JP2008169268A - Method for producing phenolic resin spherical cured product - Google Patents
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本発明は、フェノール樹脂球状硬化物の製造方法に関する。 The present invention relates to a method for producing a phenol resin spherical cured product.
フェノール樹脂は高耐熱性、高難燃性などの優れた性質を有しているため、成形材料用、繊維強化プラスチックのバインダー用、各種炭素材料の炭素源用等として広く使用されている。 Since phenolic resins have excellent properties such as high heat resistance and high flame retardancy, they are widely used for molding materials, binders for fiber-reinforced plastics, carbon sources for various carbon materials, and the like.
従来、フェノール樹脂の球状硬化物を得る方法としてはフェノール類とアルデヒド類を用いて懸濁重合プロセスを行う方法が知られており、例えば、平均粒径が１０〜５０００μｍの球状硬化物が得られている（特許文献１、２）。この球状硬化物は主として加熱成形を行うためのバインダーとして使用されている。懸濁重合プロセスにより得られた球状硬化物は、通常反応終了後に固液分離をすると分散剤の影響で凝集することから、凝集物を砕く解砕工程が必要であった。この解砕工程はそれ自体コスト上昇の要因となるだけでなく、粒子の凝集を強制的に解くことから、球状粒子に欠けが生じるなど、粒子形状が失われやすいという問題点がある。さらに解砕に用いる粉砕機の材質によっては金属不純物を巻き込み、硬化物のその後の純度に悪影響を及ぼすことになる。 Conventionally, as a method of obtaining a spherical cured product of a phenol resin, a method of performing a suspension polymerization process using phenols and aldehydes is known. For example, a spherical cured product having an average particle size of 10 to 5000 μm is obtained. (Patent Documents 1 and 2). This spherical cured product is mainly used as a binder for thermoforming. Since the spherical cured product obtained by the suspension polymerization process usually aggregates due to the influence of the dispersant when solid-liquid separation is performed after the reaction is completed, a pulverization step for crushing the aggregate is necessary. This crushing process itself not only causes an increase in cost, but also has a problem that the particle shape is easily lost, for example, the spherical particles are chipped because the particles are forcibly solved. Furthermore, depending on the material of the pulverizer used for crushing, metal impurities may be involved, which will adversely affect the subsequent purity of the cured product.
上記問題点を解消する方法として、硬化反応後に硬化物粒子を水洗する方法が報告されているが（特許文献３）、この水洗過程で発生する大量の廃液処理も大きな問題となる。 As a method for solving the above problems, there has been reported a method of washing the cured particles after the curing reaction (Patent Document 3), but a large amount of waste liquid treatment generated in the washing process is also a big problem.
このほかに、懸濁安定剤を用いない手法としては、酸性触媒下でフェノール類と大過剰のホルマリンとを反応させて、微粒子状のフェノール樹脂を製造する方法が開示されている（特許文献４）。しかしながら、この方法では大過剰のホルマリン、塩酸を用いるため製造コストが高く、反応後の廃水処理の問題が生じる。また、球状硬化物の真球度も低くなる傾向があった。
本発明の目的は、容易に固液分離が可能で、二次凝集がなく、真球度が極めて高い安価なフェノール樹脂球状硬化物を製造する方法を提供することである。 An object of the present invention is to provide a method for producing an inexpensive phenolic resin spherical cured product that can be easily separated into solid and liquid, has no secondary aggregation, and has a very high sphericity.
すなわち、本発明は以下のフェノール樹脂球状硬化物の製造方法に関する。
本発明は、（１）フェノール樹脂を懸濁安定剤の存在下、水性媒体中で硬化させてフェノール樹脂球状硬化物の懸濁液を作製する工程と、前記懸濁液に分解促進剤を添加して前記懸濁安定剤を分解し、次いで固液分離する工程とを含むことを特徴とするフェノール樹脂球状硬化物の製造方法に関する。
That is, this invention relates to the manufacturing method of the following phenol resin spherical hardened | cured materials.
The present invention includes (1) a step of curing a phenol resin in an aqueous medium in the presence of a suspension stabilizer to produce a suspension of a phenol resin spherical cured product, and adding a decomposition accelerator to the suspension And a step of decomposing the suspension stabilizer, followed by solid-liquid separation.
また、本発明は、（２）前記懸濁安定剤が、グルコースのα−１，４グリコシド結合を有する水溶性高分子であることを特徴とする前記（１）記載のフェノール樹脂球状硬化物の製造方法に関する。 The present invention also provides (2) the phenol resin spherical cured product according to (1), wherein the suspension stabilizer is a water-soluble polymer having an α-1,4 glycoside bond of glucose. It relates to a manufacturing method.
また、本発明は、（３）前記懸濁安定剤が、水溶性澱粉類であることを特徴とする前記（１）または（２）記載のフェノール樹脂球状硬化物の製造方法に関する。 The present invention also relates to (3) the method for producing a spherical cured product of phenol resin according to (1) or (2), wherein the suspension stabilizer is a water-soluble starch.
また、本発明は、（４）前記分解促進剤が、懸濁安定剤を分解可能な酵素であることを特徴とする前記（１）〜（３）記載のフェノール樹脂球状硬化物の製造方法に関する。 In addition, the present invention relates to (4) the method for producing a spherical cured product of phenol resin according to (1) to (3), wherein the decomposition accelerator is an enzyme capable of decomposing a suspension stabilizer. .
また、本発明は、（５）前記分解促進剤が、懸濁安定剤を分解可能な酸または塩基であることを特徴とする前記（１）〜（３）記載のフェノール樹脂球状硬化物の製造方法に関する。 The present invention also provides (5) the phenol resin spherical cured product according to (1) to (3) above, wherein the decomposition accelerator is an acid or a base capable of decomposing a suspension stabilizer. Regarding the method.
また、本発明は、（６）フェノール樹脂球状硬化物の平均粒径が１〜１０００μｍであることを特徴とする前記（１）〜（５）のいずれか一項に記載のフェノール樹脂球状硬化物の製造方法に関する。 Moreover, this invention is (6) phenol resin spherical hardened | cured material as described in any one of said (1)-(5) characterized by the average particle diameters being 1-1000 micrometers. It relates to the manufacturing method.
本発明の製造方法によれば、容易に固液分離が可能で、二次凝集がなく、真球度が極めて高いフェノール樹脂球状硬化物を安価に製造することができる。 According to the production method of the present invention, it is possible to produce a phenol resin spherical cured product that can be easily separated into solid and liquid, has no secondary aggregation, and has extremely high sphericity at low cost.
以下に、本発明のフェノール樹脂球状硬化物の製造方法について説明する。 Below, the manufacturing method of the phenol resin spherical hardened | cured material of this invention is demonstrated.
本発明のフェノール樹脂球状硬化物の製造方法は、フェノール樹脂を懸濁安定剤の存在下、水性媒体中で硬化させてフェノール樹脂球状硬化物の懸濁液を作製する工程と、前記懸濁液に分解促進剤を添加して前記懸濁安定剤を分解し、次いで固液分離する工程とを含むことを特徴とする。 The method for producing a spherical cured product of phenolic resin according to the present invention includes a step of curing a phenolic resin in an aqueous medium in the presence of a suspension stabilizer to produce a suspension of the spherical cured phenolic product, and the suspension. And a step of decomposing the suspension stabilizer by adding a decomposition accelerator, followed by solid-liquid separation.
本発明では、まず、フェノール樹脂を懸濁安定剤の存在下、水性媒体中で硬化させてフェノール樹脂球状硬化物の懸濁液を作製する。 In the present invention, the phenol resin is first cured in an aqueous medium in the presence of a suspension stabilizer to prepare a suspension of a phenol resin spherical cured product.
本発明において用いられるフェノール樹脂は、フェノール類とアルデヒド類を触媒の存在下に重縮合させることによって得られる樹脂である。フェノール類としては、フェノール及びフェノール誘導体である。フェノール誘導体としては、例えば、炭素数１〜９のアルキル基で置換されたｏ−アルキルフェノール、ｍ−アルキルフェノール、ｐ−アルキルフェノール、具体的には、ｏ−クレゾール、ｍ−クレゾール、ｐ−クレゾール、ｐ−ｔｅｒｔ−オクチルフェノール、ｐ−ｔｅｒｔ−ブチルフェノール、２，３−キシレノール、２，４−キシレノール、２，５−キシレノール、２，６−キシレノール、３，５−キシレノール、２，３，５−トリメチルフェノールなどのアルキルフェノール類；カテコール、レゾルシノールなどのポリフェノール類；ビスフェノール−Ａなどのビスフェノール類；及びこれらのベンゼン核またはアルキル基の水素原子の一部または全部がハロゲン原子で置換されたハロゲン化フェノール類などが例示され、特にこれらに限定されるものではない。これらフェノール類は単独あるいは２種以上を用いることができる。アルデヒド類としては、例えば、ホルムアルデヒド、パラホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド、ベンズアルデヒド、グリオキサールなどが例示され、特にこれらに限定されるものではない。これらのなかでも、コストの問題からホルムアルデヒド、パラホルムアルデヒドを使用するのが望ましい。これらアルデヒド類は単独あるいは２種以上を用いることができる。触媒としては、酸性触媒または塩基性触媒である。酸性触媒としては、塩酸、硫酸、しゅう酸、リン酸などが例示され、これらは単独あるいは２種以上を用いることができる。塩基性触媒としては、水酸化リチウム、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属の水酸化物；水酸化カルシウム、水酸化バリウムなどのアルカリ土類金属の水酸化物；アンモニアなどのアミノ水素を含有する化合物；トリエチルアミンなどの三級アンモニウム化合物などが例示され、これらは単独あるいは２種以上を用いることができる。触媒として酸性触媒を用いた場合はノボラック型のフェノール樹脂が得られ、塩基性触媒を用いた場合はレゾール型のフェノール樹脂が得られる。本発明ではレゾール型のフェノール樹脂が賞用される。また、本発明ではフェノール樹脂は単独あるいは２種以上を用いてもよく、さらに一定の割合で他のポリマ或いはフィラーと混合して用いてもよい。 The phenol resin used in the present invention is a resin obtained by polycondensation of phenols and aldehydes in the presence of a catalyst. Phenols are phenol and phenol derivatives. Examples of the phenol derivative include o-alkylphenol, m-alkylphenol, p-alkylphenol substituted with an alkyl group having 1 to 9 carbon atoms, specifically, o-cresol, m-cresol, p-cresol, p- tert-octylphenol, p-tert-butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, etc. Examples include alkylphenols; polyphenols such as catechol and resorcinol; bisphenols such as bisphenol-A; and halogenated phenols in which some or all of hydrogen atoms of these benzene nuclei or alkyl groups are substituted with halogen atoms. Especially this The present invention is not limited to. These phenols can be used alone or in combination of two or more. Examples of aldehydes include, but are not limited to, formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, glyoxal, and the like. Of these, it is desirable to use formaldehyde and paraformaldehyde from the viewpoint of cost. These aldehydes can be used alone or in combination of two or more. The catalyst is an acidic catalyst or a basic catalyst. Examples of the acidic catalyst include hydrochloric acid, sulfuric acid, oxalic acid, phosphoric acid and the like, and these can be used alone or in combination of two or more. Basic catalysts include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide; and amino hydrogens such as ammonia. Compounds to be contained; tertiary ammonium compounds such as triethylamine are exemplified, and these can be used alone or in combination of two or more. When an acidic catalyst is used as the catalyst, a novolac type phenol resin is obtained, and when a basic catalyst is used, a resol type phenol resin is obtained. In the present invention, a resol-type phenol resin is used. In the present invention, the phenol resin may be used alone or in combination of two or more, and may be used in a mixture with other polymer or filler at a certain ratio.
本発明で用いられる懸濁安定剤としては、反応溶液中で分解可能であれば特に限定されず、例えば、馬鈴薯澱粉、甘藷澱粉、タピオカ澱粉など各種植物の地下部から得られる澱粉；小麦澱粉、米澱粉、コーンスターチなどの各種穀物から得られる澱粉；またはこれらの澱粉をアセチル化、エステル化、グラフト化またはエーテル化した澱粉誘導体；これらの澱粉や澱粉誘導体を３−クロローヒドロキシプロピルトリメチルアンモニウムクロライドやグリシジルトリメチルアンモニウムクロライド等のカチオン化剤とアルカリ触媒の存在下で反応させることによって得られるカチオン性及び両性澱粉；又は前記澱粉、澱粉誘導体、カチオン性及び両性澱粉等を澱粉分解酵素を用いて低粘度化した酵素変性澱粉；塩素、サラシ粉、次亜塩素塩、過酸化水素、過マンガン酸カリ等の酸化剤で低粘度化した酸化澱粉などの澱粉類、セルロースを水溶化したヒドロキシエチルセルロース、カルボキシメチルセルロースなどの水溶性セルロースなどがあげられる。これらのなかでも、グルコースのα−１，４グリコシド結合を有する水溶性高分子が好ましく、水溶性澱粉類がより好ましく、コーンスターチ、小麦澱粉、澱粉誘導体が特に好ましい。懸濁安定剤の種類や使用量はフェノール樹脂球状硬化物の平均粒径を左右し、例えば、懸濁安定剤の使用量が多い場合はフェノール樹脂球状硬化物の平均粒径が小さくなる傾向にあり、逆に少ない場合は該平均粒径が大きくなる傾向にあるので、適宜選択して所望の平均粒径になるよう調整する。 The suspension stabilizer used in the present invention is not particularly limited as long as it can be decomposed in the reaction solution. For example, starch obtained from underground parts of various plants such as potato starch, sweet potato starch, tapioca starch; wheat starch, Starch obtained from various cereals such as rice starch and corn starch; or starch derivatives obtained by acetylating, esterifying, grafting or etherifying these starches; converting these starches or starch derivatives into 3-chloro-hydroxypropyltrimethylammonium chloride, Cationic and amphoteric starch obtained by reacting with a cationizing agent such as glycidyltrimethylammonium chloride in the presence of an alkali catalyst; or the starch, starch derivative, cationic and amphoteric starch, etc. with low viscosity using starch degrading enzyme Enzyme-modified starch; chlorine, sardine powder, hypochlorite, excess Hydrogen, starches such as low viscosity was oxidized starch with an oxidizing agent such as potassium permanganate, hydroxyethyl cellulose water-soluble cellulose, water-soluble celluloses such as carboxymethyl cellulose and the like. Among these, water-soluble polymers having an α-1,4 glycosidic bond of glucose are preferable, water-soluble starches are more preferable, and corn starch, wheat starch, and starch derivatives are particularly preferable. The type and amount of the suspension stabilizer affects the average particle size of the phenol resin spherical cured product.For example, when the amount of the suspension stabilizer used is large, the average particle size of the phenol resin spherical cured product tends to decrease. On the contrary, when the amount is small, the average particle size tends to increase. Therefore, the average particle size is appropriately selected and adjusted to a desired average particle size.
本発明ではフェノール樹脂の硬化反応は水性媒体中、加熱下に行われる。水性媒体としては特に限定されないが、通常は水が用いられる。また、水性媒体の使用量はフェノール樹脂球状硬化物の平均粒径を左右するので、適宜選択して所望の平均粒径になるよう調整する。加熱温度は７０〜１００℃であることが好ましいが、特に限定されるものではない。また、反応容器の形状も特に限定されないが、攪拌下に反応を行うことが好ましいため撹拌翼付反応容器や攪拌装置を用いることが好適である。攪拌翼の形状は特に限定されず、通常、邪魔板を有する錨型の撹拌翼が用いられる。攪拌速度などの攪拌条件はフェノール樹脂球状硬化物の平均粒径を左右し、例えば、攪拌速度が遅い場合は粒子同士が結合し合い平均粒径の大きな硬化物が得られる傾向にあるので、適宜選択して所望の平均粒径になるよう調整する。
本発明では、前記工程により作成したフェノール樹脂球状硬化物の懸濁液に分解促進剤を添加して懸濁安定剤を分解する。
本発明で用いられる分解促進剤は、懸濁安定剤を分解するものであれば特に限定されないが、好ましくは、懸濁安定剤を分解可能な酵素、酸または塩基であり、具体的には、α−アミラーゼ、β−アミラーゼ、グルコアミラーゼなどの澱粉分解酵素；セルラーゼなどのセルロース分解酵素；塩酸、硫酸、硝酸、シュウ酸、酢酸などの酸；水酸化ナトリウム、水酸化カリウム、水酸化リチウムなどの塩基などが例示される。これらのなかでも、澱粉分解酵素または酸がより好ましく、α−アミラーゼまたは塩酸が特に好ましい。分解促進剤の使用量は、特に限定されないが、懸濁安定剤に対して、好ましくは０．００００１〜１０重量％、より好ましくは０．０００１〜１重量％である。分解促進剤の使用量が０．００００１重量％未満であると懸濁安定剤の分解が充分に進まない傾向にあり、１０重量％を超えても添加効果に格段の差が無いので経済的に好ましくない傾向にある。
本発明の方法では、分解促進剤を用いて懸濁安定剤を分解することが重要であり、これによって容易に固液分離が可能で二次凝集がなく真球度の高いフェノール樹脂球状硬化物の製造を達成できる。
In the present invention, the curing reaction of the phenol resin is carried out in an aqueous medium under heating. Although it does not specifically limit as an aqueous medium, Usually, water is used. Moreover, since the usage-amount of an aqueous medium influences the average particle diameter of a phenol resin spherical hardened | cured material, it selects suitably and adjusts so that it may become a desired average particle diameter. The heating temperature is preferably 70 to 100 ° C., but is not particularly limited. The shape of the reaction vessel is not particularly limited, but it is preferable to use a reaction vessel with a stirring blade or a stirring device because the reaction is preferably carried out with stirring. The shape of the stirring blade is not particularly limited, and usually a bowl-shaped stirring blade having a baffle plate is used. Stirring conditions such as the stirring speed influence the average particle diameter of the phenolic resin spherical cured product.For example, when the stirring speed is slow, the particles tend to combine with each other to obtain a cured product having a large average particle diameter. Select and adjust to the desired average particle size.
In this invention, a suspension accelerator is decomposed | disassembled by adding a decomposition accelerator to the suspension of the phenol resin spherical cured material created by the said process.
The degradation accelerator used in the present invention is not particularly limited as long as it decomposes the suspension stabilizer, but is preferably an enzyme, acid or base capable of decomposing the suspension stabilizer, specifically, Starch-degrading enzymes such as α-amylase, β-amylase, and glucoamylase; Cellulolytic enzymes such as cellulase; Acids such as hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, and acetic acid; Sodium hydroxide, potassium hydroxide, lithium hydroxide, etc. Examples include bases. Among these, amylolytic enzyme or acid is more preferable, and α-amylase or hydrochloric acid is particularly preferable. Although the usage-amount of a decomposition accelerator is not specifically limited, Preferably it is 0.00001-10 weight% with respect to a suspension stabilizer, More preferably, it is 0.0001-1 weight%. If the amount of the decomposition accelerator used is less than 0.00001% by weight, the suspension stabilizer tends not to decompose sufficiently, and even if it exceeds 10% by weight, there is no significant difference in the effect of addition, so economically. It tends to be undesirable.
In the method of the present invention, it is important to decompose the suspension stabilizer using a decomposition accelerator, which enables easy solid-liquid separation, and there is no secondary aggregation, and the phenolic resin spherical cured product has high sphericity. Can be achieved.
分解反応は、通常、加熱下に行われる。加熱温度は適宜選択されるが、３０〜８０℃であることが好ましい。分解促進剤として酵素を用いる場合は、酵素が失活しない温度範囲内、通常は３５〜４５℃で加熱温度が選択される。
本発明では、前記分解反応後、懸濁液からフェノール樹脂球状硬化物を固液分離する。固液分離は常法に従って行えばよく、例えば、遠心分離、濾過、噴霧乾燥などが用いられるが特にこれに限定されるものではない。
The decomposition reaction is usually performed under heating. The heating temperature is appropriately selected, but is preferably 30 to 80 ° C. When an enzyme is used as the decomposition accelerator, the heating temperature is selected within a temperature range where the enzyme is not deactivated, usually 35 to 45 ° C.
In the present invention, after the decomposition reaction, the phenol resin spherical cured product is solid-liquid separated from the suspension. Solid-liquid separation may be performed according to a conventional method, and for example, centrifugation, filtration, spray drying, and the like are used, but the invention is not particularly limited thereto.
固液分離により取得したフェノール樹脂球状硬化物は、所望により、風乾、加熱乾燥または真空乾燥などの乾燥を行ってもよい。乾燥条件は特に規定されるものではないが、好ましくは６０℃〜１５０℃の温度下に行われる。温度が６０℃未満である場合は乾燥に時間がかかり効率が悪くなる傾向にあり、１５０℃を越える場合はフェノール樹脂球状硬化物が強く凝集する傾向にある。
本発明の方法により得られるフェノール樹脂球状硬化物の平均粒径は、特に限定されないが、１〜１０００μｍであることが好ましく、１０〜５００μｍであることがより好ましい。平均粒径が１μｍ未満である場合は、フェノール樹脂球状硬化物が飛散しやすく取り扱いに支障が生じる可能性がある。また、平均粒径が１０００μｍを越える場合は、フェノール樹脂球状硬化物を製造する際の反応条件によっては粒子の形状がいびつになり、球形を保持できなくなる可能性がある。
The phenolic resin spherical cured product obtained by solid-liquid separation may be subjected to drying such as air drying, heat drying or vacuum drying, if desired. The drying conditions are not particularly defined, but are preferably performed at a temperature of 60 ° C to 150 ° C. When the temperature is less than 60 ° C., drying tends to take time and the efficiency tends to deteriorate. When the temperature exceeds 150 ° C., the phenol resin spherical cured product tends to strongly aggregate.
Although the average particle diameter of the phenol resin spherical cured product obtained by the method of the present invention is not particularly limited, it is preferably 1 to 1000 μm, and more preferably 10 to 500 μm. When the average particle size is less than 1 μm, the spherical cured product of the phenol resin is likely to be scattered, which may hinder the handling. If the average particle size exceeds 1000 μm, the shape of the particles may become distorted depending on the reaction conditions in producing the phenol resin spherical cured product, and the spherical shape may not be maintained.
なお、フェノール樹脂球状硬化物の平均粒径の調整方法としては特に限定されないが、例えば、フェノール樹脂球状硬化物の懸濁液を作製する際、懸濁安定剤の種類、懸濁安定剤の量及び水性媒体の量、攪拌条件などを適宜選択することにより所望の平均粒径に調整することができる。 The method for adjusting the average particle diameter of the phenol resin spherical cured product is not particularly limited. For example, when preparing a suspension of the phenol resin spherical cured product, the type of suspension stabilizer, the amount of suspension stabilizer And it can adjust to a desired average particle diameter by selecting the quantity of an aqueous medium, stirring conditions, etc. suitably.
フェノール樹脂球状硬化物の平均粒径は、例えば、レーザ回折／散乱式粒度分布測定装置（株式会社堀場製作所社製、ＬＡ９２０）を用いて測定することができる。粒度測定サンプルはフェノール樹脂球状硬化物の懸濁液を用いて直接測定することができる。また、フェノール樹脂球状硬化物の粒子形状は、電子顕微鏡写真で直接観察することができる。 The average particle diameter of the phenol resin spherical cured product can be measured using, for example, a laser diffraction / scattering particle size distribution measuring apparatus (LA920, manufactured by Horiba, Ltd.). The particle size measurement sample can be directly measured using a suspension of a phenol resin spherical cured product. Moreover, the particle shape of a phenol resin spherical hardened | cured material can be directly observed with an electron micrograph.
本発明の製造方法により得られたフェノール樹脂球状硬化物は、そのまま単独使用にて或いは他の素材と複合化して、冷凍機、エアコンディショナー等の加湿ユニット、工業用フィルター等に利用でき、種々のプラスチックやゴムなどの耐熱性、機械的強度の改質材としても利用できる。また、真球度が高く耐衝撃性が高いことから、種々の研磨剤や金属を被覆して導電性を付与した後、接着剤中に単分散させることにより、異方導電膜の製造に使用できる。更に、加熱時の熱融着がないことから、粉末炭素材料としても有望であり、例えば、本発明の製造方法により得られたフェノール樹脂球状硬化物を炭化、賦活化することで粉砕工程を経ずして粒状活性炭が製造できる。また、フェノール樹脂球状硬化物を炭化したものを用いれば粉末カーボン電極材や導電性フィラー、触媒担持体及び導電性流動付与材として使用できる。 The phenolic resin spherical cured product obtained by the production method of the present invention can be used alone or in combination with other materials, and can be used in humidification units such as refrigerators and air conditioners, industrial filters, etc. It can also be used as a heat and mechanical strength modifier for plastics and rubber. Also, since it has high sphericity and high impact resistance, it is used for the production of anisotropic conductive film by coating various abrasives and metals to impart conductivity and then monodispersing in adhesive. it can. Furthermore, since there is no heat fusion during heating, it is also promising as a powdered carbon material. For example, the pulverization step is performed by carbonizing and activating the phenol resin spherical cured product obtained by the production method of the present invention. Soon, granular activated carbon can be produced. Moreover, if what carbonized phenol resin spherical hardened | cured material is used, it can be used as a powder carbon electrode material, an electroconductive filler, a catalyst support body, and an electroconductive fluidity imparting material.
次に、実施例により本発明を説明する。 Next, an example explains the present invention.
得られたフェノール樹脂球状硬化物の平均粒径及び粒子の形状の測定は、それぞれ上記の方法にて実施した。 The average particle diameter and particle shape of the obtained phenol resin spherical cured product were measured by the above methods.
［実施例１］
フェノール樹脂溶液（日立化成工業株式会社製、レゾール型フェノール樹脂溶液ＶＰ−８０１）１００ｇ、コーンスターチ５ｇ、水３００ｇを反応容器に仕込んで７０℃で２時間、８５℃で２時間、１００℃で２時間撹拌しながら硬化反応を行った。反応溶液を８０℃に冷却した後α−アミラーゼ３ｍｇを加え９０℃に昇温し１０分間攪拌しながら分解反応を行った。その後、室温になるまで冷却し、得られた懸濁液を濾過して固液分離を行った。得られた固形分は目視観察で凝集物が認められなかった。固形分を８０℃のオーブンで６時間乾燥して、フェノール樹脂球状硬化物８０ｇを得た。フェノール樹脂球状硬化物の形状は真球状であり、平均粒径は４２μｍであった。
[Example 1]
A reaction vessel was charged with 100 g of a phenol resin solution (manufactured by Hitachi Chemical Co., Ltd., resol-type phenol resin solution VP-801), 5 g of corn starch, and 300 g of water, and 70 ° C. for 2 hours, 85 ° C. for 2 hours, and 100 ° C. for 2 hours. The curing reaction was carried out with stirring. The reaction solution was cooled to 80 ° C., 3 mg of α-amylase was added, the temperature was raised to 90 ° C., and the decomposition reaction was carried out with stirring for 10 minutes. Then, it cooled to room temperature, the obtained suspension was filtered, and solid-liquid separation was performed. As for the obtained solid content, the aggregate was not recognized by visual observation. The solid content was dried in an oven at 80 ° C. for 6 hours to obtain 80 g of a phenol resin spherical cured product. The shape of the phenol resin spherical cured product was a true sphere, and the average particle size was 42 μm.
［実施例２］
実施例１と同様にして硬化反応を行った。反応溶液に１Ｎ塩酸２０ｇと水３００ｇを加えさらに２時間攪拌しながら分解反応を行った。その後、室温になるまで冷却し、得られた懸濁液を濾過して固液分離を行った。得られた固形分は目視観察で凝集物が認められなかった。固形分を８０℃のオーブンで６時間乾燥して、フェノール樹脂球状硬化物７５ｇを得た。フェノール樹脂球状硬化物の形状は真球状であり、平均粒径は８５μｍであった。
[Example 2]
A curing reaction was carried out in the same manner as in Example 1. To the reaction solution, 20 g of 1N hydrochloric acid and 300 g of water were added, and a decomposition reaction was performed while stirring for 2 hours. Then, it cooled to room temperature, the obtained suspension was filtered, and solid-liquid separation was performed. As for the obtained solid content, the aggregate was not recognized by visual observation. The solid content was dried in an oven at 80 ° C. for 6 hours to obtain 75 g of a phenol resin spherical cured product. The phenol resin spherical cured product had a true spherical shape and an average particle size of 85 μm.
［実施例３］
コーンスターチを１０ｇ、水を６００ｇ用いること以外は実施例１と同様の方法で硬化反応及び分解反応を行った。その後、室温になるまで冷却し、得られた懸濁液を濾過して固液分離を行った。得られた固形分は目視観察で凝集物が認められなかった。固形分を８０℃のオーブンで６時間乾燥して、フェノール樹脂球状硬化物７８ｇを得た。フェノール樹脂球状硬化物の形状は真球状であり、平均粒径は１２μｍであった。
[Example 3]
A curing reaction and a decomposition reaction were performed in the same manner as in Example 1 except that 10 g of corn starch and 600 g of water were used. Then, it cooled to room temperature, the obtained suspension was filtered, and solid-liquid separation was performed. As for the obtained solid content, the aggregate was not recognized by visual observation. The solid content was dried in an oven at 80 ° C. for 6 hours to obtain 78 g of a phenol resin spherical cured product. The phenol resin spherical cured product had a true spherical shape and an average particle size of 12 μm.
［実施例４］
コーンスターチを２．５ｇ、水を３００ｇ用いること以外は実施例１と同様の方法で硬化反応及び分解反応を行った。その後、室温になるまで冷却し、得られた懸濁液を濾過して固液分離を行った。得られた固形分は目視観察で凝集物が認められなかった。固形分を８０℃のオーブンで６時間乾燥して、フェノール樹脂球状硬化物７８ｇを得た。フェノール樹脂球状硬化物の形状は真球状であり、平均粒径は５２０μｍであった。
[Example 4]
A curing reaction and a decomposition reaction were performed in the same manner as in Example 1 except that 2.5 g of corn starch and 300 g of water were used. Then, it cooled to room temperature, the obtained suspension was filtered, and solid-liquid separation was performed. As for the obtained solid content, the aggregate was not recognized by visual observation. The solid content was dried in an oven at 80 ° C. for 6 hours to obtain 78 g of a phenol resin spherical cured product. The phenol resin spherical cured product had a true spherical shape and an average particle size of 520 μm.
［比較例１］
フェノール樹脂溶液（日立化成工業株式会社製、レゾール型フェノール樹脂溶液ＶＰ−８０１）１００ｇ、ポリビニルアルコール（株式会社クラレ製、ＰＶＡ１１７）５g、水３００ｇを反応容器に仕込んで７０℃で２時間、８５℃で２時間、１００℃で２時間撹拌しながら硬化反応を行った。その後、室温になるまで冷却し、得られた懸濁液を濾過して固液分離を行った。得られた固形分は目視観察で凝集物が認められた。固形分を８０℃のオーブンで６時間乾燥したところ、凝集物が得られた。凝集物を市販の卓上ミルを使用して解砕し、フェノール樹脂硬化物７０ｇを得た。フェノール樹脂硬化物の形状は欠けの有る球状であり、平均粒径は３２０μｍであった。
[Comparative Example 1]
A reaction vessel was charged with 100 g of a phenol resin solution (manufactured by Hitachi Chemical Co., Ltd., resol type phenol resin solution VP-801), 5 g of polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA117), and 300 g of water at 70 ° C. for 2 hours at 85 ° C. The curing reaction was carried out with stirring for 2 hours at 100 ° C. for 2 hours. Then, it cooled to room temperature, the obtained suspension was filtered, and solid-liquid separation was performed. Aggregates were observed in the obtained solid content by visual observation. When the solid content was dried in an oven at 80 ° C. for 6 hours, an aggregate was obtained. The agglomerate was pulverized using a commercially available desk mill to obtain 70 g of a phenol resin cured product. The shape of the cured phenol resin was a chipped spherical shape, and the average particle size was 320 μm.
［比較例２］
比較例１と同様に操作して硬化反応を行い、得られた懸濁液を濾過して固液分離を行った。得られた固形分は目視観察で凝集物が認められた。固形分に水５００ｇを加え１００℃で攪拌して洗浄した。この洗浄操作を球状硬化物の凝集がなくなるまで６回行った。その後、濾過して固液分離を行い、固形分を８０℃のオーブンで６時間乾燥したところ、フェノール樹脂球状硬化物７５ｇ得た。フェノール樹脂球状硬化物の形状は真球状であり、平均粒径は１０６μｍであった。
[Comparative Example 2]
The curing reaction was carried out in the same manner as in Comparative Example 1, and the resulting suspension was filtered for solid-liquid separation. Aggregates were observed in the obtained solid content by visual observation. To the solid content, 500 g of water was added and washed by stirring at 100 ° C. This washing operation was performed 6 times until the spherical cured product was not agglomerated. Thereafter, the solid was separated by filtration, and the solid content was dried in an oven at 80 ° C. for 6 hours to obtain 75 g of a phenol resin spherical cured product. The phenol resin spherical cured product had a true spherical shape and an average particle size of 106 μm.
［比較例３］
ポリビニルアルコールの代りにカルボキシメチルセルロース（和光純薬工業株式会社製）５gを用いること以外は比較例１と同様に操作して硬化反応を行い、得られた懸濁液を濾過して固液分離を行った。得られた固形分は目視観察で凝集物が認められた。固形分に水５００ｇを加え１００℃で攪拌して洗浄した。この洗浄操作を球状硬化物の凝集がなくなるまで４回行った。その後、濾過して固液分離を行い、固形分を８０℃のオーブンで６時間乾燥したところ、フェノール樹脂球状硬化物７２ｇ得た。フェノール樹脂球状硬化物の形状は真球状であり、平均粒径は３２０μｍであった。
[Comparative Example 3]
Except for using 5 g of carboxymethylcellulose (Wako Pure Chemical Industries, Ltd.) in place of polyvinyl alcohol, the curing reaction is carried out in the same manner as in Comparative Example 1, and the resulting suspension is filtered for solid-liquid separation. went. Aggregates were observed in the obtained solid content by visual observation. To the solid content, 500 g of water was added and washed by stirring at 100 ° C. This washing operation was performed four times until there was no aggregation of the spherical cured product. Then, it filtered and solid-liquid separation was performed, and when solid content was dried for 6 hours in 80 degreeC oven, 72 g of phenol resin spherical hardened | cured materials were obtained. The phenol resin spherical cured product had a true spherical shape and an average particle size of 320 μm.
［比較例４］
ポリビニルアルコールの代りにポリアクリル酸（和光純薬工業株式会社製）５gを用いること以外は比較例１と同様に操作して硬化反応を行い、得られた懸濁液を濾過して固液分離を行った。得られた固形分は目視観察で凝集物が認められた。固形分に水５００ｇを加え１００℃で攪拌して洗浄した。この洗浄操作を６回行ったが球状硬化物の凝集はなくならなかった。その後、濾過して固液分離を行い、固形分を８０℃のオーブンで６時間乾燥し、得られた凝集物を市販の卓上ミルを使用して解砕し、フェノール樹脂硬化物６９ｇを得た。フェノール樹脂硬化物の形状は欠けの有る球状であり、平均粒径は８９μｍであった。
[Comparative Example 4]
A curing reaction is carried out in the same manner as in Comparative Example 1 except that 5 g of polyacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) is used instead of polyvinyl alcohol, and the resulting suspension is filtered and solid-liquid separated. Went. Aggregates were observed in the obtained solid content by visual observation. To the solid content, 500 g of water was added and washed by stirring at 100 ° C. This washing operation was performed 6 times, but aggregation of the spherical cured product did not disappear. Thereafter, the solid was separated by filtration, the solid content was dried in an oven at 80 ° C. for 6 hours, and the obtained aggregate was crushed using a commercially available table mill to obtain 69 g of a cured phenol resin. . The shape of the cured phenol resin was a chipped spherical shape, and the average particle size was 89 μm.
［比較例５］
フェノール樹脂溶液（日立化成工業株式会社製レゾール型フェノール樹脂溶液ＶＰ−８０１）１００ｇ、コーンスターチ５g、水３００ｇを反応容器に仕込んで７０℃で２時間、８５℃で２時間、１００℃で２時間撹拌しながら反応させた。得られた懸濁液を濾過して固液分離を行った。得られた固形分は目視観察で凝集物が認められた。固形分に水５００ｇを加え１００℃で攪拌して洗浄した。この洗浄操作を球状硬化物の凝集がなくなるまで６回行った。その後、濾過して固液分離を行い、固形分を８０℃のオーブンで６時間乾燥したところ、フェノール樹脂硬化物７０ｇを得た。フェノール樹脂球状硬化物の形状は真球状であり、平均粒径は５５μｍであった。
[Comparative Example 5]
A reaction vessel was charged with 100 g of a phenolic resin solution (Resol type phenolic resin solution VP-801 manufactured by Hitachi Chemical Co., Ltd.), 5 g of corn starch, and 300 g of water, and stirred at 70 ° C. for 2 hours, 85 ° C. for 2 hours, and 100 ° C. for 2 hours. While reacting. The resulting suspension was filtered for solid-liquid separation. Aggregates were observed in the obtained solid content by visual observation. To the solid content, 500 g of water was added and washed by stirring at 100 ° C. This washing operation was performed 6 times until the spherical cured product was not agglomerated. Then, it filtered and solid-liquid separation was performed, and when solid content was dried in 80 degreeC oven for 6 hours, the phenol resin hardened | cured material 70g was obtained. The phenol resin spherical cured product had a true spherical shape and an average particle size of 55 μm.
実施例１〜４は、容易に固液分離が可能で、二次凝集がなく、真球度が極めて高いフェノール樹脂球状硬化物を得ることが出来る。これに対し、比較例１〜５は、懸濁安定剤を分解する工程を行わないため、二次凝集が起こり、解砕を必要とするため粒子に欠けができてしまう。また、水洗を多数回行うため大量に廃液を処理する必要が生じてしまう。 In Examples 1 to 4, solid-liquid separation can be easily performed, and there is no secondary aggregation, and a phenol resin spherical cured product having extremely high sphericity can be obtained. On the other hand, Comparative Examples 1 to 5 do not perform the step of decomposing the suspension stabilizer, so that secondary aggregation occurs and the particles need to be crushed so that the particles can be chipped. Moreover, since washing with water is performed many times, it becomes necessary to treat a large amount of waste liquid.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2016519695A (en) * | 2013-03-13 | 2016-07-07 | エナジー２ テクノロジーズ，インコーポレイテッドＥｎｅｒＧ２ ＴＥＣＨＮＯＬＯＧＩＥＳ，ＩＮＣ． | Improved emulsion and suspension polymerization process, and improved electrochemical performance of carbon derived therefrom |
| CN115611349A (en) * | 2021-07-16 | 2023-01-17 | 碧儿赛福有限公司 | Filter for water treatment and preparation method of spherical activated carbon |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2016519695A (en) * | 2013-03-13 | 2016-07-07 | エナジー２ テクノロジーズ，インコーポレイテッドＥｎｅｒＧ２ ＴＥＣＨＮＯＬＯＧＩＥＳ，ＩＮＣ． | Improved emulsion and suspension polymerization process, and improved electrochemical performance of carbon derived therefrom |
| CN115611349A (en) * | 2021-07-16 | 2023-01-17 | 碧儿赛福有限公司 | Filter for water treatment and preparation method of spherical activated carbon |
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