JP2011246630A - Partially acylated lignin, epoxy resin composition using the same, and method for producing the same - Google Patents
Partially acylated lignin, epoxy resin composition using the same, and method for producing the same Download PDFInfo
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本発明は、リグニン分子中に存在するアルコール性水酸基及びフェノール性水酸基のうちアルコール性水酸基のみをアシル化した溶剤可溶性リグニン誘導体、およびそれを硬化剤として用いたエポキシ樹脂組成物に関するものである。 The present invention relates to a solvent-soluble lignin derivative obtained by acylating only an alcoholic hydroxyl group among alcoholic hydroxyl groups and phenolic hydroxyl groups present in a lignin molecule, and an epoxy resin composition using the same as a curing agent.
フェノール化合物とエポキシ樹脂の反応によってエポキシ樹脂硬化物が得られることが知られている。また、エポキシ樹脂組成物を製造する際に、石油由来のフェノール化合物ではなく、植物由来のリグニンを用いてエポキシ樹脂を製造することが最近報告された（非特許文献１）。
しかし、これにより得られるエポキシ樹脂硬化物は、吸水性が石油由来成分を利用したエポキシ樹脂硬化物と比べて若干高いことが指摘されており、硬化物分子中に存在するアルコール性水酸基の存在が一因となっていると推定される。また、リグニンは種々の溶媒に対する可溶性に乏しく、このことにより、エポキシ樹脂製造の条件が限られたものとなっていた。
It is known that a cured epoxy resin can be obtained by a reaction between a phenol compound and an epoxy resin. Moreover, when manufacturing an epoxy resin composition, it was reported recently that an epoxy resin is manufactured not using petroleum-derived phenol compounds but using plant-derived lignin (Non-patent Document 1).
However, it has been pointed out that the cured epoxy resin obtained in this way has a slightly higher water absorption than the cured epoxy resin using a petroleum-derived component, and the presence of alcoholic hydroxyl groups present in the cured product molecules. It is estimated that this is a cause. In addition, lignin is poorly soluble in various solvents, which limits the conditions for producing epoxy resins.
一方、アルコール性水酸基及びフェノール性水酸基を有する化合物において、これらの水酸基を選択的にエステル化することにより（非特許文献２）、また、これらの水酸基のエステルを選択的に分解することにより（非特許文献３）、アルコール性水酸基のみがエステル化された化合物を製造する方法が知られている。 On the other hand, in a compound having an alcoholic hydroxyl group and a phenolic hydroxyl group, by selectively esterifying these hydroxyl groups (Non-Patent Document 2), or by selectively decomposing esters of these hydroxyl groups (Non-Patent Document 2) Patent Document 3), a method for producing a compound in which only an alcoholic hydroxyl group is esterified is known.
本発明は、リグニンを硬化剤とするエポキシ樹脂組成物において、使用するリグニンのエポキシ樹脂に対する反応性を維持しつつ、その溶媒可溶性を高めることにより、穏和な条件において硬化することのできる、リグニンを硬化剤とするエポキシ樹脂組成物を提供することを課題とする。 In the epoxy resin composition using lignin as a curing agent, the present invention maintains the reactivity of the lignin used to the epoxy resin, while increasing the solvent solubility of the lignin, which can be cured under mild conditions. It is an object to provide an epoxy resin composition as a curing agent.
本発明者は、リグニン分子中に存在するアルコール性水酸基及びフェノール性水酸基のうちアルコール性水酸基のみをアシル化した溶剤可溶性リグニン誘導体を提供し、当該部分アシル化リグニンをエポキシ樹脂の硬化剤として用いることにより、上記課題を解決した。 The present inventor provides a solvent-soluble lignin derivative obtained by acylating only an alcoholic hydroxyl group among alcoholic hydroxyl groups and phenolic hydroxyl groups present in a lignin molecule, and using the partially acylated lignin as a curing agent for an epoxy resin. The above-mentioned problem was solved.
リグニン分子中に存在するアルコール性水酸基及びフェノール性水酸基をエステル化やエーテル化によって誘導体に転換することによって、リグニンが種々の溶剤に可溶となることが、従来から知られている。
しかしながら、このようにして可溶化したリグニンをエポキシ樹脂の硬化に用いた例はない。
本発明者は、リグニン分子中に存在するアルコール性水酸基及びフェノール性水酸基のうち、アルコール性水酸基のみをアシル化することにより、溶媒中でエポキシ樹脂の硬化反応を行うのに充分な溶媒可溶性が得られ、かつ、当該硬化反応を比較的穏和な条件下で行うことができる反応性が維持されることを見出し、本発明を完成したものである。
It has been conventionally known that lignin is soluble in various solvents by converting alcoholic and phenolic hydroxyl groups present in the lignin molecule into derivatives by esterification or etherification.
However, there is no example of using the lignin solubilized in this way for curing the epoxy resin.
The present inventor has obtained sufficient solvent solubility to carry out a curing reaction of an epoxy resin in a solvent by acylating only the alcoholic hydroxyl group out of the alcoholic hydroxyl group and phenolic hydroxyl group present in the lignin molecule. And the present inventors have found that the reactivity that allows the curing reaction to be performed under relatively mild conditions is maintained, and the present invention has been completed.
具体的には、本出願は、以下の発明を提供する。
〈１〉リグニン分子中のアルコール性水酸基を選択的にアシル化した可溶性リグニン誘導体。
〈２〉〈１〉の選択的アシル化リグニン誘導体からなる、エポキシ樹脂硬化剤。
〈３〉〈１〉の選択的アシル化リグニン誘導体を用いて、エポキシ樹脂を硬化させる方法。
〈４〉〈３〉の方法により硬化したエポキシ樹脂硬化物。
〈５〉〈１〉の選択的アシル化リグニン誘導体とエポキシ樹脂を含む、エポキシ樹脂組成物。
Specifically, the present application provides the following inventions.
<1> A soluble lignin derivative obtained by selectively acylating an alcoholic hydroxyl group in a lignin molecule.
<2> An epoxy resin curing agent comprising the selective acylated lignin derivative of <1>.
<3> A method of curing an epoxy resin using the selective acylated lignin derivative of <1>.
<4> A cured epoxy resin cured by the method of <3>.
<5> An epoxy resin composition comprising the selectively acylated lignin derivative of <1> and an epoxy resin.
本発明により、アルコール性水酸基をアシル化することによって、溶剤に可溶となるリグニンとしては、例えば、アルカリリグニン、クラフトリグニン、アシドリシスリグニン、加溶媒分解リグニン、蒸煮爆砕リグニン、糖化残渣リグニン、リグニンスルホン酸塩などが例示されるが、これに限られない。 According to the present invention, the lignin that becomes soluble in a solvent by acylating an alcoholic hydroxyl group includes, for example, alkaline lignin, kraft lignin, acidolysis lignin, solvolytic lignin, steamed pyrolysis lignin, saccharification residue lignin, lignin Although sulfonate etc. are illustrated, it is not restricted to this.
アルコール性水酸基のみをアシル化した溶剤可溶性リグニン誘導体は、完全アシル化したリグニンにおいて選択的にフェノール性水酸基のエステルを分解するか、リグニン原試料のアルコール性水酸基を選択的アシル化すること（化学的方法あるいはリパーゼ等を用いる生化学的方法）によって製造できる。 Solvent-soluble lignin derivatives acylated only with alcoholic hydroxyl groups can either selectively decompose phenolic hydroxyl ester in fully acylated lignin or selectively acylate alcoholic hydroxyl groups in the lignin raw sample (chemically Or a biochemical method using lipase or the like).
本発明のアルコール性水酸基が選択的にアシル化されたリグニン誘導体は、溶剤可溶性が高まり、かつ、遊離のフェノール性水酸基を有するために、溶剤中で比較的穏和な条件下でエポキシ樹脂等の反応性成分と反応させることによって、各種の有用な樹脂を製造するための原料として用いることができる。さらに、製造された樹脂中のリグニン分子中のアルコール性水酸基がエステル基で保護されているため、得られる樹脂の耐熱性の向上が期待できる。 The lignin derivative in which the alcoholic hydroxyl group of the present invention is selectively acylated has increased solvent solubility and has a free phenolic hydroxyl group, so that it can react with an epoxy resin or the like under a relatively mild condition in the solvent. By making it react with a sex component, it can be used as a raw material for producing various useful resins. Furthermore, since the alcoholic hydroxyl group in the lignin molecule in the produced resin is protected with an ester group, an improvement in the heat resistance of the resulting resin can be expected.
以下の実施例を用いて、本発明を、更に詳細に説明する。 The invention is explained in more detail using the following examples.
実施例１
完全アセチル化したアルカリリグニン１０重量部を乾燥ジオキサン５０重量部に溶解し、１０重量部のピロリジンを加えて室温で２時間撹拌した。反応混合物を０．１ＭＨＣｌ溶液１０００ｍＬに撹拌しながら注ぎ、沈殿物を得た。沈殿物をろ別し、ろ液が中性になるまで水洗した。沈殿物を風乾したのち、７０℃で真空乾燥した。試料のＦＴＩＲスペクトルには、１７３０ｃｍ−１のアルコール性水酸基の酢酸エステルに由来するピークのみが観察され、１７６０ｃｍ−１のフェノール性水酸基の酢酸エステルに由来するピークは認められなかった。表1に試料の溶剤への溶解性を示す。
Example 1
10 parts by weight of fully acetylated alkali lignin was dissolved in 50 parts by weight of dry dioxane, 10 parts by weight of pyrrolidine was added, and the mixture was stirred at room temperature for 2 hours. The reaction mixture was poured into 1000 mL of 0.1 M HCl solution with stirring to obtain a precipitate. The precipitate was filtered off and washed with water until the filtrate was neutral. The precipitate was air-dried and then vacuum-dried at 70 ° C. The FTIR spectra of the samples, only a peak derived from the acetic acid ester of an alcohol hydroxyl group of 1730 cm -1 was observed, a peak derived from the acetic acid ester of the phenolic hydroxyl group of 1760 cm -1 was observed. Table 1 shows the solubility of the sample in the solvent.
実施例２
アシドリシスリグニン１０重量部を乾燥ジオキサン３０重量部に分散させて、無水酢酸７重量部及び四オクタン酸チタン０．１重量部を加えて５０℃で１時間加熱撹拌した。得られた反応溶液を１０００ｍＬの水に撹拌しながら注ぎ、沈殿物を得た。沈殿物をろ別し、ろ液が中性になるまで水洗した。沈殿物を風乾したのち、７０℃で真空乾燥した。試料のＦＴＩＲスペクトルには、１７３０ｃｍ−１のアルコール性水酸基の酢酸エステルに由来するピークのみが観察され、１７６０ｃｍ−１のフェノール性水酸基の酢酸エステルに由来するピークは認められなかった。
表２に部分アセチル化アシドリシスリグニンの溶剤への溶解性の例を示す。
Example 2
10 parts by weight of acidolysis lignin was dispersed in 30 parts by weight of dry dioxane, 7 parts by weight of acetic anhydride and 0.1 part by weight of titanium tetraoctanoate were added, and the mixture was heated and stirred at 50 ° C. for 1 hour. The obtained reaction solution was poured into 1000 mL of water with stirring to obtain a precipitate. The precipitate was filtered off and washed with water until the filtrate was neutral. The precipitate was air-dried and then vacuum-dried at 70 ° C. The FTIR spectra of the samples, only a peak derived from the acetic acid ester of an alcohol hydroxyl group of 1730 cm -1 was observed, a peak derived from the acetic acid ester of the phenolic hydroxyl group of 1760 cm -1 was observed.
Table 2 shows examples of the solubility of partially acetylated acidolytic lignin in a solvent.
実施例３
実施例１で得られた選択的アシル化リグニン誘導体１部とノボラック系フェノール樹脂ポリグリシジルエーテル（分子量５７０）０．７部及びイミダゾール系促進剤０．０１部をテトラヒドロフランに溶解し、得られた溶液をシャーレにキャストし、これをデシケーター中に静置してテトラヒドロフランを蒸発除去した。得られた試料を、１８０℃で２時間加熱してエポキシ樹脂硬化物を得た。得られた試料のＦＴＩＲスペクトルには、エポキシ基に帰属される９７０ｃｍ−１のピークは認められなかった。また、水酸基に帰属されるピークは硬化前後で３３１５ｃｍ−１から３４２０ｃｍ−１に移動した。昇温速度１０℃／minで行った、示差走査熱量測定（ＤＳＣ）によって求めたエポキシ樹脂硬化物のガラス転移温度は１５９．０℃であった。また、窒素気流中で、昇温速度１０℃／minで行った、熱重量測定（TG）によって求めた熱分解温度は、２７４．１℃（重量減少率１％）及び３０４．７℃（重量減少率５％）であった。また、ＫＣｌ飽和水溶液で調湿したデシケーター中に試料を重量が恒値となるまで２０℃で静置して、測定した吸水率は１．１％であった。
このことから、実施例１の方法により得られた選択的アシル化リグニン誘導体が、エポキシ化合物と充分に反応し得る可溶性を有し、これを用いることにより、比較的穏和な条件でエポキシ樹脂組成物の十分な硬化がなされたことが確認できる。また、得られたエポキシ樹脂組成物中のリグニンに由来するアルコール性水酸基がアシル化されていることに起因してエポキシ樹脂組成物の耐熱性が向上する。
Example 3
A solution obtained by dissolving 1 part of the selectively acylated lignin derivative obtained in Example 1, 0.7 part of a novolak phenol resin polyglycidyl ether (molecular weight 570) and 0.01 part of an imidazole accelerator in tetrahydrofuran. Was cast in a petri dish, and left standing in a desiccator to evaporate and remove tetrahydrofuran. The obtained sample was heated at 180 ° C. for 2 hours to obtain a cured epoxy resin. In the FTIR spectrum of the obtained sample, no peak at 970 cm −1 attributable to the epoxy group was observed. Further, peaks attributable to a hydroxyl group was moved from 3315cm -1 to 3420cm -1 before and after curing. The glass transition temperature of the cured epoxy resin obtained by differential scanning calorimetry (DSC) performed at a temperature elevation rate of 10 ° C./min was 159.0 ° C. The thermal decomposition temperatures determined by thermogravimetry (TG) performed in a nitrogen stream at a rate of temperature increase of 10 ° C./min were 274.1 ° C. (weight reduction rate 1%) and 304.7 ° C. (weight). The reduction rate was 5%). The sample was allowed to stand at 20 ° C. in a desiccator conditioned with a saturated aqueous solution of KCl until the weight reached a constant value, and the measured water absorption was 1.1%.
Therefore, the selectively acylated lignin derivative obtained by the method of Example 1 has a solubility capable of sufficiently reacting with an epoxy compound, and by using this, an epoxy resin composition under relatively mild conditions. It can be confirmed that sufficient curing has been achieved. Further, the heat resistance of the epoxy resin composition is improved due to acylation of the alcoholic hydroxyl group derived from lignin in the obtained epoxy resin composition.
実施例４
実施例２で得られた選択的アシル化リグニン誘導体１部とビスフェノールAジグリシジルエーテル０．７部及びイミダゾール系促進剤０．０１部をテトラヒドロフランに溶解し、得られた溶液をシャーレにキャストし、これをデシケーター中に静置してテトラヒドロフランを蒸発除去した。得られた試料を、１８０℃で２時間加熱してエポキシ樹脂硬化物を得た。得られた試料のＦＴＩＲスペクトルには、エポキシ基に帰属される９７０ｃｍ−１のピークは認められなかった。また、水酸基に帰属されるピークは硬化前後で３４５８ｃｍ−１から３３８４ｃｍ−１に移動した。昇温速度１０℃／minで行った、示差走査熱量測定（ＤＳＣ）によって求めたエポキシ樹脂硬化物のガラス転移温度は１６３．２℃であった。また、窒素気流中で、昇温速度１０℃／minで行った、熱重量測定（TG）によって求めた熱分解温度は、２９１．２℃（重量減少率１％）及び３３０．８℃（重量減少率５％）であった。また、ＫＣｌ飽和水溶液で調湿したデシケーター中に試料を重量が恒値となるまで２０℃で静置して、測定した吸水率は１．０％であった。
このことから、実施例２の方法により得られた選択的アシル化リグニン誘導体についても、エポキシ化合物と充分に反応し得る可溶性を有し、これを用いることにより、比較的穏和な条件でエポキシ樹脂組成物の十分な硬化がなされたことが確認できる。また、得られたエポキシ樹脂組成物中のリグニンに由来するアルコール性水酸基がアシル化されていることに起因してエポキシ樹脂組成物の耐熱性が向上する。
Example 4
1 part of the selectively acylated lignin derivative obtained in Example 2, 0.7 part of bisphenol A diglycidyl ether and 0.01 part of imidazole accelerator were dissolved in tetrahydrofuran, and the resulting solution was cast into a petri dish. This was left still in a desiccator to evaporate and remove tetrahydrofuran. The obtained sample was heated at 180 ° C. for 2 hours to obtain a cured epoxy resin. In the FTIR spectrum of the obtained sample, no peak at 970 cm −1 attributable to the epoxy group was observed. Further, peaks attributable to a hydroxyl group was moved from 3458cm -1 to 3384cm -1 before and after curing. The glass transition temperature of the cured epoxy resin obtained by differential scanning calorimetry (DSC) performed at a temperature elevation rate of 10 ° C./min was 163.2 ° C. The thermal decomposition temperatures determined by thermogravimetry (TG) performed at a rate of temperature increase of 10 ° C./min in a nitrogen stream were 291.2 ° C. (weight reduction rate 1%) and 330.8 ° C. (weight). The reduction rate was 5%). The sample was allowed to stand at 20 ° C. in a desiccator conditioned with a saturated aqueous solution of KCl until the weight reached a constant value, and the measured water absorption was 1.0%.
Therefore, the selectively acylated lignin derivative obtained by the method of Example 2 also has a solubility capable of sufficiently reacting with the epoxy compound, and by using this, the epoxy resin composition can be used under relatively mild conditions. It can be confirmed that the product has been sufficiently cured. Further, the heat resistance of the epoxy resin composition is improved due to acylation of the alcoholic hydroxyl group derived from lignin in the obtained epoxy resin composition.
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| DE102013219718A1 (en) * | 2013-09-30 | 2015-04-02 | Bayerische Motoren Werke Aktiengesellschaft | A curable resin composition, a fiber composite, a kit for producing a curable resin composition and a method for producing a cured resin and a fiber composite |
| WO2015178103A1 (en) * | 2014-05-23 | 2015-11-26 | ハリマ化成株式会社 | Resin composition and method for producing same |
| WO2016063779A1 (en) * | 2014-10-20 | 2016-04-28 | ハリマ化成株式会社 | Epoxy resin and hardener for epoxy resin |
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| WO2015178103A1 (en) * | 2014-05-23 | 2015-11-26 | ハリマ化成株式会社 | Resin composition and method for producing same |
| WO2016063779A1 (en) * | 2014-10-20 | 2016-04-28 | ハリマ化成株式会社 | Epoxy resin and hardener for epoxy resin |
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