JP2022524085A - 熱伝達流体及びその使用のための腐食抑制剤配合物 - Google Patents
熱伝達流体及びその使用のための腐食抑制剤配合物 Download PDFInfo
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- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/20—Antifreeze additives therefor, e.g. for radiator liquids
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- C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
- C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
- C09K15/30—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing heterocyclic ring with at least one nitrogen atom as ring member
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- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
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- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
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- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
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- C—CHEMISTRY; METALLURGY
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- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
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- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
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Abstract
Description
[0007]前置きとして、熱伝達流体において使用するための本発明による熱伝達流体濃縮物は、(a)凝固点降下剤;及び(b)(i)銅及び銅合金のための腐食抑制剤及び(ii)ポリアルキレングリコールを含む非イオン界面活性剤;を含む。熱伝達流体濃縮物の導電率は約100μS/cm以下である。
[0022]本明細書及び添付の特許請求の範囲全体において、以下の定義を理解すべきである。
[0032]「複素環式」という用語は、3~24個の炭素原子(幾つかの態様においては4~22個の炭素原子;他の態様においては6~20個の炭素原子)、及び少なくとも1つのヘテロ原子(幾つかの態様においては1~3個のヘテロ原子)を含む、飽和、部分飽和、又は芳香族環系を指す。環は、場合によっては1以上の置換基で置換されていてもよい。更に、環は、単環式、二環式、又は多環式であってよい。本明細書において使用する「複素環式」という用語は、「ヘテロアリール」の用語を包含する。環中に含められる代表的なヘテロ原子としては、窒素、酸素、及びイオウが挙げられるが、これらに限定されない。本発明による代表的な複素環式基としては、アジリジン、アジリン、オキシラン、オキシレン、チイラン、チイレン、ジアジリン、オキサジリジン、ジオキシラン、アゼチジン、アゼト、オキセタン、オキセト、チエタン、チエト、ジアゼチジン、ジオキセタン、ジオキセト、ジチエタン、ジチエト、ピロリジン、テトラヒドロフラン、チオラン、イミダゾリジン、ピラゾリデン、オキサゾリジン、イソオキサゾリジン、チアゾリジン、イソチアゾリデン、ジオキソラン、ジチオラン、フラザン、オキサジアゾール、ジチアゾール、テトラゾール、ピペリジン、オキサン、ピラン、チアン、チオピラン、ピペラジン、ジアジン、モルホリン、オキサジン、チオモルホリン、チアジン、ジオキサン、ジオキシン、ジチアン、ジチイン、トリオキサン、トリチアン、テトラジン、アゼパン、アゼピン、オキセパン、オキセピン、チエパン、チエピン、ホモピペラジン、ジアゼピン、チアゼピン、アゾカン、アゾシン、アクリジン、ベンゾチアゾリン、ベンズイミダゾール、ベンゾフラン、ベンゾチアペン、ベンズチアゾール、ベンゾチオフェニル、カルバゾール、シンノリン、フラン、イミダゾール、1H-インダゾール、インドール、イソインドール、イソキノリン、イソチアゾール、オキサゾール、イソオキサゾール、オキサジアゾール類(例えば1,2,3-オキサジアゾール)、フェナジン、フェノチアジン、フェノキサジン、フタラジン、プテリジン、プリン、ピラジン、ピラゾール、ピリダジン、ピリジン、ピリミジン、ピロール、キナゾリン、キノリン、キノキサリン、チアゾール、チアジアゾール類(例えば1,3,4-チアジアゾール)、チオフェン、トリアジン(例えば1,3,5-トリアジン)、トリアゾール類(例えば1,2,3-トリアゾール)などが挙げられるが、これらに限定されない。
RO(CH2CH2O)j(CH2CH2CH2O)kH (I)
(式中、ここで、Rは線状第1級アルコールであり、jはエチレンオキシドの総モル数を表し、kはプロピレンオキシドの総モル数を表す)
を有する。幾つかの実施形態においては、数式(I)において、RはC4~C25線状第1級アルコール(幾つかの実施形態においてはC6~C15線状第1級アルコール、他の実施形態においてはC7~C12線状第1級アルコール)であり、jは0~15(端点を含む)の整数であり、kは0~15(端点を含む)の整数であり、j+kは1以上の整数である。
RO(CH2CH2O)nH (II)
(式中、Rは直鎖第1級アルコールであり、nはエチレンオキシドの総モル数を表す)
のエトキシル化アルコールを含む。幾つかの実施形態において、式(II)において、RはC4~C25線状第1級アルコール(幾つかの実施形態においてはC6~C15線状第1級アル、他の実施形態においてはC7~C12線状第1級アルコール)であり、nは1~15(端点を含む)の整数である。
RO(CH2CH2CH2O)mH (III)
(式中、Rは線状第1級アルコールであり、mはプロピレンオキシドの総モル数を表す)
幾つかの実施形態において、式(III)において、RはC4~C25線状第1アルコール(幾つかの実施形態においてはC6~C15線状第1アルコール、他の実施形態においてはC7~C12線状の第1級アルコール)であり、mは1~15(端点を含む)の整数である)
のプロポキシル化アルコールを含む。
[0057]幾つかの実施形態においては、本発明による熱伝達流体濃縮物には、場合により、凝固点降下剤に加えてか又はその代わりに水を含ませることができる。熱伝達流体濃縮物から(例えば希釈によって)得られるすぐに使用できる熱伝達流体は、通常は水を含む。幾つかの実施形態においては、凝固点降下剤を含む本発明による熱伝達流体濃縮物は、水で40体積%~60体積%の溶液に希釈することができる。
R{Ak[(B)nR1]m}x (IV)
(式中、Rは、アントラキノン、トリフェニルメタン、ジフェニルメタン、トリアリールメタン、ジアリールメタン、アゾ含有化合物、ジアゾ含有化合物、トリスアゾ含有化合物、ジアゾ含有化合物、キサンテン、アクリジン、インデン、チアゾール、2以上の共役芳香族基、2以上の共役複素環基、及びそれらの組み合わせからなる群から選択される有機発色団であり;Aは、発色団中の連結基であり、O、N、及びSからなる群から選択され;kは0又は1であり;Bは、1~8個の炭素原子を含む1以上のアルキレンオキシ又はアルコキシ基からなる群から選択され;nは1~100の整数であり;mは1又は2の整数であり;xは1~5の整数であり;R1は、H、C1~C6アルキル基、又は1~8個の炭素原子を含むアルコキシ基、及びそれらの組み合わせからなる群から選択される)
を有する。
[0093]13種類の熱伝達流体組成物を、下表2及び3に要約するように調製した。全ての量は、熱伝達流体の総重量に対する重量%で示す。流体No.1~4の導電率も与える。
[0096]図1は、MRI-202S合金及びC1008鋼の腐食速度に対する抑制剤添加の効果のプロットを示す。時刻「A」において、0.6gのTRITON EF-19を加えた。時刻「B」において、0.04gのベンゾトリアゾールを添加した。時刻「C」及び「D」において、0.12gのSPAN 20を加えた。時刻「E」及び「F」において、0.12gのCARBOWAX PEG 400を加えた。時刻「G」において、0.24gのCARBOWAX PEG 400を加えた。時刻「H」において、0.24gのSPAN 20を加えた。時刻「I」において、1gのDOWEX monosphere MR-450UPW混合樹脂及び0.1237gのベンゾトリアゾールを加えた。
[0099]下表6に要約されるように、4種類の更なる熱伝達流体組成物A~Dを調製した。全ての量は、熱伝達流体の総重量に対する重量%で示す。流体A~Dの導電率も与える。
[00102]2種類の更なる熱伝達流体組成物No.14及び15を、下表8に要約するように調製した。全ての量は、熱伝達流体の総重量に対する重量%で示す。流体No.14及び15の導電率も与える。
[00105]表10は、本発明による熱伝達システム組成物が、更に発泡試験にかけた場合に優れた結果を示すことを示す。実施例C及びDを、それぞれ、ASTM-D1384腐食試験にかける前及びかけた後の両方において、Nummi及びASTM-D1881発泡試験にかけた。表10に示すように、本発明による組成物は、腐食試験を実施する前及び実施した後の両方において、ASTM-D3306仕様、並びに内燃及び代替動力源用途の両方について車両製造業者によって規定される要件に準拠する発泡試験結果をもたらす。
[00106]6種類の更なる熱伝達流体組成物16~21を、下表11に要約するように調製した。全ての量は、熱伝達流体の総重量に対する重量%で示す。
Claims (45)
- 熱伝達流体濃縮物であって、
凝固点降下剤;及び
(i)銅及び銅合金のための腐食抑制剤、及び(ii)ポリアルキレングリコールを含む非イオン性界面活性剤;
を含み、
前記熱伝達流体濃縮物の導電率は約100μS/cm以下である、上記熱伝達流体濃縮物。 - 前記熱伝達流体濃縮物の導電率が約25μS/cm以下である、請求項1に記載の熱伝達流体濃縮物。
- 前記熱伝達流体濃縮物の導電率が約10μS/cm以下である、請求項1に記載の熱伝達流体濃縮物。
- 前記凝固点降下剤がアルコールを含む、請求項1に記載の熱伝達流体濃縮物。
- 前記凝固点降下剤が、エチレングリコール、1,2-プロピレングリコール、1,3-プロパンジオール、又はそれらの組み合わせを含む、請求項1に記載の熱伝達流体濃縮物。
- 前記凝固点降下剤が、前記熱伝達流体濃縮物の総重量を基準として約10重量%~約99.85重量%の量で存在する、請求項1に記載の熱伝達流体濃縮物。
- 前記凝固点降下剤が、前記熱伝達流体濃縮物の総重量を基準として約30重量%~約99.5重量%の量で存在する、請求項1に記載の熱伝達流体濃縮物。
- 前記凝固点降下剤が、前記熱伝達流体濃縮物の総重量を基準として約40重量%~約99重量%の量で存在する、請求項1に記載の熱伝達流体濃縮物。
- 前記銅及び銅合金のための腐食抑制剤がアゾール化合物を含む、請求項1に記載の熱伝達流体濃縮物。
- 前記アゾール化合物が、場合により置換されているベンゾトリアゾール、場合により置換されているトリルトリアゾール、場合により置換されているC2~C20アルキルベンゾトリアゾール、場合により置換されているメルカプトベンゾチアゾール、場合により置換されているチアゾール、場合により置換されているイミダゾール、場合により置換されているベンズイミダゾール、場合により置換されているインダゾール、場合により置換されているテトラゾール、及びそれらの組合せからなる群から選択される、請求項9に記載の熱伝達流体濃縮物。
- 前記場合により置換されているC2~C20アルキルベンゾトリアゾールが、メチルベンゾトリアゾール、ブチルベンゾトリアゾール、又はそれらの組合せを含む、請求項10に記載の熱伝達流体濃縮物。
- 前記銅及び銅合金のための腐食抑制剤が、前記熱伝達流体濃縮物の総重量を基準として約0.01重量%~約4重量%の量で存在する、請求項1に記載の熱伝達流体濃縮物。
- 前記ポリアルキレングリコールが、ポリエチレングリコール、ポリプロピレングリコール、メトキシポリエチレングリコール、又はそれらの組み合わせを含む、請求項1に記載の熱伝達流体濃縮物。
- 前記非イオン性界面活性剤が、前記熱伝達流体濃縮物の総重量を基準として約0.001重量%~約2重量%の量で存在する、請求項1に記載の熱伝達流体濃縮物。
- 前記非イオン性界面活性剤が、前記熱伝達流体濃縮物の総重量を基準として約0.005重量%~約1重量%の量で存在する、請求項1に記載の熱伝達流体濃縮物。
- 前記非イオン性界面活性剤が、前記熱伝達流体濃縮物の総重量を基準として約0.01重量%~約0.5重量%の量で存在する、請求項1に記載の熱伝達流体濃縮物。
- 更なる非イオン性界面活性剤を更に含む、請求項1に記載の熱伝達流体濃縮物。
- 前記更なる非イオン性界面活性剤が、ソルビタン脂肪酸エステル、アルコキシル化アルコール、ポリアルキレングリコールエステル、エチレンオキシドとプロピレンオキシドとのコポリマー、ソルビタン脂肪酸エステルのポリオキシアルキレン誘導体、及びそれらの組み合わせからなる群から選択される、請求項17に記載の熱伝達流体濃縮物。
- 前記更なる非イオン性界面活性剤がソルビタン脂肪酸エステル及びアルコキシル化アルコールを含む、請求項17に記載の熱伝達流体濃縮物。
- 前記アルコキシル化アルコールが、式:
RO(CH2CH2O)j(CH2CH2CH2O)kH
(式中、RはC4~C25線状第1級アルコールであり、jは0~15の整数であり、kは0~15の整数であり、j+kは1以上の整数である)
を有する、請求項18に記載の熱伝達流体濃縮物, - RがC6~C15線状第1級アルコールである、請求項20に記載の熱伝達流体濃縮物。
- 前記アルコキシル化アルコールが、エトキシル化アルコール、プロポキシル化アルコール、又はそれらの組み合わせを含む、請求項18に記載の熱伝達流体濃縮物。
- 前記エトキシル化アルコールが、式:
RO(CH2CH2O)nH
(式中、RはC4~C25線状第1級アルコールであり、nは1~15の整数である)
を有する、請求項22に記載の熱伝達流体濃縮物。 - RがC6~C15線状第1級アルコールである、請求項23に記載の熱伝達流体濃縮物。
- 前記プロポキシル化アルコールが、式:
RO(CH2CH2CH2O)mH
(式中、RはC4~C25線状第1級アルコールであり、mは1~15の整数である)
を有する、請求項22に記載の熱伝達流体濃縮物 - RがC6~C15線状第1級アルコールである、請求項25に記載の熱伝達流体濃縮物。
- 前記アルコキシル化アルコールが、前記熱伝達流体濃縮物の総重量を基準として約0.001重量%~約1重量%の量で存在する、請求項18に記載の熱伝達流体濃縮物。
- シロキサン化合物、コロイダルシリカ、シクロヘキセンカルボキシレートのアミン塩、アミン化合物、又はそれらの組み合わせからなる群から選択される低導電性腐食抑制剤を更に含む、請求項1に記載の熱伝達流体濃縮物。
- 水を更に含む、請求項1に記載の熱伝達流体濃縮物。
- 前記水が、脱イオン水、脱塩水、軟化水、又はそれらの組み合わせである、請求項29に記載の熱伝達流体濃縮物。
- 前記水が、前記熱伝達流体濃縮物の総重量を基準として約0.1重量%~約90重量%の量で存在する、請求項29に記載の熱伝達流体濃縮物。
- 前記水が、前記熱伝達流体濃縮物の総重量を基準として約0.5重量%~約70重量%の量で存在する、請求項29に記載の熱伝達流体濃縮物。
- 前記水が、前記熱伝達流体濃縮物の総重量を基準として約1重量%~約60重量%の量で存在する、請求項29に記載の熱伝達流体濃縮物。
- C1~C20テトラアルキルオルトケイ酸エステル、着色剤、湿潤剤、殺生物剤、消泡剤、界面活性剤、更なる腐食抑制剤、非イオン性分散剤、及びそれらの組合せからなる群から選択される更なる成分を更に含む、請求項1に記載の熱伝達流体濃縮物。
- 熱伝達流体であって、
水;
前記熱伝達流体の総重量を基準として約10重量%~約99.85重量%の量の凝固点降下剤;
前記熱伝達流体の総重量を基準として約0.001重量%~約2重量%の量の、(i)アゾール化合物及び(ii)ポリアルキレングリコールを含む非イオン界面活性剤;
を含み;
前記熱伝達流体濃縮物の導電率は約50μS/cm以下である、上記熱伝達流体。 - 前記凝固点降下剤が、エチレングリコール、1,2-プロピレングリコール、1,3-プロパンジオール、又はそれらの組み合わせを含む、請求項35に記載の熱伝達流体。
- 前記ポリアルキレングリコールが、ポリエチレングリコール、ポリプロピレングリコール、メトキシポリエチレングリコール、又はそれらの組み合わせを含む、請求項35に記載の熱伝達流体。
- 前記アゾール化合物が、場合により置換されているベンゾトリアゾール、場合により置換されているトリルトリアゾール、場合により置換されているC2~C20アルキルベンゾトリアゾール、場合により置換されているメルカプトベンゾチアゾール、場合により置換されているチアゾール、場合により置換されているイミダゾール、場合により置換されているベンズイミダゾール、場合により置換されているインダゾール、場合により置換されているテトラゾール、及びそれらの組合せからなる群から選択される、請求項35に記載の熱伝達流体。
- ソルビタン脂肪酸エステル、アルコキシル化アルコール、ポリアルキレングリコールエステル、エチレンオキシドとプロピレンオキシドとのコポリマー、ソルビタン脂肪酸エステルのポリオキシアルキレン誘導体、及びそれらの組み合わせからなる群から選択される更なる非イオン性界面活性剤を更に含む、請求項35に記載の熱伝達流体。
- シロキサン化合物、コロイダルシリカ、シクロヘキセンカルボキシレートのアミン塩、アミン化合物、又はそれらの組み合わせからなる群から選択される低導電性腐食抑制剤を更に含む、請求項35に記載の熱伝達流体。
- C1~C20テトラアルキルオルトケイ酸エステル、着色剤、湿潤剤、殺生物剤、消泡剤、界面活性剤、更なる腐食抑制剤、非イオン性分散剤、及びそれらの組合せからなる群から選択される更なる成分を更に含む、請求項35に記載の熱伝達流体。
- 熱伝達システムにおける腐食を抑制する方法であって、
前記熱伝達システムの少なくとも一部を熱伝達流体と接触させること;
を含み;
前記熱伝達流体は、
凝固点降下剤;
水;及び
(i)銅及び銅合金のための腐食抑制剤、及び(ii)ポリアルキレングリコールを含む非イオン性界面活性剤;
を含み;
前記熱伝達流体の導電率は、約100μS/cm以下である、上記方法。 - 前記熱伝達システムが、炭素鋼、アルミニウム、アルミニウム合金、マグネシウム、マグネシウム合金、イエローメタル、又はそれらの組み合わせを含む部品を含む、請求項42に記載の方法。
- 前記熱伝達システムが、マグネシウム、マグネシウム合金、又はそれらの組み合わせを含む部品を含む、請求項42に記載の方法。
- 前記熱伝達システムが燃料電池を含む、請求項42に記載の方法。
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PCT/US2020/021523 WO2020185611A1 (en) | 2019-03-08 | 2020-03-06 | Heat transfer fluids and corrosion inhibitor formulations for use thereof |
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