JP2009076288A - Electric insulating oil - Google Patents
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Abstract
Description
本発明は電気絶縁油に関し、詳しくは環境負荷が低減され且つ動粘度、流動点等の物性が改善された絶縁油に関する。 The present invention relates to an electrical insulating oil, and more particularly to an insulating oil with reduced environmental load and improved physical properties such as kinematic viscosity and pour point.
変圧器、ケーブル、遮断機、コンデンサー等の絶縁、冷却の目的で使用される電気絶縁油は、古くは大豆油、菜種油、ヒマシ油等の天然の植物油が使用されていたが、その後、重質原油から分留・精製された石油系絶縁油や、アルキルベンゼン等の炭化水素系油、塩化ジフェニル等の塩素化炭化水素系油、エステル系油、シリコーン油等の合成絶縁油が使用されるようになった。
しかしながら、石油系絶縁油は引火点が低い等の防災上の問題や、近年の環境問題を考慮した場合、地球温暖化防止対策における二酸化炭素排出量削減の観点から見ればカーボンニュートラルの考え上、地球環境に対し好ましいものではない。
また、合成系絶縁油は、フタル酸エステル類における内分泌撹乱作用の疑いや、PCBの毒性問題など、安全性や環境汚染に問題を有していた。
このような経緯より、安全性に優れる植物油を電気絶縁油として再び活用できれば石油系や合成系絶縁油が有する上記のような問題が解決できることになるが、植物油は粘度が高いことや流動点が高いという問題を有している。
植物油が有する上記問題を解決するために、天然植物油の低級アルコールエステル化物を電気絶縁油として使用する提案がなされている(例えば、特許文献1、2、3、4参照)。
しかしながら、これらの絶縁油では低粘度化は実現できるが、引火点が低く、また流動点が高いため物性上満足のいくものではなかった。
植物油と類似の化学構造を持つ化合物としてポリグリセリン脂肪酸エステルを挙げることができる。ポリグリセリン脂肪酸エステルはその分子を構成する脂肪酸とポリグリセリンの選択により常温で固体から液体まで種々の性状の化合物を調製することが可能であり、電気絶縁油としての使用可能性が考えられるが、ポリグリセリン脂肪酸エステルを電気絶縁油として使用する提案はなされていない。
However, when considering petroleum-related insulating oils for disaster prevention such as low flash point and environmental issues in recent years, from the viewpoint of reducing carbon dioxide emissions in global warming prevention measures, in terms of carbon neutral, It is not preferable for the global environment.
Synthetic insulating oils have problems in safety and environmental pollution, such as suspicion of endocrine disrupting action in phthalates and toxicity of PCBs.
From these circumstances, if vegetable oils with excellent safety can be reused as electrical insulating oils, the above problems of petroleum-based and synthetic insulating oils can be solved. However, vegetable oils have high viscosity and pour points. It has the problem of being expensive.
In order to solve the above problems of vegetable oils, proposals have been made to use lower alcohol esterified natural vegetable oils as electrical insulating oils (see, for example, Patent Documents 1, 2, 3, and 4).
However, these insulating oils can achieve a low viscosity, but they are not satisfactory in terms of physical properties because of their low flash point and high pour point.
Examples of the compound having a chemical structure similar to that of vegetable oil include polyglycerol fatty acid esters. Polyglycerin fatty acid ester can prepare various properties of compounds from solid to liquid at room temperature by selecting fatty acid and polyglycerin constituting the molecule, and it can be used as electrical insulating oil, No proposal has been made to use polyglycerol fatty acid esters as electrical insulating oils.
本発明が解決しようとする課題は、環境負荷が低減され且つ植物油より低粘度、低流動点の物性をもち、植物油と同等の電気特性を有する電気絶縁油を提供することにある。 The problem to be solved by the present invention is to provide an electrical insulating oil that has reduced environmental impact, has lower viscosity and lower pour point properties than vegetable oil, and has electrical properties equivalent to vegetable oil.
本発明者らは、上記課題を解決すべく鋭意検討を重ねた結果、炭素数8〜20の脂肪酸と平均重合度が2〜10のポリグリセリンとのエステル化物が粘度、流動点、引火点等の物性に優れ、本発明の上記目的を達成するに至ったものである。
すなわち本発明は、以下の構成である。
1.炭素数8〜20の脂肪酸と平均重合度2〜10のポリグリセリンより構成されるポリグリセリン脂肪酸エステルを含有することを特徴とする電気絶縁油。
2.前記脂肪酸がカプリル酸及び/又はカプリン酸であることを特徴とする前記1記載の電気絶縁油。
3.前記ポリグリセリンの平均重合度が2であることを特徴とする前記1又は2記載の電気絶縁油。
4.前記1、2又は3記載のポリグリセリン脂肪酸エステル50〜100質量%と植物油及び/又は中鎖脂肪酸トリグリセライド0〜50質量%よりなることを特徴とする電気絶縁油。
As a result of intensive studies to solve the above problems, the present inventors have found that an esterified product of a fatty acid having 8 to 20 carbon atoms and a polyglycerin having an average polymerization degree of 2 to 10 has viscosity, pour point, flash point, etc. It is excellent in the physical properties of the present invention and has reached the above object of the present invention.
That is, the present invention has the following configuration.
1. An electrical insulating oil comprising a polyglycerol fatty acid ester composed of a fatty acid having 8 to 20 carbon atoms and a polyglycerol having an average polymerization degree of 2 to 10.
2. 2. The electrical insulating oil as described in 1 above, wherein the fatty acid is caprylic acid and / or capric acid.
3. 3. The electrical insulating oil according to 1 or 2, wherein the polyglycerin has an average degree of polymerization of 2.
4). An electrically insulating oil comprising 50 to 100% by mass of the polyglycerin fatty acid ester according to 1, 2 or 3, and 0 to 50% by mass of vegetable oil and / or medium chain fatty acid triglyceride.
本発明によれば、植物油より低粘度、低流動点の物性をもち、植物油と同等の電気特性を有し且つ、植物由来原料より構成することにより石油系や合成系絶縁油に比べ環境負荷を低減可能な電気絶縁油を提供することができる。 According to the present invention, it has lower viscosity and lower pour point properties than vegetable oils, has electrical properties equivalent to vegetable oils, and is composed of plant-derived raw materials, thereby reducing environmental burden compared to petroleum-based and synthetic insulating oils. Electric insulating oil that can be reduced can be provided.
以下、発明を実施するための最良の形態により、本発明を詳細に説明する。
本発明に使用されるポリグリセリン脂肪酸エステルを構成する脂肪酸は、炭素数が8〜22であり、例えば、カプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ベヘン酸、エルカ酸、パルミトレイン酸、オレイン酸、リノール酸、リノレン酸、イソステアリン酸等が挙げられ、これらの1種もしくはこれらを任意の比率に混合して使用することができる。また、これら脂肪酸の原料起源は動植物油であることが好ましい。
Hereinafter, the present invention will be described in detail according to the best mode for carrying out the invention.
The fatty acid constituting the polyglycerol fatty acid ester used in the present invention has 8 to 22 carbon atoms, for example, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, erucic acid , Palmitoleic acid, oleic acid, linoleic acid, linolenic acid, isostearic acid, and the like. One of these or a mixture of these in any ratio can be used. Moreover, it is preferable that the raw material origin of these fatty acids is animal and vegetable oils.
本発明に使用されるポリグリセリン脂肪酸エステルを構成するポリグリセリンは、グリセリンの重合物として平均重合度2〜100のものが知られているが、人体・環境に対する安全性の見地から、平均重合度2〜10のものが好ましい。また、その原料起源が動植物油であることが更に好ましい。 The polyglycerin constituting the polyglycerin fatty acid ester used in the present invention is known to have an average polymerization degree of 2 to 100 as a polymer of glycerin. From the viewpoint of safety to human body and environment, the average polymerization degree The thing of 2-10 is preferable. More preferably, the starting material is animal or vegetable oil.
本発明に使用されるポリグリセリン脂肪酸エステルは上記脂肪酸とポリグリセリンを原料として公知の種々のエステル化法を用いて製造することができる。例えば、ポリグリセリンと脂肪酸を、(脂肪酸のカルボキシル基のモル数)/(ポリグリセリンの水酸基のモル数)=1.05〜1.3の比率で仕込み無触媒、アルカリ触媒或いは酸触媒を用いて、不活性ガス雰囲気下、200℃〜250℃で常圧或いは減圧反応を5〜20時間行い、過剰の脂肪酸を減圧留去或いは水蒸気蒸留により留去する。このとき、生成されたポリグリセリン脂肪酸エステルの品質は、酸価が1以下、好ましくは0.1以下であり、水酸基価が10以下、好ましくは5以下である。酸価が1より大きい或いは水酸基価が10より大きい場合、ポリグリセリン脂肪酸エステルの電気特性を悪化させる。 The polyglycerol fatty acid ester used in the present invention can be produced by using various known esterification methods using the above fatty acid and polyglycerol as raw materials. For example, polyglycerin and fatty acid are charged in a ratio of (number of moles of carboxyl group of fatty acid) / (number of moles of hydroxyl group of polyglycerin) = 1.05 to 1.3, using no catalyst, alkali catalyst or acid catalyst. In an inert gas atmosphere, a normal pressure or reduced pressure reaction is performed at 200 ° C. to 250 ° C. for 5 to 20 hours, and excess fatty acid is distilled off under reduced pressure or steam distillation. At this time, the quality of the produced polyglycerin fatty acid ester has an acid value of 1 or less, preferably 0.1 or less, and a hydroxyl value of 10 or less, preferably 5 or less. If the acid value is greater than 1 or the hydroxyl value is greater than 10, the electrical properties of the polyglycerol fatty acid ester are deteriorated.
また、本発明のポリグリセリン脂肪酸エステルは、上記エステル化反応後、活性白土、活性アルミナ等の無機合成吸着剤や活性炭等の吸着剤を用いてエステル中に含有される微量の遊離脂肪酸や不純物を吸着除去することが好ましい。さらに、真空下、脱気処理を行い、空気および水分を除去することが好ましい。 In addition, the polyglycerin fatty acid ester of the present invention contains a small amount of free fatty acid and impurities contained in the ester using an inorganic synthetic adsorbent such as activated clay and activated alumina and an adsorbent such as activated carbon after the esterification reaction. It is preferable to remove by adsorption. Furthermore, it is preferable to perform a deaeration process under vacuum to remove air and moisture.
また、本発明の電気絶縁油は、上記ポリグリセリン脂肪酸エステルと植物油及び/又は中鎖脂肪酸トリグリセライドを混合して使用することができる。植物油及び/又は中鎖脂肪酸トリグリセライドの電気絶縁油全量に対する混合比率は50質量%以下であり、好ましくは40質量%以下、より好ましくは30質量%以下である。植物油の混合は、引火点を高めることに有効であるが、電気絶縁油全量に対する混合比率が50質量%を超えると流動点が高くなり過ぎるため好ましくない。中鎖脂肪酸トリグリセライドの混合は、粘度低下に有効であるが、電気絶縁油全量に対する混合比率が50質量%を超えると引火点の低下が大きく好ましくない。 Moreover, the electrical insulation oil of this invention can mix and use the said polyglyceryl fatty acid ester, vegetable oil, and / or medium chain fatty acid triglyceride. The mixing ratio of the vegetable oil and / or medium chain fatty acid triglyceride to the total amount of the electrical insulating oil is 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less. Mixing vegetable oils is effective in increasing the flash point, but if the mixing ratio with respect to the total amount of the electrical insulating oil exceeds 50% by mass, the pour point becomes too high, which is not preferable. Mixing of medium-chain fatty acid triglycerides is effective in reducing the viscosity, but if the mixing ratio with respect to the total amount of the electric insulating oil exceeds 50% by mass, the flash point is undesirably reduced.
上記植物油としては例えば、大豆油、菜種油、ヒマシ油、コーン油、紅花油、ヒマワリ油等を挙げることができ、中鎖脂肪酸トリグリセライドとしてはトリカプリル酸グリセリド、トリカプリン酸グリセリド、トリ(カプリル酸/カプリン酸)グリセリドを挙げることができる。 Examples of the vegetable oil include soybean oil, rapeseed oil, castor oil, corn oil, safflower oil, sunflower oil, and the like. ) Glycerides can be mentioned.
本発明の電気絶縁油は、これ自体単独でも使用することができるが、発明の効果を損なわない範囲でこれに酸化防止剤、流動点降下剤、流動帯電防止剤等の添加剤を配合して使用することができる。 The electrical insulating oil of the present invention can be used alone, but an additive such as an antioxidant, a pour point depressant, a fluid antistatic agent and the like is blended in the range without impairing the effects of the invention. Can be used.
本発明の電気絶縁油の適用対象物には特に制限は無く、従来より電気絶縁油の使用が知られた電気機器、例えば変圧器、ケーブル、遮断機、コンデンサーなどに適用することができる。 There is no restriction | limiting in particular in the application object of the electrical insulation oil of this invention, It can apply to the electric equipment conventionally used for electrical insulation oil, for example, a transformer, a cable, a circuit breaker, a capacitor | condenser etc.
次に、本発明の実施例を挙げ更に詳しく説明するが、本発明はこれらの実施例に制限されるものではない。 Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
実施例1〜3、比較例1〜2
下記合成方法により電気絶縁油A〜Cを作成し、物性及び電気特性の評価を行った。また、比較例として菜種白絞油とトリカプリル酸グリセリドについて同様の評価を行った。物性及び電気特性を表1に示す。
尚、試験に用いた試料の分析、物性及び電気特性の評価方法は以下の試験法に準拠して行った。
全酸価:JIS C 2101
水酸基価:油化学会法(2.3.6−1996)
水分:JIS C 2101(カールフィッシャー式容量滴定法)
動粘度:ASTM D7042
流動点:ASTM D6749
引火点:JIS K 2265(クリーブランド開放式)
絶縁破壊電圧:JIS C 2101
体積抵抗率:JIS C 2101
誘電正接:JIS C 2101
Examples 1-3, Comparative Examples 1-2
Electrical insulating oils A to C were prepared by the following synthesis method, and physical properties and electrical characteristics were evaluated. Moreover, the same evaluation was performed about rapeseed white squeezed oil and tricaprylic acid glyceride as a comparative example. Table 1 shows the physical properties and electrical characteristics.
In addition, the analysis of the sample used for the test, the physical property, and the evaluation method of an electrical property were performed based on the following test methods.
Total acid value: JIS C 2101
Hydroxyl value: The Oil Chemical Society of Japan (2.3.6-1996)
Moisture: JIS C 2101 (Karl Fischer type volumetric titration method)
Kinematic viscosity: ASTM D7042
Pour point: ASTM D6749
Flash point: JIS K 2265 (Cleveland open type)
Dielectric breakdown voltage: JIS C 2101
Volume resistivity: JIS C 2101
Dielectric loss tangent: JIS C 2101
〈電気絶縁油Aの作成〉
ジグリセリン(ジグリセリンS:阪本薬品工業(株)社製)325gとカプリル酸(NAA−82:日本油脂(株)社製、以下同様)1276gを4つ口フラスコに仕込み、撹拌下、窒素ガスを吹き込みながら230℃で8時間反応を行った。次に1.5kPaの減圧下、水蒸気を吹き込みながら未反応の脂肪酸を留去してジグリセリンカプリレートを得た。
このジグリセリンカプリレート100質量部に対し無機吸着剤(キョーワード500SH:協和化学工業(株)社製)を2質量部添加し、120℃で1時間吸着処理をした後、ろ過により無機吸着剤を除去した。更に1.5kPaの減圧下、120℃で1時間脱気処理を行い電気絶縁油Aを得た。
得られた電気絶縁油Aは全酸価0.07、水酸基価0.4、水分92ppmであった。
〈電気絶縁油Bの作成〉
デカグリセリン(ポリグリセリン#750:阪本薬品工業(株)社製)558gとカプリル酸(NAA−82:日本油脂(株)社製、以下同様)1328gを4つ口フラスコに仕込み、撹拌下、窒素ガスを吹き込みながら230℃で8時間反応を行った。次に1.5kPaの減圧下、水蒸気を吹き込みながら未反応の脂肪酸を留去してデカグリセリンカプリレートを得た。
このデカグリセリンカプリレート100質量部に対し無機吸着剤(キョーワード500SH:協和化学工業(株)社製)を2質量部添加し、120℃で1時間吸着処理をした後、ろ過により無機吸着剤を除去した。更に1.5kPaの減圧下、120℃で1時間脱気処理を行い電気絶縁油Bを得た。
得られた電気絶縁油Bは全酸価0.09、水酸基価2.2、水分123ppmであった。
〈電気絶縁油Cの作成〉
上記電気絶縁油A960gとトリ(カプリル酸/カプリン酸)グリセリド(アクターM−1:理研ビタミン(株)社製)640gを4つ口フラスコに仕込み、窒素ガスを吹き込みながら80℃で30分間撹拌して電気絶縁油Cを得た。
得られた電気絶縁油Cは全酸価0.07、水酸基価0.4、水分88ppmであった。
<Creation of electrical insulating oil A>
325 g of diglycerin (Diglycerin S: Sakamoto Yakuhin Kogyo Co., Ltd.) and 1276 g of caprylic acid (NAA-82: Nippon Oil & Fats Co., Ltd., hereinafter the same) are charged into a four-necked flask and stirred under nitrogen gas. The reaction was carried out at 230 ° C. for 8 hours while blowing. Next, under reduced pressure of 1.5 kPa, unreacted fatty acid was distilled off while blowing water vapor to obtain diglycerin caprylate.
2 parts by mass of an inorganic adsorbent (KYOWARD 500SH: manufactured by Kyowa Chemical Industry Co., Ltd.) is added to 100 parts by mass of the diglycerin caprylate, and after an adsorption treatment at 120 ° C. for 1 hour, the inorganic adsorbent is filtered. Was removed. Furthermore, the deaeration process was performed at 120 degreeC under pressure reduction of 1.5 kPa for 1 hour, and the electrically insulating oil A was obtained.
The resulting electrical insulating oil A had a total acid value of 0.07, a hydroxyl value of 0.4, and a moisture content of 92 ppm.
<Creation of electrical insulating oil B>
Decaglycerin (polyglycerin # 750: manufactured by Sakamoto Pharmaceutical Co., Ltd.) 558 g and caprylic acid (NAA-82: manufactured by Nippon Oil & Fats Co., Ltd., the same shall apply hereinafter) 1328 g were charged into a four-necked flask and stirred under nitrogen. The reaction was carried out at 230 ° C. for 8 hours while blowing gas. Next, unreacted fatty acid was distilled off under reduced pressure of 1.5 kPa while blowing water vapor to obtain decaglycerin caprylate.
2 parts by mass of an inorganic adsorbent (KYOWARD 500SH: manufactured by Kyowa Chemical Industry Co., Ltd.) is added to 100 parts by mass of this decaglycerin caprylate, and after an adsorption treatment at 120 ° C. for 1 hour, the inorganic adsorbent is filtered. Was removed. Furthermore, deaeration treatment was performed at 120 ° C. for 1 hour under a reduced pressure of 1.5 kPa to obtain an electric insulating oil B.
The obtained electrical insulating oil B had a total acid value of 0.09, a hydroxyl value of 2.2, and a moisture content of 123 ppm.
<Creation of electrical insulating oil C>
960 g of the above electric insulating oil A and 640 g of tri (caprylic acid / capric acid) glyceride (Actor M-1: manufactured by Riken Vitamin Co., Ltd.) are charged into a four-necked flask and stirred at 80 ° C. for 30 minutes while blowing nitrogen gas. As a result, an electric insulating oil C was obtained.
The obtained electrical insulating oil C had a total acid value of 0.07, a hydroxyl value of 0.4, and a water content of 88 ppm.
本発明は、植物油より低粘度、低流動点でありながら植物油と同等の電気特性を有し且つ、植物由来原料より製造することにより石油系や合成系絶縁油に比べ環境負荷が低減された電気絶縁油を提供することができ、変圧器、ケーブル、遮断機、コンデンサーなど従来より電気絶縁油の使用が知られている電気機器に適用することができる。 The present invention has an electrical property equivalent to that of vegetable oil while having a lower viscosity and a lower pour point than vegetable oil, and has an environmental impact reduced compared to petroleum-based or synthetic insulating oil by being manufactured from plant-derived raw materials. Insulating oil can be provided, and the present invention can be applied to electrical devices that are conventionally known to use electrical insulating oil, such as transformers, cables, circuit breakers, and capacitors.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102613313A (en) * | 2011-01-31 | 2012-08-01 | 日清奥利友集团株式会社 | Oil-fat composition for heat cooking, manufacturing method thereof, and acid-value increase inhibitor for oil-fat composition for heat cooking |
CN116731773A (en) * | 2023-06-13 | 2023-09-12 | 上海江天高分子材料有限公司 | Degradable soybean-based natural ester insulating oil and preparation method and application thereof |
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2007
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CN102613313A (en) * | 2011-01-31 | 2012-08-01 | 日清奥利友集团株式会社 | Oil-fat composition for heat cooking, manufacturing method thereof, and acid-value increase inhibitor for oil-fat composition for heat cooking |
CN102613313B (en) * | 2011-01-31 | 2016-05-25 | 日清奥利友集团株式会社 | Composition thing and manufacture method thereof and the heating cooking composition thing acid number inhibitor that rises for heating cooking |
CN116731773A (en) * | 2023-06-13 | 2023-09-12 | 上海江天高分子材料有限公司 | Degradable soybean-based natural ester insulating oil and preparation method and application thereof |
CN116731773B (en) * | 2023-06-13 | 2023-12-12 | 上海江天高分子材料有限公司 | Degradable soybean-based natural ester insulating oil and preparation method and application thereof |
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