JPH05279658A - Stabilization of hydrogen-containing fluoroalkane composition for refrigerator - Google Patents
Stabilization of hydrogen-containing fluoroalkane composition for refrigeratorInfo
- Publication number
- JPH05279658A JPH05279658A JP4110746A JP11074692A JPH05279658A JP H05279658 A JPH05279658 A JP H05279658A JP 4110746 A JP4110746 A JP 4110746A JP 11074692 A JP11074692 A JP 11074692A JP H05279658 A JPH05279658 A JP H05279658A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen
- composition
- acid
- containing fluoroalkane
- refrigerator
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Lubricants (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、冷媒である水素含有フ
ルオロアルカン、好ましくは１，１，１，２−テトラフ
ルオロエタン（Ｒ−１３４ａ）に対し、−２０℃ないし
はそれ以下の温度から、＋４０℃ないしはそれ以上の温
度で、自由な比率で相溶し、吸湿性が低く、粘度指数、
流動点等潤滑油特性に優れたエステル化合物と水素含有
フルオロアルカンからなる冷凍機用組成物の安定化方法
に関するものである。The present invention relates to a hydrogen-containing fluoroalkane as a refrigerant, preferably 1,1,1,2-tetrafluoroethane (R-134a), from a temperature of -20 ° C or lower, At + 40 ° C or higher, they are compatible with each other in a free ratio, have low hygroscopicity, and have a viscosity index,
The present invention relates to a method for stabilizing a refrigerator composition comprising an ester compound having excellent pour point and other lubricating oil properties and a hydrogen-containing fluoroalkane.
【０００２】[0002]
【従来の技術】従来冷蔵庫やカ−エアコンなどの冷媒と
してＲ−１２（ジクロロジフルオロメタン）が使用され
ているが、オゾン層破壊問題に関し、これへの影響が無
い新しいタイプの冷媒としてＲ−１３４ａが検討されて
いる。2. Description of the Related Art R-12 (dichlorodifluoromethane) has been conventionally used as a refrigerant for refrigerators, car air conditioners, etc., but regarding the problem of ozone layer depletion, R-134a is a new type of refrigerant that has no effect on it. Is being considered.
【０００３】一方、フロン圧縮機用潤滑油としては従来
から鉱油系が使用されてきているが、Ｒ−１３４ａに対
しては鉱油系は相溶性が悪く使用できない。Ｒ−１３４
ａと比較的良く相溶する物質としてポリアルキレングリ
コ−ル系およびエステル系が知られている。On the other hand, although a mineral oil type has been conventionally used as a lubricating oil for a CFC compressor, a mineral oil type is not compatible with R-134a and cannot be used. R-134
Polyalkylene glycol-based and ester-based substances are known as substances that are relatively well compatible with a.
【０００４】しかしながらこれまでのポリアルキレング
リコ−ル系およびエステル系潤滑油ではＲ−１３４ａと
の相溶性が十分でなく、また吸湿性が高いというような
問題があり、本発明者らは特定のエステル構造を組合わ
せることにより前記問題を解決した。However, the conventional polyalkylene glycol-based and ester-based lubricating oils have problems such as insufficient compatibility with R-134a and high hygroscopicity. The above problem was solved by combining the ester structures.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、冷凍機
の圧縮機内部は、金属表面が露出しており、そこに冷凍
機油と冷媒が共存しているため、高温で長時間の運転中
に金属が触媒作用を起こしていて冷凍機油と冷媒が反応
しやすく、全酸価の上昇、金属の腐食およびスラッジの
発生等が起り、冷凍機の故障原因となる。However, since the metal surface is exposed inside the compressor of the refrigerator, and the refrigerating machine oil and the refrigerant coexist there, the metal may be removed during operation at high temperature for a long time. Due to the catalytic action, the refrigerating machine oil and the refrigerant are likely to react with each other, resulting in an increase in the total acid value, corrosion of metal, generation of sludge, etc., which causes a failure of the refrigerator.
【０００６】[0006]
【課題を解決するための手段】本発明は前記課題を解決
すべくなされたものであり、下記一般式化３The present invention has been made to solve the above-mentioned problems, and is represented by the following general formula 3
【化３】 から選ばれるエステル化合物の少なくとも一種（Ａ）と
脂肪族モノカルボン酸（Ｂ）および必要に応じて多価カ
ルボン酸（Ｃ）とから得られるエステル化合物および水
素含有フルオロアルカンからなる水素含有フルオロアル
カン系冷凍機用組成物をフェノ−ル系抗酸化剤を用いて
安定化することを特徴とする水素含有フルオロアルカン
系冷凍機用組成物の安定化方法及び、下記一般式化４[Chemical 3] A hydrogen-containing fluoroalkane system consisting of an ester compound obtained from at least one ester compound (A) selected from the above, an aliphatic monocarboxylic acid (B) and optionally a polyvalent carboxylic acid (C), and a hydrogen-containing fluoroalkane A method for stabilizing a hydrogen-containing fluoroalkane-based refrigerator composition, which comprises stabilizing a refrigerator composition using a phenol-based antioxidant, and the following general formula 4
【化４】 から選ばれるエステル化合物の少なくとも一種（Ａ）と
脂肪族モノカルボン酸（Ｂ）、多価カルボン酸（Ｃ）お
よび多価アルコ−ル（Ｄ）とから得られるエステル化合
物および水素含有フルオロアルカンからなる水素含有フ
ルオロアルカン系冷凍機用組成物をフェノ−ル系抗酸化
剤を用いて安定化することを特徴とする水素含有フルオ
ロアルカン系冷凍機用組成物の安定化方法に関するもの
である。[Chemical 4] An ester compound obtained from at least one ester compound (A) selected from the group consisting of (A), an aliphatic monocarboxylic acid (B), a polyvalent carboxylic acid (C) and a polyvalent alcohol (D), and a hydrogen-containing fluoroalkane. The present invention relates to a method for stabilizing a hydrogen-containing fluoroalkane-based refrigerator composition, which comprises stabilizing a hydrogen-containing fluoroalkane-based refrigerator composition with a phenol-based antioxidant.
【０００７】一般式中Ｘ1，Ｘ2，Ｘ3は炭素数２〜１０
の脂肪族炭化水素基であり、同一でも異なっていてもよ
く、炭素数２〜１０の脂肪族炭化水素基の内、ヒンダ−
ド構造のものが安定性及びフロンとの相溶性から特に好
ましい。炭素数が１０を越えるとエステルの安定性が悪
くなり、また冷凍機油として使用した場合フロン冷媒と
の相溶性が悪くなる。In the general formula, X 1 , X 2 , and X 3 have 2 to 10 carbon atoms.
Which may be the same or different, and among the aliphatic hydrocarbon groups having 2 to 10 carbon atoms, hinder
The one having a destructure is particularly preferable in terms of stability and compatibility with Freon. If the carbon number exceeds 10, the stability of the ester will deteriorate, and if it is used as a refrigerating machine oil, the compatibility with the fluorocarbon refrigerant will deteriorate.
【０００８】一般式中Ｒ1，Ｒ2，Ｒ3，Ｒ4はエチレン
基、プロピレン基、イソブチレン基、イソペンチレン基
等のアルキレン基であり同一でも異なっていてもよい。
これらはエステルの安定性から分枝構造のものが好まし
い。In the general formula, R 1 , R 2 , R 3 and R 4 are alkylene groups such as ethylene group, propylene group, isobutylene group and isopentylene group and may be the same or different.
These are preferably those having a branched structure in view of the stability of the ester.
【０００９】又一般式中ｌ、ｍ、ｎ、ｈは正数であり同
一でも異なっていてもよい（但し、ｌ、ｍ、ｎ、ｈはす
べてが０となることはない）。 これらは主に冷凍機油
の必要粘度に合せて選択される。 一般式（１）〜
（３）のエステル化物は単独でもこれらの混合物でも使
用することができる。In the general formula, l, m, n and h are positive numbers and may be the same or different (provided that all of l, m, n and h are not 0). These are selected mainly according to the required viscosity of the refrigerating machine oil. General formula (1)-
The esterified product of (3) can be used alone or in a mixture thereof.
【００１０】使用される脂肪族モノカルボン酸（Ｂ）と
しては酢酸、プロピオン酸、酪酸、バレリン酸、カプロ
ン酸、エナント酸、カプリル酸、ペラルゴン酸等の直鎖
酸、イソ酪酸、イソバレリン酸、ピバリン酸、ネオヘキ
サン酸、ネオペンタン酸、２−エチルヘキサン酸、３，
３，５−トリメチルヘキサン酸等の分枝酸があげられ、
これらは単独でも２個以上の併用でもよい。As the aliphatic monocarboxylic acid (B) used, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, linear acids such as pelargonic acid, isobutyric acid, isovaleric acid, pivalin are used. Acid, neohexanoic acid, neopentanoic acid, 2-ethylhexanoic acid, 3,
Branched acids such as 3,5-trimethylhexanoic acid are listed,
These may be used alone or in combination of two or more.
【００１１】使用される多価カルボン酸（Ｃ）としては
シュウ酸、マロン酸、コハク酸、アジピン酸、２，２−
ジメチルコハク酸、３−メチルアジピン酸、アゼライン
酸、セバシン酸等があげられ、これらは単独でも２個以
上の併用でもよい。The polycarboxylic acid (C) used is oxalic acid, malonic acid, succinic acid, adipic acid, 2,2-
Examples thereof include dimethylsuccinic acid, 3-methyladipic acid, azelaic acid and sebacic acid, and these may be used alone or in combination of two or more.
【００１２】使用される多価アルコ−ル（Ｄ）としては
ネオペンチルグリコ−ル、トリメチロ−ルプロパン、ペ
ンタエリスリト−ル、２，２−ジエチル−１，３−プロ
パンジオ−ル、エチレングリコ−ル、プロピレングリコ
−ル、グリセリン、ソルビト−ル等が挙げられる。 本
発明の冷凍機油組成物として使用されるエステル化合物
と水素含有フルオロアルカンの重量比は１／９９〜９９
／１、好ましくは５／９５〜６０／４０である。The polyhydric alcohol (D) used is neopentyl glycol, trimethylolpropane, pentaerythritol, 2,2-diethyl-1,3-propanediol, ethylene glycol. And propylene glycol, glycerin, sorbitol and the like. The weight ratio of the ester compound and the hydrogen-containing fluoroalkane used as the refrigerator oil composition of the present invention is 1/99 to 99.
/ 1, preferably 5/95 to 60/40.
【００１３】本発明の組成物を安定化するためのフェノ
−ル系抗酸化剤としては、２，６−ジ−ｔ−ブチル−４
−メチルフェノ−ル，２，６−ジ−ｔ−ブチルフェノ−
ル，２，６−ジ−ｔ−ブチル−４−ｓｅｃ−ブチルフェ
ノ−ル，ｎ−オクタデシル−３−（３，５−ジ−ｔ−ブ
チル−４−ヒドロキシフェニル）プロピオネ−ト，２，
２’−メチレン−ビス（４−メチル−６−ｔ−ブチル−
フェノ−ル），２−ｔ−ブチル−６−（３−ｔ−ブチル
−２−ヒドロキシ−５−メチルベンジル）−４−メチル
フェニルアクリレ−ト，４，４’−ブチリデンビス（３
−メチル−６−ｔ−ブチルフェノ−ル），４，４’−チ
オビス（３−メチル−６−ｔ−ブチルフェノ−ル）等を
挙げることができる。Examples of phenolic antioxidants for stabilizing the composition of the present invention include 2,6-di-t-butyl-4.
-Methylphenol, 2,6-di-t-butylpheno-
2,6-di-t-butyl-4-sec-butylphenol, n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,
2'-methylene-bis (4-methyl-6-t-butyl-
Phenol), 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 4,4'-butylidene bis (3
-Methyl-6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol) and the like.
【００１４】本発明のフェノ−ル系抗酸化剤の冷凍機油
への配合量は０．００５〜５重量％、好ましくは０．０
５〜１重量％である。配合量がこれより少ないと抗酸化
剤としての効果が得られず、また多量に配合してもそれ
ほど効果は増大しない。The amount of the phenolic antioxidant of the present invention added to the refrigerating machine oil is 0.005 to 5% by weight, preferably 0.0.
It is 5 to 1% by weight. If the compounding amount is less than this, the effect as an antioxidant cannot be obtained, and even if it is compounded in a large amount, the effect does not increase so much.
【００１５】本発明のエステル化合物は相溶性を満足す
る範囲内において従来使用されている鉱油、アルキルベ
ンゼン系合成油、ポリαオレフィン系合成油、フッソ系
潤滑油等と混合使用することが可能である。The ester compound of the present invention can be used as a mixture with conventionally used mineral oil, alkylbenzene synthetic oil, poly-α-olefin synthetic oil, fluorine-containing lubricating oil, etc. within a range satisfying compatibility. ..
【００１６】また必要により通常使用される極圧剤、消
泡剤、金属不活性剤等の添加剤を本発明の組成物にさら
に添加してもよい。If desired, additives such as an extreme pressure agent, an antifoaming agent and a metal deactivator which are usually used may be further added to the composition of the present invention.
【００１７】[0017]
【発明の効果】本発明のフェノ−ル系抗酸化剤を用いる
安定化方法は、水素含有フルオロアルカン系冷凍機用組
成物にたいして高い安定効果が得られる。INDUSTRIAL APPLICABILITY The stabilization method using the phenol-based antioxidant of the present invention has a high stabilizing effect on the hydrogen-containing fluoroalkane-based refrigerator composition.
【００１８】[0018]
実施例 １〜５、比較例 １〜３ 実施例 １〜５及び比較例 １〜３に用いた油の構造、
動粘度、添加剤の構造及びシ−ルドチュ−ブ試験前後に
おける酸価、着色の結果を表１に示す。Examples 1 to 5, Comparative Examples 1 to 3 Structures of oils used in Examples 1 to 5 and Comparative Examples 1 to 3,
Table 1 shows the kinematic viscosity, the structure of the additive, the acid value before and after the shield tube test, and the result of coloring.
【００１９】＜シ−ルドチュ−ブ試験＞３００ｍｌのス
テンレス製オ−トクレ−ブ中に試料油７０ｇとフロンＲ
−１３４ａ、７０ｇおよび銅、鉄、アルミののテストピ
−スを入れて密封し、１７５℃で１４日間加熱した後、
フロンガスを十分に減圧除去して、色調および酸価の測
定を行った。<Shield tube test> 70 g of sample oil and Freon R were placed in a 300 ml stainless steel autoclave.
-134a, 70g and a test piece of copper, iron, aluminum were put and sealed, and after heating at 175 ° C for 14 days,
Freon gas was sufficiently removed under reduced pressure, and color tone and acid value were measured.
【表１】 [Table 1]
フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ１０Ｍ 105:40 105:24 105:26） (Ｃ１０Ｍ 111/06 105:16 109:02） Ｃ１０Ｎ 30:10 30:12 40:30 Continuation of the front page (51) Int.Cl. 5 Identification number Reference number within the agency FI Technical display area C10M 105: 40 105: 24 105: 26) (C10M 111/06 105: 16 109: 02) C10N 30:10 30 : 12 40:30
Claims (2)
脂肪族モノカルボン酸（Ｂ）および必要に応じて多価カ
ルボン酸（Ｃ）とから得られるエステル化合物および水
素含有フルオロアルカンからなる水素含有フルオロアル
カン系冷凍機用組成物をフェノ−ル系抗酸化剤を用いて
安定化することを特徴とする水素含有フルオロアルカン
系冷凍機用組成物の安定化方法。1. The following general formula 1 A hydrogen-containing fluoroalkane system consisting of an ester compound obtained from at least one ester compound (A) selected from the above, an aliphatic monocarboxylic acid (B) and optionally a polyvalent carboxylic acid (C), and a hydrogen-containing fluoroalkane A method for stabilizing a hydrogen-containing fluoroalkane-based composition for refrigerators, which comprises stabilizing the composition for refrigerators with a phenol-based antioxidant.
脂肪族モノカルボン酸（Ｂ）、多価カルボン酸（Ｃ）お
よび多価アルコ−ル（Ｄ）とから得られるエステル化合
物および水素含有フルオロアルカンからなる水素含有フ
ルオロアルカン系冷凍機用組成物をフェノ−ル系抗酸化
剤を用いて安定化することを特徴とする水素含有フルオ
ロアルカン系冷凍機用組成物の安定化方法。2. The following general formula 2 An ester compound obtained from at least one ester compound (A) selected from the group consisting of (A), an aliphatic monocarboxylic acid (B), a polyvalent carboxylic acid (C) and a polyvalent alcohol (D), and a hydrogen-containing fluoroalkane. A method for stabilizing a hydrogen-containing fluoroalkane-based refrigerator composition, comprising stabilizing the hydrogen-containing fluoroalkane-based refrigerator composition with a phenol-based antioxidant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4110746A JPH05279658A (en) | 1992-04-02 | 1992-04-02 | Stabilization of hydrogen-containing fluoroalkane composition for refrigerator |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4110746A JPH05279658A (en) | 1992-04-02 | 1992-04-02 | Stabilization of hydrogen-containing fluoroalkane composition for refrigerator |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05279658A true JPH05279658A (en) | 1993-10-26 |
Family
ID=14543497
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4110746A Pending JPH05279658A (en) | 1992-04-02 | 1992-04-02 | Stabilization of hydrogen-containing fluoroalkane composition for refrigerator |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05279658A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009110584A1 (en) * | 2008-03-07 | 2009-09-11 | 出光興産株式会社 | Lubricant composition for refrigerating machine |
| US8568609B2 (en) | 2007-11-22 | 2013-10-29 | Idemitsu Kosan Co., Ltd. | Lubricating oil composition for refrigerating machine |
| US8906250B2 (en) | 2007-11-22 | 2014-12-09 | Idemitsu Kosan Co., Ltd. | Lubricant composition for refrigerating machine and compressor using the same |
-
1992
- 1992-04-02 JP JP4110746A patent/JPH05279658A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8568609B2 (en) | 2007-11-22 | 2013-10-29 | Idemitsu Kosan Co., Ltd. | Lubricating oil composition for refrigerating machine |
| US8906250B2 (en) | 2007-11-22 | 2014-12-09 | Idemitsu Kosan Co., Ltd. | Lubricant composition for refrigerating machine and compressor using the same |
| WO2009110584A1 (en) * | 2008-03-07 | 2009-09-11 | 出光興産株式会社 | Lubricant composition for refrigerating machine |
| JP2009235111A (en) * | 2008-03-07 | 2009-10-15 | Idemitsu Kosan Co Ltd | Lubricant composition for refrigerating machine |
| US8673169B2 (en) | 2008-03-07 | 2014-03-18 | Idemitsu Kosan Co., Ltd. | Lubricant composition for refrigerating machine |
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