JP2007532767A - テトラフルオロフ゜ロヘ゜ンとヘ゜ンタフルオロフ゜ロヘ゜ンとの共沸性組成物 - Google Patents
テトラフルオロフ゜ロヘ゜ンとヘ゜ンタフルオロフ゜ロヘ゜ンとの共沸性組成物 Download PDFInfo
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- JP2007532767A JP2007532767A JP2007508632A JP2007508632A JP2007532767A JP 2007532767 A JP2007532767 A JP 2007532767A JP 2007508632 A JP2007508632 A JP 2007508632A JP 2007508632 A JP2007508632 A JP 2007508632A JP 2007532767 A JP2007532767 A JP 2007532767A
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Abstract
Description
本発明は、1,1,1,2-テトラフルオロフ゜ロヘ゜ンと1,1,1,2,3-ヘ゜ンタフルオロフ゜ロヘ゜ンのZ異性体との共沸性組成物、および、その使用を提供する。
フルオロカーボンベースの流体は、冷媒、エアゾール噴射剤、発泡剤、熱伝達媒体、及びガス状誘電体を含む多くの適用において工業的に広範囲な用途を見出している。いくつかのこれらの流体の使用に伴って予想される環境問題(これらが有する比較的高い地球温暖化係数を含む)のために、オゾン破壊係数が低いかむしろゼロである流体(例えば、ハイドロフルオロカーボン(「HFC」)など)を使用することが好ましい。したがって、クロロフルオロカーボン(「CFC」)又はハイドロクロロフルオロカーボン(「HCFC」)を含有しない流体の使用が好ましい。さらに、単一成分流体、又は、沸騰及び蒸発によって分留しない共沸混合物の使用が好ましい。さらに、HFC流体の中には、比較的高い地球温暖化係数を有するものがあり、使用特性において所望する性能を維持しつつ、可能な限り低い地球温暖化係数を有するハイドロフルオロカーボン又は他のフッ素化された流体を使用することが好ましい。さらに、単一成分流体、又は、沸騰及び蒸発において実質的に分留されない共沸性混合物の使用が好ましい。しかしながら、共沸混合物の形成が容易に予想できないという事実のために、環境的に安全で分留されない新規混合物を見出すことは難しい。
本発明人は、CFC及びHCFCの代替物に対する長年のニーズを満足することに役立つ数種の組成物を開発した。ある態様によれば、本発明は、1,1,1,2-テトラフルオロフ゜ロヘ゜ン(「HFO-1234yf」)と(Z)-1,1,1,2,3-ヘ゜ンタフルオロフ゜ロヘ゜ン(「HFO-1225yeZ」)とを含んでなる共沸性組成物を提供する。
シ゛クロロシ゛フルオロメタン(CFC-12)などのCFC;
クロロシ゛フルオロメタン(HCFC-22)などのHCFC;
テトラフルオロエタン(HFC-134a)などのHFC;および
CFC-12と1,1-シ゛フルオロエタン(HFC-152a)との組合わせなどのHFCとCFCとの組合わせ(CFC-12:HFC-152aの73.8:26.2の質量比の組合わせはR-500として知られる)。
本明細書において使用する場合、「共沸性」との用語は、その広い意味であって、厳密に共沸である組成物と共沸混合物のように挙動する組成物との両方を含むことを意図している。基本法則によれば、流体の熱力学的状態は、圧力、温度、液体の組成、及び蒸気の組成によって定義される。共沸混合物とは、特定の圧力及び温度において液体組成と蒸気組成とが等しい2以上の成分からなる系である。実際上、これは、共沸混合物の成分が定沸点であり、相変化中に分離することができないことを意味する。
本発明の共沸性組成物は、潤滑剤、安定剤、金属不動態化剤、腐食防止剤、可燃性抑制剤等を始めとする各種の所望による添加剤のいずれかをさらに含むことができる。
式中:Rは、水素、ヒドロキシル、アルキル、フルオロアルキル、アリール、フルオロアリール、又は以下の式:
Arは、置換又は未置換のフェニレン或いはナフチレン部分である。ある種の好ましい式Iの芳香族エポキシドは、Arがフェニレン、或いはアルキル、アルケニル、アルキニル、アリール、アルキルアリール、ハロゲン、ハロゲン化アルキル、ハロゲン化アルケニル、ハロゲン化アルキニル、ハロゲン化アリール、ハロゲン化アリールアルキル、ヒドロキシル、異種原子部分、等を含む一つ又はそれより多い置換基で置換されたフェニレンを含む。Arが、未置換又は置換のフェニレンである式Iの適した化合物の例は、ブチルフェニルグリシジルエーテル;ペンチルフェニルグリシジルエーテル;ヘキシルフェニルグリシジルエーテル;ヘプチルフェニルグリシジルエーテル;オクチルフェニルグリシジルエーテル;ノニルフェニルグリシジルエーテル;デシルフェニルグリシジルエーテル;グリシジルメチルフェニルエーテル;1,4−ジグリシジルフェニルジエーテル;4−メトキシフェニルグリシジルエーテル;これらの誘導体;等を含む。
式中、Ralkは、置換又は未置換のアルキル又はアルケニル基である。式IIのある種の好ましいエポキシドは、Ralkが、約1〜約10個の炭素原子(より好ましくは約1〜約6個)の炭素原子を有するアルキル基であるアルキルエポキシド化合物を含んでなり、そしてここにおいてアルキルは、置換されていないか、或いはアルキル、アルケニル、アルキニル、アリール、アルキルアリール、ハロゲン、ハロゲン化アルキル、ハロゲン化アルケニル、ハロゲン化アルキニル、ハロゲン化アリール、ハロゲン化アリールアルキル、ヒドロキシル、異種原子部分、等を含む一つ又はそれより多い置換基でさらに置換されていることができる。式IIのこのような好ましいアルキルエポキシドの例は、n−ブチルグリシジルエーテル、イソブチルグリシジルエーテル、ヘキサンジオールグリシジルエーテル、等、並びにフッ素化及び過フッ素化されたアルキルエポキシド、等を含む。ある種のさらに好ましいアルキルエポキシドは、ヘキサンジオールジグリシジルエーテル、等を含んでなる。
本発明の組成物は、広い範囲の適用に用途を有する。例えば、本発明に含まれるものは、熱伝達への適用、フォーム及び発泡剤への適用、噴射剤への適用、噴射性組成物への適用、殺菌への適用、及びその他に関連する、本発明の共沸性組成物を含んでなる方法及び組成物である。
トリクロロフルオロメタン(CFC-11)
シ゛クロロシ゛フルオロメタン(CFC-12)
シ゛フルオロメタン(HFC-32)
ヘ゜ンタフルオロエタン(HFC-125)
1,1,2,2-テトラフルオロエタン(HFC-134)
1,1,1,2-テトラフルオロエタン(HFC-134a)
シ゛フルオロエタン(HFC-152a)
1,1,1,2,3,3,3-ヘフ゜タフルオロフ゜ロハ゜ン(HFC-227ea)
1,1,1,3,3,3-ヘキサフルオロフ゜ロハ゜ン(HFC-236fa)
1,1,1,3,3-ヘ゜ンタフルオロフ゜ロハ゜ン(HFC-245fa)
1,1,1,3,3-ヘ゜ンタフルオロフ゛タン(HFC-365mfc)
水
CO2。
本発明は、さらに以下の実施例において例示され、これは、例示を意図したものであり、いずれかの方法ででも制約するものではない。
頂部に凝縮器を持ち、石英温度計K96S4771を備えた、真空ジャケットされた管からなる沸点測定器を使用する。約17gのHFO-1234yfを沸点測定器に入れ、次いで、HFO-1225yeZを、少量の測定された増分にて加えた。HFO-1225yeZがHFO-1234yfに加えられたとき、温度降下が観察され、二成分の最小沸点共沸混合物が形成されたことを示した。約0より大きく約50重量パーセントまでのHFO-1225yeZにおいて、組成物の沸点は約3℃又はそれより少なく変化した。表1に示した二成分混合物を研究したところ、組成物の沸点は約3℃又はそれより少なく変化した。組成物は、この範囲において共沸特性及び/又は共沸性特性を示す。
Claims (33)
- 有効量のHFO-1234yfとHFO-1225yeZとを含んでなる共沸性組成物。
- 約50から100重量パーセントより少ないHFO-1234yfと
ゼロより多く約50重量パーセントまでのHFO-1225yeZと
から本質的になる、請求項1に記載の共沸性組成物。 - 約93から100重量パーセントより少ないHFO-1234yfと
ゼロより多く約7重量パーセントまでのHFO-1225yeZと
から本質的になる、請求項1に記載の共沸性組成物。 - 約14.2psiaの圧力において、約−26℃〜約−30℃の沸点を有する、請求項1に記載の共沸性組成物。
- 約14.2psiaの圧力において、約−27℃〜約−30℃の沸点を有する、請求項2に記載の共沸性組成物。
- 請求項1に記載の組成物と、
補助潤滑剤、相溶化剤、界面活性剤、補助燃焼抑制剤、可溶化剤、分散剤、気泡安定剤、化粧品、研磨剤、医薬、洗浄剤、燃焼防止剤、着色剤、化学的殺菌剤、安定剤、ポリオール、ポリオールプレミックス成分およびこれらの2以上の組み合わせからなる群から選択される少なくとも1つのアジュバントと
を含んでなる組成物。 - 請求項10に記載の組成物を含んでなり、前記アジュバントが少なくとも一つの潤滑剤を含んでなる熱伝達組成物。
- 前記補助潤滑剤が、鉱油、シリコーン油、ポリアルキルベンゼン(PAB)、ポリオールエステル(POE)、ポロアルキレングリコール(PAG)、ポリアルキレングリコールエステル(PAGエステル)、ポリビニルエーテル(PVE)、ポリ(α−オレフィン)(PAO)、及びこれらの組合わせからなる群から選択される、請求項11に記載の熱伝達組成物。
- 前記アジュバントが、少なくとも一つの相溶化剤をさらに含む、請求項12に記載の熱伝達組成物。
- 約0.5〜約5重量パーセントの前記少なくとも一つの相溶化剤を含んでなる、請求項13に記載の熱伝達組成物。
- 加えられた前記補助潤滑剤(類)が、熱伝達組成物の約5〜約50重量パーセントの量で存在する、請求項12に記載の熱伝達組成物。
- 一つ又はそれより多い補助燃焼抑制剤を含んでなる、請求項11に記載の熱伝達組成物。
- 加えられた前記一つ又はそれより多い燃焼抑制剤(類)が、熱伝達組成物の約0.5%〜約30重量%の量で存在する、請求項16に記載の熱伝達組成物。
- 請求項1に記載の共沸性組成物を含んでなる、熱伝達組成物。
- 少なくとも約50重量%の請求項1記載の共沸性組成物を含んでなる、熱伝達組成物。
- 請求項15に記載の熱伝達組成物による冷媒を含んでなる冷蔵システム。
- 自動車用空調システム、住宅用空調システム、商業用空調システム、住宅用冷蔵庫システム、住宅用冷凍庫システム、商業用冷蔵庫システム、商業用冷凍庫システム、チラー空調システム、チラー冷蔵庫システム、ヒートポンプシステム、及び一つ又はそれより多いこれらの組合わせからなる群から選択される、請求項16に記載の冷蔵システム。
- 請求項1に記載の共沸性組成物を含んでなる発泡剤。
- 少なくとも約5重量%の請求項1に記載の共沸性組成物を含んでなる発泡剤。
- フォームを形成することが可能な一つ又はそれより多い成分と
請求項1に記載の共沸性組成物と
を含んでなる発泡性組成物。 - 前記フォームを形成することが可能な一つ又はそれより多い成分が、熱可塑性フォーム、ポリスチレンフォーム、ポリエチレンフォーム、低密度ポリエチレンフォーム、押出し成型熱可塑性フォーム、ポリウレタンフォーム、及びポリイソシアヌレートフォームからなる群から選択されるフォームを形成することが可能な一つ又はそれより多い成分を含んでなる、請求項20に記載の発泡性組成物。
- 分散剤、気泡安定剤、界面活性剤、燃焼防止剤及び2以上のこれらの組合わせからなる群から選択される少なくとも一つの添加剤をさらに含んでなる、請求項21に記載の発泡性組成物。
- 請求項22に記載の発泡性組成物から形成されるフォーム。
- 請求項23に記載のフォームを含んでなる独立気泡フォーム。
- 冷媒システムに含有された既存の冷媒を置換する方法であって、
前記既存の冷媒の少なくとも一部を前記システムから除去し、
請求項1に記載の共沸性組成物を含んでなる冷媒組成物を前記システムに導入することによって、前記既存の冷媒の少なくとも一部を置換すること
を含んでなる、上記方法。 - 前記既存の冷媒が、HFC-134a、R-12、R-500、HFC-152a、及びHFC-22並びにこれらの組合わせからなる群から選択される、請求項25に記載の方法。
- 前記既存の冷媒が、HFC-134a、HFC-143a、HFC-125、HFC-32及びこれらの組合わせからなる群から選択される、請求項25に記載の方法。
- 前記既存の冷媒が、HFC-143a、HFC-125、HFC-32及びこれらの組合わせからなる群から選択される、請求項25に記載の方法。
- 前記既存の冷媒システムが、自動車用空調システム、住宅用空調システム、商業用空調システム、住宅用冷蔵庫システム、住宅用冷凍庫システム、商業用冷蔵庫システム、商業用冷凍庫、チラー空調システム、チラー冷蔵システム、ヒートポンプシステム、及び二つ又はそれより多いこれあの組合わせからなる群から選択される、請求項25に記載の方法。
- 請求項10に記載の前記冷媒が、約1000より大きくない地球温暖化係数(GWP)を有する、請求項30に記載の方法。
- 噴霧する物質と
請求項1に記載の共沸性組成物を含んでなる噴射剤と
を含んでなる噴霧可能な組成物。 - エアゾールの形態の、請求項40に記載の噴霧可能な組成物。
- 物品を滅菌する方法であって、請求項1に記載の組成物を含んでなる組成物と前記物品を接触させることを含んでなる、上記方法。
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