは、溶液の状態で取り出すことができるので、広く利用が可能である。
(Filtrate (liquid layer))
The results of GPC analysis for the obtained filtrate are shown in FIG. A fraction having a large UV absorption intensity up to about 44 minutes elution time is lignin. Subsequent fractions with large RI intensity were measured using an enzymatic glucose detection kit (glucose CII-Test Wako, manufactured by Wako Pure Chemical Industries, Ltd.). It was found that the polysaccharide was contained. It was possible to specify that the liquid layer contained lignin, lignocellulose and cellulose-derived glucose. The liquid layer can be used as lignocellulose or used as a fuel. Since lignin can be taken out in the state of a solution, it can be widely used.
［実施例２〜１２、比較例１〜１４］
表１に示した条件で、実施例１と同様に、酸分解工程、濾過工程、酸不溶性リグニンの分離工程を行った。
[Examples 2 to 12, Comparative Examples 1 to 14]
Under the conditions shown in Table 1, as in Example 1, an acid decomposition step, a filtration step, and a separation step of acid-insoluble lignin were performed.
実施例６で取り出した残渣（セルロース、リグニン含量７．７質量％）２ｇ、ｎ−メチルピロリドン（ＮＭＰ）９８ｇおよび２ｍｍ径のガラスビーズ１００ｇをマヨネーズ瓶に量り取り、ペイントシェーカーで２４時間振とうした。振とう後、ガラスビーズを分別濾過し、粘度が約１５０ｃｐｓの茶褐色の粘稠液体を得た。得られた粘稠液体を、♯３４のバーコータを用いて１２ｃｍ×２０ｃｍのアルミ板に塗装し、熱風循環式オーブン（佐竹化学機械工業株式会社製）を用いて、２１５℃で１２０秒間乾燥したところ、厚さ約１μｍの、均一な外観の親水性塗膜が得られた、得られた塗膜の鉛筆硬度はＨであった。 2 g of the residue taken out in Example 6 (cellulose, lignin content 7.7% by mass), 98 g of n-methylpyrrolidone (NMP) and 100 g of 2 mm diameter glass beads were weighed into a mayonnaise bottle and shaken with a paint shaker for 24 hours. . After shaking, the glass beads were fractionally filtered to obtain a dark brown viscous liquid having a viscosity of about 150 cps. The resulting viscous liquid was coated on a 12 cm × 20 cm aluminum plate using a # 34 bar coater and dried at 215 ° C. for 120 seconds using a hot air circulating oven (Satake Chemical Machinery Co., Ltd.). A hydrophilic coating film having a uniform appearance and a thickness of about 1 μm was obtained. The pencil hardness of the coating film obtained was H.
実施例６で取り出した濾液を、エバポレーターを用いて、８０℃で真空乾燥を行い、ブチルセロソルブを蒸発させ、濃縮した。濃縮液をＭＥＫで希釈したものを、刷毛でポリカーボネートテストパネルに塗装し、１００℃で２時間乾燥した。塗膜は鼈甲のような透明感のある色をしていた。物性は鉛筆硬度ＨＢ、ＭＥＫラビング７５回、碁盤目密着も問題ない強靭な塗膜であった。蒸発させたブチルセロソルブは蒸留して、回収再利用が可能であった。 The filtrate taken out in Example 6 was vacuum-dried at 80 ° C. using an evaporator to evaporate and concentrate butyl cellosolve. A concentrate diluted with MEK was applied to a polycarbonate test panel with a brush and dried at 100 ° C. for 2 hours. The paint film had a translucent color such as a shell. The physical properties were a tough coating film with pencil hardness HB, 75 MEK rubbing, and no cross-cut adhesion. The evaporated butyl cellosolve was distilled and could be recovered and reused.
［実施例１３〜１９］
実施例１３〜１９は、原料の材料に含まれる水分の影響をみた実施例である。実施例１３は、実施例１で使用したおが粉を、パルピングの叩解に倣って、水中でハンマーで叩いて繊維をほぐしたものを使用した。実施例１４および１５は、実施例１と同じおが粉を用い、反応系に水を添加することで、仮想的に含水率の高い材料を用いた系を作ったものである。実施例１６〜１９は、おが粉ではなく、チップを使用した。その他は、表２に示した条件で、実施例１と同様に、酸分解工程、濾過工程、酸不溶性リグニンの分離工程を行った。
[Examples 13 to 19]
Examples 13 to 19 are examples in which the influence of moisture contained in the raw material is considered. In Example 13, the sawdust used in Example 1 was struck with a hammer in water to loosen the fibers following the beating of pulping. In Examples 14 and 15, the same sawdust as in Example 1 was used, and water was added to the reaction system to create a system using a virtually high water content material. In Examples 16 to 19, chips were used instead of sawdust. Others were the same as in Example 1 under the conditions shown in Table 2, and an acid decomposition step, a filtration step, and a separation step of acid-insoluble lignin were performed.
表１に、実施例１〜１２および比較例１〜１４の結果を、表２に、実施例１３〜１９の結果を示す。実施例では、いずれも、わた状の形態の色の薄い濾過残渣であり、原料である木粉の残存は見られなかった。また、濾過性も良好であった。実施例で得られた残渣は、リグニン含量が１０ｗｔ％以下と少なく、セルロースからリグニンが高い割合で分離できていることがわかる。 Table 1 shows the results of Examples 1-12 and Comparative Examples 1-14, and Table 2 shows the results of Examples 13-19. In each of the examples, the residue was a thin filtration residue having a wrinkled form, and no residual wood flour as a raw material was observed. The filterability was also good. The residue obtained in the Examples has a low lignin content of 10 wt% or less, indicating that lignin can be separated from cellulose at a high rate.
一方、比較例では、木粉の断片が残ったり、反応が進んでいないと思われる外観の濾過残渣が得られた。比較例１および比較例２は、酸分解工程では溶媒と材料との馴染みがよく、一見反応がうまく進行しているかのようであったが、得られた濾過残渣のリグニン含有量が多く（反応前と比べてほとんど減っていない）、セルロースとリグニンとの分離はうまくできていなかった。比較例３では、酸分解工程において、反応温度の１５０℃を維持できず、また、激しい異臭がした。１５０℃での留出分があることから、別の分解反応が進んでいる可能性がある。比較例４および比較例６では、外観上も、反応が進んでいないようであった。溶媒とリグニンとの相溶性が低いことが原因と考えられる。比較例５では、わた状で薄い茶色の残渣が見られ、分解が良好に起こっている可能性はあるが、反応液は、分解工程後に濾過ができないほど粘度が高くなり、濾過が不可能だった。比較例９〜１４は、スルホン酸系ではない酸を用いた例である。塩酸を用いた場合（比較例９）では、若干分解が起こっているようであるが、木粉の断片が残り、また、黒色になった。酢酸（比較例１０）、燐酸（比較例１１〜１４）を用いた場合には、酸分解が進まなかった。 On the other hand, in the comparative example, a filter residue having an external appearance in which a piece of wood flour remained or the reaction did not proceed was obtained. In Comparative Example 1 and Comparative Example 2, it seemed that the solvent and the material were familiar in the acid decomposition step, and the reaction seemed to proceed well, but the lignin content of the obtained filtration residue was large (reaction) Separation of cellulose and lignin was not successful. In Comparative Example 3, in the acid decomposition step, the reaction temperature of 150 ° C. could not be maintained, and an intense odor was generated. Since there is a distillate at 150 ° C., another decomposition reaction may be in progress. In Comparative Example 4 and Comparative Example 6, the reaction did not seem to progress in terms of appearance. The cause is considered to be low compatibility between the solvent and lignin. In Comparative Example 5, a wrinkled and light brown residue was observed, and the decomposition might have occurred well, but the reaction solution became so viscous that it could not be filtered after the decomposition step, and filtration was impossible. It was. Comparative Examples 9 to 14 are examples using acids that are not sulfonic acid-based. In the case of using hydrochloric acid (Comparative Example 9), it seems that the decomposition is slightly occurring, but the wood flour fragments remain and become black. When acetic acid (Comparative Example 10) and phosphoric acid (Comparative Examples 11 to 14) were used, acid decomposition did not proceed.
実施例１３〜１９の結果からは、水分の含有（添加）が多い場合であっても、酸分解反応が良好に進んでいることがわかる。水分があったとしても、１００℃を超える反応温度であることから、反応温度まで昇温させる途中で水分が飛んでしまい、反応には影響を及ぼさないためと考えられる。従来、木質材料等を使用する際には、絶乾状態まで乾燥した後に使用される場合が多かったが、本発明の製造方法によると、原料や反応系に含まれる水分量を考慮する必要がないことがわかる。 From the results of Examples 13 to 19, it can be seen that the acid decomposition reaction proceeds well even when the moisture content (addition) is large. Even if there is water, it is considered that the reaction temperature exceeds 100 ° C., so that water will fly off while raising the temperature to the reaction temperature and the reaction will not be affected. Conventionally, when using wood materials, etc., it was often used after drying to an absolutely dry state, but according to the production method of the present invention, it is necessary to consider the amount of water contained in the raw materials and reaction system. I understand that there is no.
［実施例２０］
（リグニン回収工程）
マグネチックスターラー、温度計、冷却管のついた３００ｍｌ二つ口フラスコに、実施例１で用いたのと同じ木粉１０．２ｇ、フェニル グリコール１０．２ｇ、ブチルセロソルブ８０．３ｇ、ドデシルベンゼンスルホン酸０．６６３ｇを加え、２時間還流・攪拌（１６２〜１６４℃）し、放冷後、実施例１と同様にして濾過し、濾液を回収した。そして、濾紙上の濾過残渣をジエチレングリコールモノエチルエーテル１００ｇおよびメチルエチルケトン１００ｇで洗浄し、先の濾液とこれらの洗液とを併せて１６０℃、５時間ロータリーエバポレータで減圧濃縮を行い、リグニン（収量５．９３ｇ）を回収した。
得られたリグニンは、アセトン、２−ブタノン、クロロホルムに可溶、酢酸エチルに部分可溶であり、ヘキサン、トルエン、１−ブタノール、２−プロパノールに不溶であった。ＧＰＣにより求めたリグニンの重量平均分子量は４７０と低分子化されていた。また、アセチル化後の遊離酢酸の滴定により求められた水酸基価は３８ｍｇ／ｇであった。
[Example 20]
(Lignin recovery process)
In a 300 ml two-necked flask equipped with a magnetic stirrer, thermometer and condenser, the same wood flour as used in Example 1 10.2 g, phenyl glycol 10.2 g, butyl cellosolve 80.3 g, dodecylbenzenesulfonic acid 0 .663 g was added, refluxed and stirred (162 to 164 ° C.) for 2 hours, allowed to cool, and then filtered in the same manner as in Example 1 to collect the filtrate. Then, the filtration residue on the filter paper was washed with 100 g of diethylene glycol monoethyl ether and 100 g of methyl ethyl ketone, and the previous filtrate and these washings were combined and concentrated under reduced pressure on a rotary evaporator at 160 ° C. for 5 hours to give lignin (yield 5. 93 g) was recovered.
The obtained lignin was soluble in acetone, 2-butanone and chloroform, partially soluble in ethyl acetate, and insoluble in hexane, toluene, 1-butanol and 2-propanol. The weight average molecular weight of lignin determined by GPC was 470, which was low. The hydroxyl value determined by titration of free acetic acid after acetylation was 38 mg / g.
（ポリエステル合成工程）
得られた低分子化リグニン０．２ｇをアセトン０．３ｇに溶かし、リグニンの含有する水酸基に対して当量のカルボキシル基となるだけのジカルボン酸クロリドと、前記ジカルボン酸クロリドに対し二倍ｍｏｌ量のトリエチルアミンを氷浴中で加えて撹拌した。前記ジカルボン酸クロリドとしては、塩化アジポイル（０．１５ｇ）、塩化セバコイル（０．２８ｇ）、二塩化テレフタロイル（０．１５ｇ）を使用し、それぞれを用いてポリエステル合成を行った。なお、二塩化テレフタロイルは固体のため、アセトン０．３ｇに溶解させてからリグニン溶液に添加した。これらの反応により、アセトンに不溶な沈殿としてポリエステルが得られた。これらの反応溶液をそれぞれ濾過し、濾過残渣（沈殿）をアセトン洗浄した後、前記沈殿を風乾した。風乾後の前記沈殿の重量は、塩化アジポイルを用いたもので０．３３ｇ、塩化セバコイルを用いたもので０．４８ｇ、二塩化テレフタロイルを用いたもので０．２９ｇであった。
(Polyester synthesis process)
0.2 g of the obtained low molecular weight lignin was dissolved in 0.3 g of acetone, and a dicarboxylic acid chloride that was equivalent to a carboxyl group equivalent to the hydroxyl group contained in the lignin, and a double molar amount of the dicarboxylic acid chloride. Triethylamine was added in an ice bath and stirred. As the dicarboxylic acid chloride, adipoyl chloride (0.15 g), sebacoyl chloride (0.28 g) and terephthaloyl dichloride (0.15 g) were used, and polyester synthesis was performed using each. Since terephthaloyl dichloride was a solid, it was dissolved in 0.3 g of acetone and then added to the lignin solution. By these reactions, polyester was obtained as an insoluble precipitate in acetone. Each of these reaction solutions was filtered, and the filtration residue (precipitate) was washed with acetone, and then the precipitate was air-dried. The weight of the precipitate after air drying was 0.33 g using adipoyl chloride, 0.48 g using sebacoyl chloride, and 0.29 g using terephthaloyl dichloride.
（ポリエステルの特性解析）
種々のジカルボン酸クロリドを用いて作製した前記ポリエステルについて、それぞれ、ＴＧ／ＤＴＡ装置（リガクＴＧ−８１２０）を用いて相転移および熱分解挙動の観測を行った。結果を図４に示す。ＴＧ曲線（図４（ａ））からは、いずれのポリエステルでも、２００℃付近までの重量減少が僅かであることがわかる。また、ＤＴＡ曲線（図４（ｂ））において、いずれのポリエステルも７１℃で吸熱ピークを示したほか、塩化アジポイルを用いたポリエステルで２１２℃、塩化セバコイルを用いたポリエステルで１９７℃、二塩化テレフタロイルを用いたポリエステルで１９０℃において、それぞれ吸熱ピークが観測された。これらの吸熱ピークは、融解および相転移を示しており、このように複数の吸熱ピークを有するポリエステルは、液晶性を示すものと考えられる。さらに、前記塩化アジポイルを用いたポリエステルについて、ホットステージ付偏光顕微鏡観察（Ｎｉｋｏｎ ＥＣＬＩＰＳＥ５０ｉＰＯＬ偏光顕微鏡とＬｉｎｋａｍ １００１３Ｌホットステージ使用）で、昇温速度１０Ｋ／ｍｉｎで昇温させながら状態を観察した。結果を図５に示す。図５に示すように、固相から溶融しながらも、２００℃付近で複屈折を示す液晶相への転移が観測されたことから、前記ポリエステルがサーモトロピック液晶性を有することが確認できた。
(Characteristic analysis of polyester)
With respect to the polyesters prepared using various dicarboxylic acid chlorides, phase transition and thermal decomposition behavior were observed using a TG / DTA apparatus (Rigaku TG-8120). The results are shown in FIG. From the TG curve (FIG. 4A), it can be seen that any polyester has a slight weight loss up to around 200 ° C. In addition, in the DTA curve (FIG. 4 (b)), all the polyesters showed an endothermic peak at 71 ° C., polyester at 212 ° C. using adipoyl chloride, 197 ° C. at polyester using sebacoyl chloride, terephthaloyl dichloride. An endothermic peak was observed at 190 ° C. for each of the polyesters using. These endothermic peaks indicate melting and phase transition, and thus the polyester having a plurality of endothermic peaks is considered to exhibit liquid crystallinity. Furthermore, the state of the polyester using adipoyl chloride was observed with a hot stage with a polarizing microscope (using a Nikon ECLIPSE 50iPOL polarizing microscope and a Linkam 10013L hot stage) while the temperature was raised at a heating rate of 10 K / min. The results are shown in FIG. As shown in FIG. 5, since the transition to the liquid crystal phase exhibiting birefringence was observed at around 200 ° C. while melting from the solid phase, it was confirmed that the polyester had thermotropic liquid crystallinity.
本発明によると、リグノセルロース含有材料から、リグニン等の従来までは分離が困難であった物質を、分離や精製が容易な液化状態で得ることができる液化樹脂原料組成物とともに、セルロースを溶剤に易分散である形で得ることができる。本発明の製造方法においては、酸分解の工程において添加する酸の量を少量とすることができるので、後工程における処理での水、中和剤および溶媒の使用量を削減することができる。また、本発明によると、溶媒可溶性リグニンを回収することができ、このリグニンを原料として各種の機能性ポリマー、特にポリエステルを合成することができる。 According to the present invention, together with a liquefied resin raw material composition that can be obtained from a lignocellulose-containing material, such as lignin, which has been difficult to separate in the past in a liquefied state that can be easily separated and purified, cellulose is used as a solvent. It can be obtained in a form that is easy to disperse. In the production method of the present invention, since the amount of acid added in the acid decomposition step can be reduced, the amount of water, neutralizing agent and solvent used in the treatment in the subsequent step can be reduced. Further, according to the present invention, solvent-soluble lignin can be recovered, and various functional polymers, particularly polyesters, can be synthesized using this lignin as a raw material.
Claims (7)
前記酸分解工程は、芳香族系グリコールエーテル、３−メトキシブタノールおよび４−メトキシブタノールからなる群から選ばれる少なくとも１つを含む溶媒中で、酸としてスルホン酸系の酸を用いて行い、
前記酸の添加量が、絶乾状態のリグノセルロース含有材料１０ｇに対して０．１〜５ｍｍｏｌの範囲内であることを特徴とするリグノセルロース含有材料からの機能材料の製造方法。 A method for producing a functional material comprising an acid decomposition step of acid decomposition by adding an acid to a lignocellulose-containing material in a solvent, and a filtration step,
The acid decomposition step is performed using a sulfonic acid acid as an acid in a solvent containing at least one selected from the group consisting of aromatic glycol ether, 3-methoxybutanol and 4-methoxybutanol,
The method for producing a functional material from a lignocellulose-containing material, wherein the added amount of the acid is within a range of 0.1 to 5 mmol with respect to 10 g of the lignocellulose-containing material in an absolutely dry state.
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| JP2015006997A (en) * | 2013-06-24 | 2015-01-15 | 花王株式会社 | Ultraviolet absorber |
| US10526500B2 (en) | 2014-12-02 | 2020-01-07 | Seiko Epson Corporation | Film-forming ink, film formation method, device with film, and electronic apparatus |
| CN115897274A (en) * | 2022-11-22 | 2023-04-04 | 中国科学院广州能源研究所 | Method for synchronously preparing high-purity cellulose by separating components of lignocellulose biomass |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5083501A (en) * | 1973-11-23 | 1975-07-05 | ||
| JP2006016522A (en) * | 2004-07-02 | 2006-01-19 | Kanai Educational Institution | Amphiphilic biodegradable polyester and its manufacturing process |
| JP2007006827A (en) * | 2005-07-01 | 2007-01-18 | Tokyo Univ Of Marine Science & Technology | Method for synthesis of lignin-polyester copolymer using enzyme |
| JP2011084493A (en) * | 2009-10-14 | 2011-04-28 | Kyoto Univ | Ultraviolet absorber |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5083501A (en) * | 1973-11-23 | 1975-07-05 | ||
| JP2006016522A (en) * | 2004-07-02 | 2006-01-19 | Kanai Educational Institution | Amphiphilic biodegradable polyester and its manufacturing process |
| JP2007006827A (en) * | 2005-07-01 | 2007-01-18 | Tokyo Univ Of Marine Science & Technology | Method for synthesis of lignin-polyester copolymer using enzyme |
| JP2011084493A (en) * | 2009-10-14 | 2011-04-28 | Kyoto Univ | Ultraviolet absorber |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015006997A (en) * | 2013-06-24 | 2015-01-15 | 花王株式会社 | Ultraviolet absorber |
| US10526500B2 (en) | 2014-12-02 | 2020-01-07 | Seiko Epson Corporation | Film-forming ink, film formation method, device with film, and electronic apparatus |
| CN115897274A (en) * | 2022-11-22 | 2023-04-04 | 中国科学院广州能源研究所 | Method for synchronously preparing high-purity cellulose by separating components of lignocellulose biomass |
| CN115897274B (en) * | 2022-11-22 | 2024-05-03 | 中国科学院广州能源研究所 | Method for synchronously preparing high-purity cellulose by separating lignocellulose biomass components |
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