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JP2004512388A - Methods for providing fluid compositions with improved fire resistance - Google Patents

Methods for providing fluid compositions with improved fire resistance Download PDF

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Publication number
JP2004512388A
JP2004512388A JP2001587038A JP2001587038A JP2004512388A JP 2004512388 A JP2004512388 A JP 2004512388A JP 2001587038 A JP2001587038 A JP 2001587038A JP 2001587038 A JP2001587038 A JP 2001587038A JP 2004512388 A JP2004512388 A JP 2004512388A
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Prior art keywords
weight
antioxidant
oxide
ethylene oxide
fluid composition
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JP2001587038A
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Japanese (ja)
Inventor
トッテン，ジョージ　エドワード
マトロック，ポール　ランプキン
ブラウン，ウィリアム　ローウェル
Original Assignee
ユニオン・カーバイド・ケミカルズ・アンド・プラスティックス・テクノロジー・コーポレイション
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Publication of JP2004512388A publication Critical patent/JP2004512388A/en
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    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
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  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Lubricants (AREA)
  • Fireproofing Substances (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

本発明は、無水ポリアルキレングリコール系流体組成物に、第一群または第二群耐火特性を与えるための方法を提供する。前記方法によると、前記流体組成物には、８．０×１０４未満の噴霧燃焼性パラメータを前記流体組成物に与えるに充分なエチレンオキシド／アルキレンオキシド質量（重量）パーセント比および／または前記パラメータ値を与えるに充分な酸化防止剤の量が配合される。本発明により処方された流体組成物は、液圧油および急冷剤として、耐火性が向上した流体が必要とされる他の工業用途および商業用途において有用である。The present invention provides a method for imparting first or second group fire resistance properties to anhydrous polyalkylene glycol-based fluid compositions. According to the method, the fluid composition may have an ethylene oxide / alkylene oxide mass (weight) percent ratio and / or the parameter value sufficient to provide a spray flammability parameter of less than 8.0 × 10 4 to the fluid composition. A sufficient amount of antioxidant is provided to provide The fluid compositions formulated according to the present invention are useful as hydraulic oils and quenchers in other industrial and commercial applications where fluids with improved fire resistance are required.

Description

【０００１】
本発明は、耐火特性が改良された流体を与える方法に関する。より詳細には、本発明は、無水ポリアルキレングリコール系流体組成物に、流体のエンタルピーを表す噴霧燃焼性パラメータを計算することにより測定される第一群または第二群の耐火特性を与える方法を提供する。
【０００２】
最近まで、耐火性流体は通常、噴霧燃焼性試験または熱水路試験を利用して分類されてきた。しかし、当業者は、これらの試験プロトコルが、さまざまな流体種類の耐火特性の観測可能な差異と有意な差異を適切に区別しないことを長い間認識してきた。そのため、マサチューセッツ州ノーウッドのファクトリーミュチュアル　リサーチ　コーポレーション（Ｆａｃｔｏｒｙ Ｍｕｔｕａｌ）は、実験により求められた噴霧燃焼性パラメータ（Ｓ．Ｆ．Ｐ．）により表される、流体のエンタルピーに基づく新しい試験プロトコルを開発した。この新しい Ｓ．Ｆ．Ｐ．プロトコルは、異なる流体の耐火特性の定量的な目安を提供し、流体種類間の正確な区別を考慮している。ファクトリーミュチュアルは、さまざまな物質の耐火特性を決定するための非常に権威ある情報供給源と当業者に認識されており、前記Ｓ．Ｆ．Ｐ．プロトコルは、耐火性流体を類別する基準になると期待されている。
【０００３】
新しいプロトコルによれば、実験的なＳ．Ｆ．Ｐ．パラメータは、実験データから以下の式により計算される。
【０００４】
【数１】

Figure 2004512388
【０００５】
上式において、Ｑｃｈ＝噴霧炎の化学放熱量（キロワット）
ρｆ＝流体密度（立方メートルあたりのキログラム）
Ｔｆ＝発火点温度（ケルビン温度）
ｍｆ＝流体の質量流量（秒あたりのグラム）
【０００６】
Ｓ．Ｆ．Ｐ．は、燃焼効率１００パーセントを仮定する以下の式により推定することもできる。
【０００７】
【数２】
Figure 2004512388
【０００８】
上式において、ΔＨＴ＝完全燃焼の正味の熱量（グラムあたりのキロジュール）
【０００９】
前記Ｓ．Ｆ．Ｐ．プロトコルを用いると、流体は表１に示される以下の群のいずれかに分類される。
【００１０】
（表１）
流体の分類
【表１】
Figure 2004512388
【００１１】
Ｓ．Ｆ．Ｐ．推定値の計算は、耐火性の予備的スクリーニング法として利用される。例えば、ある流体が第一群または第二群であるかを決定することが目的であって、４．０×１０４よりはるかに低いＳ．Ｆ．Ｐ．が得られた場合、さらに試験することなくその流体はファクトリーミュチュアルにより第一群であると認定されるであろう。しかし、Ｓ．Ｆ．Ｐ．推定値が４．０×１０４に近い場合、その流体を試験して適切な区分に正確に分類しなくてはならない。類似の手順を利用して、第二群または第三群に流体を分類する。
【００１２】
本発明は、無水ポリアルキレングリコール系流体組成物に少なくとも第二群耐火特性を与える方法を提供する。本発明によると、流体組成物に８．０×１０４未満の噴霧燃焼性パラメータを与えるに充分なエチレンオキシド／アルキレンオキシド質量（重量）パーセント比および／または前記パラメータ値を与えるに充分な酸化防止剤の量が組成物に配合されている。
【００１３】
より詳細には、本発明は、無水ポリアルキレングリコール系流体組成物に少なくとも第二群の耐火性を与える方法であって、前記流体組成物に８．０×１０４未満の噴霧燃焼性パラメータを与えるに充分なエチレンオキシド／アルキレンオキシド質量（重量）パーセント比と前記パラメータ値を与えるに充分な酸化防止剤の量との少なくとも一方を前記組成物に配合する工程を特徴とする方法を提供する。
【００１４】
本発明は、さらに、液圧系に少なくとも第二群の耐火特性を与える方法であって、無水ポリアルキレングリコール系液圧油に８．０×１０４未満の噴霧燃焼性パラメータを与えるに充分なエチレンオキシド／アルキレンオキシド質量（重量）パーセント比と前記パラメータ値を与えるに充分な酸化防止剤の量との少なくとも一方が配合された液圧油を系に加える工程を特徴とする方法を提供する。
【００１５】
本発明は、さらに、金属加工用熱処理系に少なくとも第二群の耐火特性を与える方法であって、無水ポリアルキレングリコール系急冷剤に８．０×１０４未満の噴霧燃焼性パラメータを与えるに充分なエチレンオキシド／アルキレンオキシド質量（重量）パーセント比と前記パラメータ値を与えるに充分な酸化防止剤の量との少なくとも一方が配合された急冷剤を系に加える工程を特徴とする方法を提供する。
【００１６】
無水ポリアルキレングリコール系流体組成物は、アルキレンオキシドモノマーと求核開始剤、通常アルコールとの反応から作製されるポリアルキレングリコール（ＰＡＧ）のポリマーを含む。これらのポリマーは以下の一般式により表される。
【００１７】
Ｒ‘Ｒ”
上式において、Ｚ＝メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、グリセリンおよびスクロースなどの炭素数１〜２０のアルコール開始剤。Ｚは、アンモニア、モノエタノールアミン、トリエタノールアミンおよびジエタノールアミンなどのアミン開始剤でもよい；
Ｒ‘Ｒ”＝ブロックまたはランダム構造を与える、任意の組合せでもよいＨ、ＣＨ３、任意のアリールまたはＣ２〜Ｃ１６アルキル基でもよく；
Ｒ‘“＝Ｈ、ＣＨ３、任意のアリール、エステルまたはＣ２〜Ｃ１６アルキル基でもよく；
ｎ＝５〜５００；
ｘ＝１〜６。
【００１８】
この一般式を有するＰＡＧポリマーはいかなるものでも、本発明による流体組成物を処方するのに使用できるが、これらの流体組成物は通常エチレンオキシドおよび／またはアルキレンオキシドポリマーを用いて処方される。エチレンオキシドはオキシド供給量の０〜１００質量（重量）パーセントの範囲でよく、残部はアルキレンオキシドモノマー、典型的にはプロピレンオキシドであるが、ブチレンオキシドまたはスチレンオキシドなどの他のオキシドも使用できる。上述のとおり、オキシドモノマーの配列はランダムでもブロックでもよい。
【００１９】
本発明によると、流体組成物は、前記組成物に０：１〜１：０のエチレンオキシド／アルキレンオキシド質量（重量）パーセント比を与えることにより、少なくとも第二群耐火性を与えられる。酸化防止剤を含む配合物では、組成物は少なくとも０．１質量（重量）パーセントの酸化防止剤、好ましくは０．５〜１０質量（重量）パーセントの酸化防止剤、最も好ましくは１〜２質量（重量）パーセントの酸化防止剤を含む。
【００２０】
前記流体組成物は、第一群耐火性を備えることが好ましく、すなわち、４．０×１０４以下の噴霧燃焼性パラメータを与えるに充分なエチレンオキシド／アルキレンオキシド質量（重量）パーセント比および／または前記パラメータ値を与えるに充分な酸化防止剤の量が配合されていることが好ましい。これは、ある実施様態において、少なくとも２：１〜１：０のエチレンオキシド／プロピレンオキシド比を組成物に配合することにより達成される。第二の実施様態においては、１：３〜３：１のエチレンオキシド／プロピレンオキシドパーセント質量（重量）比および１質量（重量）パーセント〜２質量（重量）パーセントの酸化防止剤を組成物に配合することにより、第一群耐火性が提供される。さらに別の実施様態において、０：１のエチレンオキシド／プロピレンオキシド質量（重量）パーセント比および１〜２質量（重量）パーセントの酸化防止剤を組成物に配合することにより、第一群／第二群境界線上の耐火性が提供される。
【００２１】
本発明の方法により処方された流体は、火事の危険性が重大な関心事であるさまざまな工業用途および商業用途に使用できる。例えば、液圧系の障害は多くの場合、死者を出す大規模な火災につながった。したがって、液圧油は高圧特性および潤滑特性に優れるばかりでなく、液圧系の障害から甚大な火災の危険性が生じかねないこれらの用途において耐火性を提供しなくてはならない。金属加工用途の熱処理系に使用される急冷剤流体も甚大な火災の危険性を有する。これは、ひび割れを生じやすい鋼合金の高温熱処理に使用されるマルテンパー流体に特に当てはまる。
【００２２】
本発明により処方される無水ポリアルキレングリコール系流体組成物は、液圧油として使用するのに特に好適である。このような組成物は高圧特性および耐火特性に優れるだけでなく、潤滑性も優れている。さらに、生分解性が良好で水中毒性の低い耐火性無水（ＰＡＧ）系液圧油を処方することが可能である。本発明により教示される流体組成物は優れた急冷剤でもあり、そのため熱処理用途での使用に特に適している。このような組成物は、当業界で通常使用されている特別処方の鉱物油急冷剤と同等の急冷特性を有し、耐火性という重要な利点も与える。前記組成物は、水溶性または生分解性になるように処方することも可能であり、鉱物油急冷剤に比較して著しく低い沈澱傾向を示す。
【００２３】
本発明により処方される流体組成物は、前記流体の使用される特定の工業用途または商業用途に応じて追加の成分を含んでいてもよい。したがって、これらの組成物は、例えば、潤滑性調整剤、腐食防止剤（鉄系および非鉄系の両方）、摩耗防止剤、極圧調整剤、染料、殺生物剤、消泡剤、湿潤剤、粘度調整剤、熱安定剤および洗剤を含んでいてもよい。
【００２４】
無水ポリアルキレングリコール（ＰＡＧ）系流体組成物のエチレンオキシド／アルキレンオキシド含量が、当組成物の耐火特性に著しい影響を与えることが明らかにされた。より詳細には、無水ＰＡＧ系流体組成物のエチレンオキシド含量を増やすことにより、当組成物のＳ．Ｆ．Ｐ．が低下することが見出された。無水ＰＡＧ系流体組成物に一種または複数種の酸化防止剤を添加すると、当組成物のエチレンオキシド／アルキレンオキシド質量（重量）パーセント比に関わらず、当組成物のＳ．Ｆ．Ｐ．が低下することも見出された。酸化防止剤により与えられるＳ．Ｆ．Ｐ．低下効果は、少なくとも特定の濃度レベルまでは酸化防止剤の構造および流体組成物中の濃度に依存する。上述のとおり、一種または複数種の酸化防止剤を用いて、所望のレベルの耐火性を与えることができる。
【００２５】
無水ＰＡＧ系流体組成物の耐火特性の向上に対するエチレンオキシド／アルキレンオキシド質量（重量）パーセント比ならびに酸化防止剤の選択および濃度の影響を明らかにするために、上記の式ＩＩを用いて数種の流体組成物に関してＳ．Ｆ．Ｐ．を推定した。研究用に選択された流体組成物およびこれらの流体に関して得られたデータを以下の表２に実施例１〜１５として簡単に示す。各流体組成物は、特定のエチレンオキシド／プロピレンオキシド（ＥＯ／ＰＯ）質量（重量）パーセント比を有する基本流体からなるか、もしくは酸化防止剤を含むそのような基本流体からなる。実施例１〜１５に使用される流体組成物のそれぞれは、エチレンオキシドポリマーまたはプロピレンオキシドポリマーあるいはエチレンオキシド／プロピレンオキシドコポリマーのいずれかを含むが、本発明はこの点で限定されるものでなく、上記の一般式を有する他のポリアルキレングリコールでも類似の結果が期待できることを理解されたい。
【００２６】
【表２】
Figure 2004512388
【００２７】
【表３】
Figure 2004512388
【００２８】
【表４】
Figure 2004512388
【００２９】
【表５】
Figure 2004512388
【００３０】
１　発火点（ｆｉｒｅ ｐｏｉｎｔ）は、Ａ．Ｓ．Ｔ．Ｍ．Ｄ９２に従い測定した。
２　燃焼熱は、Ａ．Ｓ．Ｔ．Ｍ．Ｄ２４０に従い測定した。
３　この基本流体は、Ｏｒｔｈｏｌｅｕｍ　５３５（基本流体の０．２５質量（重量）パーセント）およびＴｏｌｙｔｒｉａｚｏｌｅ（基本流体の０．０１質量（重量）パーセント）も含む。
【００３１】
ＵＣＯＮ　ルブリカント　ＬＢ−２８５は、アルコールを開始剤とするプロピレンオキシドのポリマーであり、３８℃で２８５セーボルトユニバーサル秒（ＳＵＳ）の粘度を有する。このポリマーは、コネチカット州ダンベリーのユニオンカーバイド　コーポレーションから市販されている。
【００３２】
ＵＣＯＮ　ルブリカント　ＬＢ−１６５は、アルコールを開始剤とするプロピレンオキシドのポリマーであり、３８℃で１６５ＳＵＳの粘度を有する。このポリマーは、コネチカット州ダンベリーのユニオンカーバイド　コーポレーションから市販されている。
【００３３】
ＵＣＯＮ　ルブリカント　５０−ＨＰ−２６０は、質量（重量）で等量のエチレンオキシドとプロピレンオキシドを含みアルコールを開始剤とするコポリマーである。このコポリマーは、３８℃で２６０ＳＵＳの粘度を有し、コネチカット州ダンベリーのユニオンカーバイド　コーポレーションから市販されている。
【００３４】
ＣＡＲＢＯ　ＷＡＸ　ＴＰＥＧ−９９０は、１モルあたり９９０グラムの分子量を有する、グリセリンを開始剤とするエチレンオキシドのポリマーである。ＣＡＲＢＯＷＡＸ　ＴＰＥＧ−９９０は、コネチカット州ダンベリーのユニオンカーバイド　コーポレーションから市販されている。
【００３５】
表２に示されたデータは、無水ＰＡＧ系流体組成物のエチレンオキシド含量が増加すると、当流体の耐火特性が上昇することを示している。特に、エチレンオキシド１００質量（重量）パーセントを含み酸化防止剤を含まない実施例１５が３．０２×１０４というＳ．Ｆ．Ｐ．を有することに留意されたい。すなわち、このＰＡＧ系流体組成物は第一群耐火特性を示している。実施例２も酸化防止剤を含まないが、エチレンオキシド／プロピレンオキシドの質量（重量）パーセント比が１：１である。実施例２はＳ．Ｆ．Ｐ．が４．７１×１０４であり、したがって第二群耐火性流体として分類される。しかし、実施例２の組成物のＳ．Ｆ．Ｐ．は、１００質量（重量）パーセントのプロピレンオキシドである実施例３の組成物のＳ．Ｆ．Ｐ．より著しく低い。
【００３６】
当業者は、無水ＰＡＧ系流体組成物のエチレンオキシド対アルキレンオキシド質量（重量）パーセント比の制御のみで、前記流体に第一群および第二群耐火性を提供できることを今まで認識していなかった。これらの流体は、過去に液圧油として使用されてきたが、米国特許第５，１４１，６６３号に開示されているとおり、流体へ水を混合するか、または流体の液滴の大きさを制御する添加剤を添加するかいずれかの方法により耐火性が得られていた。
【００３７】
液圧油への水の混合にはいくつかの欠点がある。これらの流体は一般的に無水流体に比べ液圧ポンプ性能が劣り、潤滑保護が低く、キャビテーションの可能性がはるかに高い。前記の米国特許第５，１４１，６６３号に開示されている無水ＰＡＧ系流体はこのような欠点を克服している。しかし、上述のとおり、前記組成物には流体の液滴の大きさを制御する添加剤を添加しなくてはならない。そのような添加剤を使用しないと、ノズルから噴霧される際の流体の液滴の大きさおよび分布を制御して許容可能な耐火性を与えることができない。
【００３８】
水溶性ポリマーを含む急冷剤は当業界に公知である。しかし、このような急冷剤は、鋼にひび割れを起こすほどの過大な冷却速度を特徴とすることが多い。さらに、これらの急冷剤中の水の蒸発は、熱処理環境を汚染することがある。無水の流体組成物を使用すると、このような重大になりかねない問題がなくなる。ごく限られた場合に、１００質量（重量）パーセントのエチレンオキシドを含む無水ＰＡＧ系流体組成物が急冷剤として過去に使用されてきた。しかし、これらの流体の優れた耐火特性と流体のエチレンオキシド含量を制御することにより耐火性が得られるという事実のいずれも当業者に認識されていなかった。
【００３９】
本発明は、水の添加および液滴の大きさを制御する添加剤の使用のいずれも必要としない。 表２に示すとおり、第一群および第二耐火性は、充分に有利なエチレンオキシド対プロピレンオキシド質量（重量）パーセント比を与えることにより達成される。 より詳細には、第一群耐火性は、無水ＰＡＧ系流体に、少なくとも２：１であるエチレンオキシド／プロピレンオキシド質量（重量）パーセント比を与えることにより達成される。エチレンオキシド／プロピレンオキシド質量（重量）パーセント比が少なくとも１：１である無水ＰＡＧ系流体組成物は第二群耐火性を示す。
【００４０】
表２のデータは、無水ＰＡＧ系流体組成物の耐火特性が、当組成物のエチレンオキシド／プロピレンオキシド質量（重量）パーセント比に関わらず、一種または複数種の酸化防止剤の添加により向上することも示している。さらに、前記データは、前記組成物が１００質量（重量）パーセントのプロピレンオキシドを含む場合でも、無水ＰＡＧ系流体組成物への酸化防止剤の添加により第二群耐火性が与えられることを示している。特に、実施例３、５〜８および１０の結果から、第一群耐火性に非常に近い耐火特性が、充分な量の適切な酸化防止剤または酸化防止剤の組合せの添加により提供されうることが分かる。
【００４１】
酸化防止剤の構造は、Ｓ．Ｆ．Ｐ．低下効果に重要な役割を果たしている。数種の酸化防止剤が、ＰＡＧ系流体の耐火特性を改善するのに特に効果的であることが見出されてきた。好ましい酸化防止剤には、フェノール酸化防止剤、ビスフェノールＡをターモノマーとして含むフェノールホルムアルデヒド樹脂、フェニル−α−ナフチルアミン（ＰＡＮＡ）などのアミン系酸化防止剤、フェノチアジンおよびこれらの酸化防止剤の混合物がある。しかし、本発明はこれらの酸化防止剤に限定されず、当業界に公知の他の酸化防止剤を使用してもよいことを理解されたい。例えば、亜リン酸トリフェニルなど亜リン酸エステル官能性酸化防止剤を使用してもよい。しかし、これらの酸化防止剤のＳ．Ｆ．Ｐ．低下効果は、上述の好ましい酸化防止剤により得られる効果より一般的に劣る。
【００４２】
実施例３、５〜８および１０は、Ｓ．Ｆ．Ｐ．の低下に対する酸化防止剤構造の効果を示している。これらの実施例は全て、１００質量（重量）パーセントのプロピレングリコールを含む同一の無水ＰＡＧ系流体を使用している。前記データは、この研究で評価された中でフェノチアジンが最も効果的な酸化防止剤であることを示している（実施例７）。アミン系酸化防止剤であるＰＡＮＡとニューヨーク州タリータウンのチバ（Ｃｉｂａ）スペシャルティ　ケミカルズ　コーポレーションから市販されているフェノール系酸化防止剤であるＩＲＧＡＮＯＸ　Ｅ−３２０１のどちらも、前記基本流体のＳ．Ｆ．Ｐ．を低下させるのに同程度効果的であった（実施例５および１３）。亜リン酸トリフェニル（実施例１０）は、実験した酸化防止剤の中で効果が一番低かった。他の効果的な酸化防止剤としては、ＩＲＧＡＮＯＸ　Ｌ−０６およびＩＲＧＡＮＯＸ　１０１０があり、どちらもニューヨーク州タリータウンのチバ　スペシャルティ　ケミカルズ　コーポレーションから市販されているアミン系酸化防止剤である。
【００４３】
酸化防止剤の濃度に関して、表２の結果は、酸化防止剤により得られるＳ．Ｆ．Ｐ．低下効果が、流体組成物中の酸化防止剤のある濃度までしか顕著でないことを示している。さらに酸化防止剤を添加しても、組成物の耐火特性はわずかしか改善しない。特に、実施例３〜５は同一の無水ＰＡＧ系流体を含むが、含まれる酸化防止剤Ｎ−フェニルアルファナフチルアミン（ＰＡＮＡ）の量が異なることに留意されたい。実施例４および５は、酸化防止剤を全く含まない実施例３よりも著しく低いＳ．Ｆ．Ｐ．を有する。しかし、実施例４における１質量（重量）パーセントから実施例５における２質量（重量）パーセントに酸化防止剤濃度を２倍にしても、耐火性の向上はわずかである。
【００４４】
一般的に、酸化防止剤により得られる耐火性は、流体組成物のエチレンオキシド含量が増加するにつれ上昇する。したがって、実施例１１に見られるように、酸化防止剤を含み１００質量（重量）パーセントのエチレンオキシドを含むＰＡＧ系組成物で最も低いＳ．Ｆ．Ｐ．結果が得られた。それよりわずかに高いがそれでも第一群である耐火性が、エチレンオキシドをわずか５０質量（重量）パーセントしか含まない流体組成物中において酸化防止剤の使用により得られた。無水ＰＡＧ系流体組成物がエチレンオキシドを全く含まない場合、少なくとも２質量（重量）パーセントの酸化防止剤が好ましい。流体組成物が、１：３〜３：１のエチレンオキシド／プロピレンオキシド質量（重量）パーセント比を特徴とする場合、当組成物は１質量（重量）パーセント〜２質量（重量）パーセントの酸化防止剤を含むことが好ましい。
【００４５】
以上で議論したとおり、実施例１〜１５のそれぞれにおけるＳ．Ｆ．Ｐ．を、１００パーセント燃焼を仮定する式ＩＩを用いて推定した。すなわち、表２に記載した流体組成物のいくつか（実施例３〜１０）のＳ．Ｆ．Ｐ．を実験的に導き、Ｓ．Ｆ．Ｐ．推定値とＳ．Ｆ．Ｐ．実験値の一致の度合を確認した。本研究の結果を以下の表３に示す。
【００４６】
（表３）
【表６】
Figure 2004512388
【００４７】
表３に示すとおり、Ｓ．Ｆ．Ｐ．推定値は、実験的に導いたＳ．Ｆ．Ｐ．の値に非常に近いが、全ての場合で常にそれより高い。式ＩＩでは１００パーセント燃焼を仮定しているため、これは予想通りである。この結果から、式ＩＩを用いて、実験的に導かれるＳ．Ｆ．Ｐ．値と非常に近いＳ．Ｆ．Ｐ．推定値を提供できることが確認された。
【００４８】
既に議論のとおり、本発明の方法により調製された無水ＰＡＧ系流体組成物は、耐火性液圧油、急冷剤および潤滑流体として使用できる。しかし、本発明がこれらの特定の用途に限定されず、本発明により教示される方法により調製される流体が、第一群および第二群の耐火性を有する流体組成物が必要とされる広範囲の工業用途および商業用途に使用可能であることを当業者は理解するであろう。[0001]
The present invention relates to a method for providing a fluid with improved fire resistance. More specifically, the present invention provides a method of providing an anhydrous polyalkylene glycol-based fluid composition with a first or second group of refractory properties measured by calculating a spray flammability parameter representing the enthalpy of the fluid. provide.
[0002]
Until recently, refractory fluids have usually been classified using a spray flammability test or a hot water test. However, those skilled in the art have long recognized that these test protocols do not adequately distinguish between observable and significant differences in refractory properties of various fluid types. Therefore, Factory Mutual Research Corporation of Norwood, Mass., Has developed a new test protocol based on enthalpy of fluid, represented by experimentally determined spray flammability parameters (SFP). . This new S.M. F. P. The protocol provides a quantitative measure of the refractory properties of different fluids and allows for an accurate distinction between fluid types. Factory Mutual is recognized by those skilled in the art as a very authoritative source of information for determining the refractory properties of various materials. F. P. The protocol is expected to be the standard for categorizing refractory fluids.
[0003]
According to the new protocol, the experimental S.D. F. P. The parameters are calculated from the experimental data by the following formula.
[0004]
(Equation 1)
Figure 2004512388
[0005]
In the above equation, Q ch = the amount of chemical radiation of the spray flame (kilowatt)
ρ f = fluid density (kg per cubic meter)
T f = ignition point temperature (Kelvin temperature)
m f = mass flow rate of fluid (grams per second)
[0006]
S. F. P. Can also be estimated by the following equation assuming 100% combustion efficiency.
[0007]
(Equation 2)
Figure 2004512388
[0008]
In the above equation, ΔH T = net heat of complete combustion (kilojoules per gram)
[0009]
S. F. P. Using the protocol, fluids are classified into any of the following groups shown in Table 1.
[0010]
(Table 1)
Fluid classification [Table 1]
Figure 2004512388
[0011]
S. F. P. The calculation of the estimates is used as a preliminary screening method for fire resistance. For example, the goal is to determine if a fluid is in the first or second group and the S.M. is much lower than 4.0 × 10 4 . F. P. If obtained, the fluid will be identified by Factory Mutual as a first group without further testing. However, S.M. F. P. If the estimate is close to 4.0 × 10 4 , the fluid must be tested and correctly classified into the appropriate category. A similar procedure is used to classify fluids into a second or third group.
[0012]
The present invention provides a method of providing an anhydrous polyalkylene glycol-based fluid composition with at least a second group of fire resistance properties. According to the present invention, an ethylene oxide / alkylene oxide weight (weight) percent ratio sufficient to provide a spray composition with a spray flammability parameter of less than 8.0 × 10 4 and / or sufficient antioxidant to provide a value for said parameter Is incorporated into the composition.
[0013]
More specifically, the present invention is a method of providing at least a second group of fire resistance to an anhydrous polyalkylene glycol-based fluid composition, wherein the fluid composition has a spray flammability parameter of less than 8.0 × 10 4. Providing a method comprising incorporating into the composition at least one of an ethylene oxide / alkylene oxide weight (weight) percent ratio sufficient to provide and an amount of an antioxidant sufficient to provide the parameter value.
[0014]
The present invention is further directed to a method of imparting at least a second group of fire resistance properties to a hydraulic system, wherein the anhydrous polyalkylene glycol-based hydraulic oil is provided with a spray flammability parameter of less than 8.0 × 10 4. A method is provided which comprises adding a hydraulic oil to the system that is blended with at least one of an ethylene oxide / alkylene oxide mass (weight) percent ratio and an amount of an antioxidant sufficient to provide the parameter value.
[0015]
The present invention is further directed to a method of imparting at least a second group of refractory properties to a metalworking heat treatment system, wherein the anhydrous polyalkylene glycol-based quenching agent is provided with a spray flammability parameter of less than 8.0 × 10 4. Adding a quenching agent to the system, wherein the quenching agent is blended with at least one of a weight percent by weight ethylene oxide / alkylene oxide ratio and an amount of an antioxidant sufficient to provide the parameter value.
[0016]
The anhydrous polyalkylene glycol-based fluid composition comprises a polymer of polyalkylene glycol (PAG) made from the reaction of an alkylene oxide monomer with a nucleophilic initiator, usually an alcohol. These polymers are represented by the following general formula:
[0017]
R'R "
In the above formula, Z = C1-C20 alcohol initiator such as methanol, ethanol, propanol, isopropanol, butanol, glycerin and sucrose. Z may be an amine initiator such as ammonia, monoethanolamine, triethanolamine and diethanolamine;
R′R ″ = H, CH 3 , any aryl or C 2 -C 16 alkyl group, which may be in any combination, giving a block or random structure;
R '"= H, CH 3 , any aryl may be an ester or C 2 -C 16 alkyl group;
n = 5-500;
x = 1-6.
[0018]
Although any PAG polymer having this general formula can be used to formulate the fluid compositions according to the present invention, these fluid compositions are usually formulated with ethylene oxide and / or alkylene oxide polymers. Ethylene oxide may range from 0 to 100 weight percent of the oxide feed, with the balance being an alkylene oxide monomer, typically propylene oxide, although other oxides such as butylene oxide or styrene oxide can be used. As described above, the sequence of the oxide monomers may be random or block.
[0019]
In accordance with the present invention, the fluid composition is provided with at least a second group fire resistance by providing the composition with an ethylene oxide / alkylene oxide percent by weight ratio of 0: 1 to 1: 0. In formulations that include an antioxidant, the composition may comprise at least 0.1 weight percent antioxidant, preferably 0.5 to 10 weight percent antioxidant, and most preferably 1 to 2 weight percent. Contains (by weight) percent antioxidants.
[0020]
Said fluid composition preferably includes a first group of refractory, i.e., sufficient ethylene oxide / alkylene oxide mass give the spray combustion parameter of 4.0 × 10 4 or less (by weight) percent ratio and / or the Preferably, an amount of antioxidant sufficient to provide the parameter value is included. This is achieved, in one embodiment, by incorporating an ethylene oxide / propylene oxide ratio of at least 2: 1 to 1: 0 into the composition. In a second embodiment, an ethylene oxide / propylene oxide percent by weight (weight) ratio of from 1: 3 to 3: 1 and from 1 to 2 weight percent of an antioxidant are incorporated into the composition. This provides first class fire resistance. In yet another embodiment, Group 1 / Group 2 by incorporating 0: 1 ethylene oxide / propylene oxide weight (weight) percent ratio and 1-2 weight (weight) percent antioxidant into the composition. Fire resistance on the perimeter is provided.
[0021]
Fluids formulated according to the method of the present invention can be used in a variety of industrial and commercial applications where fire risk is a significant concern. For example, hydraulic system failures have often led to large-scale fires leading to death. Therefore, hydraulic oils must not only have excellent high pressure and lubricating properties, but must also provide fire resistance in these applications where failure of the hydraulic system can result in significant fire hazard. Quenchant fluids used in heat treatment systems for metalworking applications also have significant fire hazards. This is especially true for martemper fluids used for high temperature heat treatment of crack prone steel alloys.
[0022]
The anhydrous polyalkylene glycol-based fluid compositions formulated according to the present invention are particularly suitable for use as hydraulic oils. Such a composition is excellent not only in high pressure properties and fire resistance properties but also in lubricity. Further, it is possible to formulate a refractory anhydrous (PAG) hydraulic oil having good biodegradability and low water toxicity. The fluid compositions taught by the present invention are also excellent quenchers and are therefore particularly suitable for use in heat treatment applications. Such compositions have quenching properties comparable to specially formulated mineral oil quenchers commonly used in the art, and also provide the important advantage of fire resistance. The compositions can also be formulated to be water-soluble or biodegradable and exhibit a significantly lower tendency to settle as compared to mineral oil quenchers.
[0023]
Fluid compositions formulated according to the present invention may include additional components depending on the particular industrial or commercial application for which the fluid is used. Thus, these compositions include, for example, lubricity modifiers, corrosion inhibitors (both ferrous and non-ferrous), antiwear agents, extreme pressure modifiers, dyes, biocides, defoamers, wetting agents, Viscosity modifiers, heat stabilizers and detergents may be included.
[0024]
It has been found that the ethylene oxide / alkylene oxide content of the anhydrous polyalkylene glycol (PAG) based fluid composition has a significant effect on the fire resistance properties of the composition. More specifically, by increasing the ethylene oxide content of the anhydrous PAG-based fluid composition, the S.A. F. P. Was found to decrease. The addition of one or more antioxidants to the anhydrous PAG-based fluid composition results in a S.P.O. of the composition regardless of the ethylene oxide / alkylene oxide weight (weight) percent ratio of the composition. F. P. Was also found to decrease. S.I. provided by antioxidants F. P. The reducing effect depends on the structure of the antioxidant and the concentration in the fluid composition, at least up to a certain concentration level. As mentioned above, one or more antioxidants can be used to provide the desired level of fire resistance.
[0025]
To demonstrate the effect of ethylene oxide / alkylene oxide weight (weight) percent ratio and the choice and concentration of antioxidants on improving the refractory properties of anhydrous PAG-based fluid compositions, several fluids were used using Formula II above. The S.P. F. P. Was estimated. The fluid compositions selected for the study and the data obtained for these fluids are briefly shown in Table 2 below as Examples 1-15. Each fluid composition consists of a base fluid having a specific ethylene oxide / propylene oxide (EO / PO) weight (weight) percentage ratio or consists of such a base fluid containing an antioxidant. Each of the fluid compositions used in Examples 1-15 includes either an ethylene oxide polymer or a propylene oxide polymer or an ethylene oxide / propylene oxide copolymer, but the invention is not limited in this respect and It should be understood that similar results can be expected with other polyalkylene glycols having the general formula.
[0026]
[Table 2]
Figure 2004512388
[0027]
[Table 3]
Figure 2004512388
[0028]
[Table 4]
Figure 2004512388
[0029]
[Table 5]
Figure 2004512388
[0030]
1 The ignition point (fire point) S. T. M. Measured according to D92.
2 The heat of combustion is A. S. T. M. Measured according to D240.
3 This base fluid also includes Ortholeum 535 (0.25 weight percent by weight of base fluid) and Tolytriazole (0.01 weight percent by weight of base fluid).
[0031]
UCON Lubricant LB-285 is a polymer of propylene oxide initiated with alcohol and has a viscosity of 285 Saybolt Universal Seconds (SUS) at 38 ° C. This polymer is commercially available from Union Carbide Corporation of Danbury, Connecticut.
[0032]
UCON Lubricant LB-165 is a polymer of propylene oxide initiated with alcohol and has a viscosity of 165SUS at 38 ° C. This polymer is commercially available from Union Carbide Corporation of Danbury, Connecticut.
[0033]
UCON Lubricant 50-HP-260 is a copolymer containing equal parts by weight (by weight) of ethylene oxide and propylene oxide and initiated by an alcohol. This copolymer has a viscosity of 260 SUS at 38 ° C. and is commercially available from Union Carbide Corporation of Danbury, CT.
[0034]
CARBO WAX TPEG-990 is a glycerin-initiated polymer of ethylene oxide having a molecular weight of 990 grams per mole. CARBOWAX TPEG-990 is commercially available from Union Carbide Corporation of Danbury, CT.
[0035]
The data shown in Table 2 shows that as the ethylene oxide content of the anhydrous PAG-based fluid composition increases, the refractory properties of the fluid increase. In particular, Example 15 with 100 weight percent ethylene oxide and no antioxidant had an S.D. of 3.02 × 10 4 . F. P. Note that That is, this PAG-based fluid composition exhibits the first group refractory properties. Example 2 also contains no antioxidants, but with a 1: 1 ethylene oxide / propylene oxide weight (weight) ratio. Example 2 is based on S.I. F. P. Is 4.71 × 10 4 and is therefore classified as a second group refractory fluid. However, the S.V. F. P. Is 100% by weight of propylene oxide. F. P. Significantly lower.
[0036]
One of ordinary skill in the art has never been aware that merely controlling the ethylene oxide to alkylene oxide weight (weight) percent ratio of the anhydrous PAG-based fluid composition can provide first and second class fire resistance to the fluid. These fluids have been used as hydraulic oils in the past, but as disclosed in US Pat. No. 5,141,663, water is added to the fluid or the size of the fluid droplets is reduced. Fire resistance was obtained either by adding additives to be controlled or by any method.
[0037]
Mixing water with hydraulic oil has several disadvantages. These fluids generally have poor hydraulic pump performance, poor lubrication protection and much higher cavitation potential than anhydrous fluids. The anhydrous PAG-based fluid disclosed in the aforementioned U.S. Pat. No. 5,141,663 overcomes such disadvantages. However, as noted above, additives must be added to the composition to control the size of the fluid droplets. Without such additives, the size and distribution of the fluid droplets as sprayed from the nozzles cannot be controlled to provide acceptable fire resistance.
[0038]
Quenchers comprising water-soluble polymers are known in the art. However, such quenching agents are often characterized by excessive cooling rates that cause the steel to crack. In addition, the evaporation of water in these quenchers can contaminate the heat treatment environment. The use of anhydrous fluid compositions eliminates this potentially serious problem. In very limited cases, anhydrous PAG-based fluid compositions containing 100 weight percent ethylene oxide have been used in the past as quenchers. However, neither the excellent fire resistance properties of these fluids nor the fact that fire resistance is obtained by controlling the ethylene oxide content of the fluid was recognized by those skilled in the art.
[0039]
The present invention requires neither the addition of water nor the use of additives to control droplet size. As shown in Table 2, the first and second refractories are achieved by providing a fully advantageous ethylene oxide to propylene oxide mass (weight) percent ratio. More specifically, first class fire resistance is achieved by providing anhydrous PAG-based fluids with an ethylene oxide / propylene oxide weight (weight) percent ratio of at least 2: 1. Anhydrous PAG-based fluid compositions having an ethylene oxide / propylene oxide weight (weight) percent ratio of at least 1: 1 exhibit a second group fire resistance.
[0040]
The data in Table 2 also shows that the refractory properties of the anhydrous PAG-based fluid composition can be improved by the addition of one or more antioxidants, regardless of the ethylene oxide / propylene oxide weight (weight) percent ratio of the composition. Is shown. Furthermore, the data show that the addition of antioxidants to anhydrous PAG-based fluid compositions provides a second class fire resistance, even when the composition contains 100 weight percent propylene oxide. I have. In particular, the results of Examples 3, 5 to 8 and 10 show that fire resistance properties very close to Group 1 fire resistance can be provided by the addition of a sufficient amount of a suitable antioxidant or antioxidant combination. I understand.
[0041]
The structure of the antioxidant is described in F. P. It plays an important role in the reduction effect. Several antioxidants have been found to be particularly effective in improving the refractory properties of PAG-based fluids. Preferred antioxidants include phenol antioxidants, phenol formaldehyde resins containing bisphenol A as a termonomer, amine antioxidants such as phenyl-α-naphthylamine (PANA), phenothiazine and mixtures of these antioxidants. . However, it should be understood that the invention is not limited to these antioxidants, and that other antioxidants known in the art may be used. For example, a phosphite-functional antioxidant such as triphenyl phosphite may be used. However, the S.I. F. P. The lowering effect is generally inferior to the effect obtained with the preferred antioxidants described above.
[0042]
Examples 3, 5 to 8 and 10 are based on S. F. P. The effect of the antioxidant structure on the reduction of All of these examples use the same anhydrous PAG-based fluid containing 100 weight percent propylene glycol. The data indicate that phenothiazine is the most effective antioxidant evaluated in this study (Example 7). Both PANA, an amine-based antioxidant, and IRGANOX E-3201, a phenolic antioxidant, commercially available from Ciba Specialty Chemicals Corporation of Tarrytown, NY, use the basic fluid S.I. F. P. Was as effective in lowering the A. (Examples 5 and 13). Triphenyl phosphite (Example 10) was the least effective of the antioxidants tested. Other effective antioxidants include IRGANOX L-06 and IRGANOX 1010, both amine-based antioxidants commercially available from Ciba Specialty Chemicals Corporation of Tarrytown, NY.
[0043]
With respect to the concentration of the antioxidant, the results in Table 2 show that the S.O. F. P. It shows that the reducing effect is only noticeable up to a certain concentration of antioxidant in the fluid composition. The addition of further antioxidants only slightly improves the refractory properties of the composition. In particular, it should be noted that Examples 3-5 contain the same anhydrous PAG-based fluid, but differ in the amount of antioxidant N-phenyl alpha naphthylamine (PANA) included. Examples 4 and 5 have significantly lower S.D. than Example 3 without any antioxidant. F. P. Having. However, even if the antioxidant concentration is doubled from 1% by weight (weight) in Example 4 to 2% by weight (weight) in Example 5, the fire resistance is slightly improved.
[0044]
Generally, the fire resistance provided by antioxidants increases as the ethylene oxide content of the fluid composition increases. Thus, as seen in Example 11, the lowest S.A.P. in the PAG-based composition with the antioxidant and 100 weight percent ethylene oxide. F. P. The result was obtained. A slightly higher, but still first class, fire resistance was obtained by the use of antioxidants in fluid compositions containing only 50 percent by weight ethylene oxide. If the anhydrous PAG-based fluid composition does not contain any ethylene oxide, at least 2 weight percent antioxidant is preferred. If the fluid composition is characterized by an ethylene oxide / propylene oxide weight (weight) percent ratio of 1: 3 to 3: 1, the composition may comprise from 1 weight percent to 2 weight percent antioxidant. It is preferable to include
[0045]
As discussed above, the S.I. F. P. Was estimated using Equation II assuming 100 percent combustion. That is, some of the fluid compositions described in Table 2 (Examples 3 to 10) had a S.I. F. P. Was experimentally derived, and S.P. F. P. Estimates and S.D. F. P. The degree of agreement between the experimental values was confirmed. The results of this study are shown in Table 3 below.
[0046]
(Table 3)
[Table 6]
Figure 2004512388
[0047]
As shown in Table 3, S.D. F. P. The estimates are based on experimentally derived S.M. F. P. Is very close to, but always higher in all cases. This is expected, as Equation II assumes 100 percent combustion. From these results, the experimentally derived S.M. F. P. S. values very close to F. P. It was confirmed that an estimate could be provided.
[0048]
As previously discussed, anhydrous PAG-based fluid compositions prepared by the method of the present invention can be used as refractory hydraulic oils, quenchers and lubricating fluids. However, the present invention is not limited to these particular applications, and the fluids prepared by the methods taught by the present invention can be used in a wide variety of applications where a first and second group of refractory fluid compositions are required. One of ordinary skill in the art will appreciate that it can be used for industrial and commercial applications.

Claims (15)

無水ポリアルキレングリコール系流体組成物に少なくとも第二群の耐火性を与える方法であって、前記流体組成物に８．０×１０４未満の噴霧燃焼性（ｓｐｒａｙ ｆｌａｍｍａｂｉｌｉｔｙ）パラメータを与えるに充分なエチレンオキシド／アルキレンオキシド質量（重量）パーセント比と前記パラメータ値を与えるに充分な酸化防止剤の量との少なくとも一方を前記組成物に配合する工程を特徴とする方法。A method of imparting at least a second group of fire resistance to an anhydrous polyalkylene glycol-based fluid composition, wherein the ethylene oxide is sufficient to impart a spray flammability parameter of less than 8.0 × 10 4 to the fluid composition. A method comprising incorporating into the composition at least one of a weight / weight percentage of alkylene oxide and an amount of an antioxidant sufficient to provide the parameter value. 前記アルキレンオキシドがプロピレンオキシド、ブチレンオキシドまたはスチレンオキシドである、請求項１に記載の方法。The method according to claim 1, wherein the alkylene oxide is propylene oxide, butylene oxide or styrene oxide. 前記エチレンオキシド／アルキレンオキシド質量（重量）パーセント比が少なくとも１：１である、請求項１に記載の方法。The method of claim 1, wherein the ethylene oxide / alkylene oxide weight (weight) percent ratio is at least 1: 1. 前記エチレンオキシド／アルキレンオキシド比が少なくとも２：１である、請求項３に記載の方法。4. The method of claim 3, wherein said ethylene oxide / alkylene oxide ratio is at least 2: 1. 前記流体組成物が少なくとも０．１質量（重量）パーセントの酸化防止剤を含む、請求項１に記載の方法。The method of claim 1, wherein the fluid composition comprises at least 0.1 weight percent by weight antioxidant. 前記流体組成物が０．５〜１０質量（重量）パーセントの酸化防止剤を含む、請求項５に記載の方法。The method of claim 5, wherein the fluid composition comprises 0.5 to 10 weight percent antioxidant. 前記流体組成物が１〜２質量（重量）パーセントの酸化防止剤を含む、請求項６に記載の方法。The method of claim 6, wherein the fluid composition comprises 1-2 weight percent antioxidant. 前記流体組成物が基本的に１００質量（重量）パーセントのエチレンオキシドからなる、請求項１に記載の方法。The method of claim 1, wherein the fluid composition consists essentially of 100 weight percent ethylene oxide. 前記流体組成物が基本的にエチレンオキシドおよび酸化防止剤からなる、請求項１に記載の方法。The method of claim 1, wherein the fluid composition consists essentially of ethylene oxide and an antioxidant. 前記エチレンオキシド／アルキレンオキシド質量（重量）パーセント比が３：１である、請求項１に記載の方法。The method of claim 1, wherein the ethylene oxide / alkylene oxide weight (weight) percent ratio is 3: 1. 前記エチレンオキシド／アルキレンオキシド質量（重量）パーセント比が１：３〜３：１であり、前記流体組成物が１質量（重量）パーセント〜２質量（重量）パーセントの酸化防止剤を含む、請求項１に記載の方法。2. The fluid composition of claim 1, wherein the ethylene oxide / alkylene oxide weight (weight) percent ratio is from 1: 3 to 3: 1 and the fluid composition comprises 1 weight percent to 2 weight percent antioxidant. The method described in. 前記アルキレンオキシドがプロピレンオキシドであり、前記組成物が０：１のエチレンオキシド／プロピレンオキシド比を有し、前記組成物が１〜２質量（重量）パーセントの酸化防止剤を含む、請求項２に記載の方法。3. The composition of claim 2, wherein the alkylene oxide is propylene oxide, the composition has an ethylene oxide / propylene oxide ratio of 0: 1, and the composition comprises 1-2 weight percent antioxidant. the method of. 前記酸化防止剤がアミン系酸化防止剤、フェノール酸化防止剤、ビスフェノールＡをターモノマーとして含むフェノールホルムアルデヒド樹脂、亜リン酸エステル官能性酸化防止剤またはこれらの混合物である、請求項１に記載の方法。The method according to claim 1, wherein the antioxidant is an amine antioxidant, a phenol antioxidant, a phenol formaldehyde resin containing bisphenol A as a termonomer, a phosphite-functional antioxidant, or a mixture thereof. . 液圧（ｈｙｄｒａｕｌｉｃ）系に少なくとも第二群の耐火特性を与える方法であって、無水ポリアルキレングリコール系液圧油に８．０×１０４未満の噴霧燃焼性パラメータを与えるに充分なエチレンオキシド／アルキレンオキシド質量（重量）パーセント比と前記パラメータ値を与えるに充分な酸化防止剤の量との少なくとも一方が配合された液圧油を系に加える工程を特徴とする方法。A method of providing fire characteristic of at least a second group of a hydraulic (Hydraulic) system, sufficient ethylene oxide / alkylene to give a spray combustion parameter of 8.0 × 10 than 4 in anhydrous polyalkylene glycol liquid pressure oil A method comprising adding a hydraulic oil to the system, wherein the oil comprises at least one of an oxide weight (weight) percent ratio and an amount of an antioxidant sufficient to provide the parameter value. 金属加工用熱処理系に少なくとも第二群の耐火特性を与える方法であって、無水ポリアルキレングリコール系急冷剤に８．０×１０４未満の噴霧燃焼性パラメータを与えるに充分なエチレンオキシド／アルキレンオキシド質量（重量）パーセント比と前記パラメータ値を与えるに充分な酸化防止剤の量との少なくとも一方が配合された急冷剤を系に加える工程を特徴とする方法。A method of imparting at least a second group of refractory properties to a heat treatment system for metalworking, the ethylene / alkylene oxide mass being sufficient to provide a spray flammability parameter of less than 8.0 × 10 4 to the anhydrous polyalkylene glycol-based quenchant Adding a quenching agent to the system, wherein the quenching agent is blended with at least one of a (weight) percent ratio and an amount of an antioxidant sufficient to provide the parameter value.
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