JPH04173751A - Method for stabilizing 1,1-dichloro-2,2,2-trifluoroethane - Google Patents
Method for stabilizing 1,1-dichloro-2,2,2-trifluoroethaneInfo
- Publication number
- JPH04173751A JPH04173751A JP29972290A JP29972290A JPH04173751A JP H04173751 A JPH04173751 A JP H04173751A JP 29972290 A JP29972290 A JP 29972290A JP 29972290 A JP29972290 A JP 29972290A JP H04173751 A JPH04173751 A JP H04173751A
- Authority
- JP
- Japan
- Prior art keywords
- trifluoroethane
- dichloro
- generation
- decomposition product
- title compound
- 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
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 title claims abstract description 5
- 238000000034 method Methods 0.000 title claims description 5
- 230000000087 stabilizing effect Effects 0.000 title claims 2
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 13
- 150000002430 hydrocarbons Chemical group 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 abstract description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 6
- MMSLOZQEMPDGPI-UHFFFAOYSA-N p-Mentha-1,3,5,8-tetraene Chemical compound CC(=C)C1=CC=C(C)C=C1 MMSLOZQEMPDGPI-UHFFFAOYSA-N 0.000 abstract description 4
- CYXIKYKBLDZZNW-UHFFFAOYSA-N 2-Chloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)CCl CYXIKYKBLDZZNW-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 2
- 239000000443 aerosol Substances 0.000 abstract description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004088 foaming agent Substances 0.000 abstract description 2
- 229930195733 hydrocarbon Natural products 0.000 abstract description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 abstract description 2
- 229940029284 trichlorofluoromethane Drugs 0.000 abstract description 2
- XSQYYLSXKMCPJQ-UHFFFAOYSA-N 1,2-dimethyl-4-prop-1-en-2-ylbenzene Chemical group CC(=C)C1=CC=C(C)C(C)=C1 XSQYYLSXKMCPJQ-UHFFFAOYSA-N 0.000 abstract 1
- 239000003183 carcinogenic agent Substances 0.000 abstract 1
- 239000002609 medium Substances 0.000 abstract 1
- 238000005057 refrigeration Methods 0.000 abstract 1
- 239000003381 stabilizer Substances 0.000 description 8
- 229920002635 polyurethane Polymers 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- 238000005187 foaming Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- 238000011109 contamination Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- IZSKYMMOWORXFB-UHFFFAOYSA-N 1-but-1-en-2-yl-4-prop-1-en-2-ylbenzene Chemical compound CCC(=C)C1=CC=C(C(C)=C)C=C1 IZSKYMMOWORXFB-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000012611 container material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、１．１−ジクロロ−２，２，２−トリフルオ
ロエタン（以下、Ｒ１２３という）の安定化を行い、分
解生成物である１−クロロ−２，２，２−トリフルオロ
エタン（以下、Ｒ１３３ａという）の発生を抑制する方
法に関するものである。Detailed Description of the Invention [Industrial Application Field] The present invention stabilizes 1,1-dichloro-2,2,2-trifluoroethane (hereinafter referred to as R123), which is a decomposition product. The present invention relates to a method for suppressing the generation of 1-chloro-2,2,2-trifluoroethane (hereinafter referred to as R133a).
［従来の技術］
従来、ポリウレタン発泡、ターボ冷凍機、洗浄等におい
て、トリクロロフルオロメタン（以下、Ｒ１１という）
が使用されてきた。しかし、完全ハロゲン化炭化水素類
は、オゾン層に対する環境問題が指摘されており、代替
物質の開発が急務となっている。[Prior Art] Conventionally, trichlorofluoromethane (hereinafter referred to as R11) has been used in polyurethane foaming, turbo chillers, cleaning, etc.
has been used. However, fully halogenated hydrocarbons have been pointed out to pose environmental problems to the ozone layer, and there is an urgent need to develop alternative substances.
Ｒ１１代替物質としてＲ１２３が有力視されている。R123 is considered to be a promising substitute for R11.
Ｒ１２３は安定性が優れているが、各種化合物が共存す
る場合には、安定性が低下し、各種分解生成物を生じる
といわれている。分解を促進する共存物質としては、例
えば、溶剤においては溶解性を高める目的より、アルコ
ールが添加されていると共に、洗浄機や被洗物材料との
接触、油等の汚れ成分や水分の混入等があげられる。一
方、プロペラントにおいては水溶性有効成分を溶解させ
る目的よりアルコールが添加されていると共に、容器材
料があげられる。Although R123 has excellent stability, it is said that when various compounds coexist, the stability decreases and various decomposition products are produced. Coexisting substances that promote decomposition include, for example, alcohol is added to solvents to increase solubility, contact with washing machines and materials to be washed, contamination components such as oil, and moisture contamination. can be given. On the other hand, in propellants, alcohol is added for the purpose of dissolving water-soluble active ingredients, and container materials are also included.
又、発泡剤として使用するポリウレタン発泡においては
、ポリウレタン原料であるポリオールや触媒、整泡剤や
発泡機とＲ１２３が接触する。ターボ冷凍機等の冷媒と
して使用する場合には、冷凍機を構成する材料や潤滑油
があげられる。In addition, in polyurethane foaming that is used as a foaming agent, R123 comes into contact with polyol, which is a polyurethane raw material, a catalyst, a foam stabilizer, and a foaming machine. When used as a refrigerant for a centrifugal refrigerator or the like, examples include materials constituting the refrigerator and lubricating oil.
Ｒ１２３の分解が起こると、例えば、エアゾール製品に
おいては、アルコールの酸化されたものによる臭気や液
の着色、あるいは分解生成物であるハロゲン化水素によ
る容器の腐食、又、ポリウレタン発泡においては、触媒
の不活性化による発泡倍率の低下、原料ポリオールの粘
度の上昇、製品の黄褐色化、冷凍機においては、分解生
成物であるハロゲン化水素により機械の腐食や潤滑油の
劣化に基づく機械の故障等好ましからざる問題を発生さ
せる。更に、大きな問題としては、Ｒ】２３の分解の結
果、Ｒ１３３ａが発生する。When decomposition of R123 occurs, for example, in aerosol products, it causes odor and coloring of the liquid due to oxidized alcohol, or corrosion of the container due to hydrogen halide, which is a decomposition product, and in polyurethane foaming, it causes damage to the catalyst. Decrease in expansion ratio due to inactivation, increase in the viscosity of the raw material polyol, yellowing of the product, corrosion of the machine due to hydrogen halide which is a decomposition product in refrigerators, machine failure due to deterioration of lubricating oil, etc. cause undesirable problems. Furthermore, a major problem is that R133a is generated as a result of the decomposition of R23.
［発明が解決しようとする課題］
Ｒ１２３の分解の結果生成するＲ］３３ａは発癌性の疑
いが持たれており、安全性の点より、発生を抑制するの
が極めて重要である。[Problems to be Solved by the Invention] R]33a produced as a result of the decomposition of R123 is suspected of being carcinogenic, and from the viewpoint of safety, it is extremely important to suppress its occurrence.
［課題を解決するための手段］
本発明は前述の問題点を解決すべく、Ｒ１２３の安定剤
検討を重ねた結果、本発明者らは。[Means for Solving the Problems] In order to solve the above-mentioned problems, the present inventors have developed the present invention as a result of repeated studies on stabilizers for R123.
下記−膜化式（１）で表される化合物（以下化合物（１
）という）が、著しいＲ１３３ａ生成抑制効果を発揮で
きることを見いだし本発明を完成するに至った。Compound (hereinafter referred to as compound (1)) represented by the following - film formation formula (1)
)) has been found to have a remarkable effect of suppressing R133a production, and have completed the present invention.
（Ｒ”、Ｒ２、Ｒ３及びＲ４は水素又は炭素原子数１〜
３個の炭化水素基）
すなわち、本発明は、前記化合物（１）を含有せしめる
ことを特徴とするＲ１２３がらのＲ１３３ａ発生を抑制
する方法に関するものである。(R”, R2, R3 and R4 are hydrogen or have 1 to 1 carbon atoms
3 hydrocarbon groups) That is, the present invention relates to a method for suppressing the generation of R133a from R123, which is characterized by containing the compound (1).
本発明における化合物（１）としては、公知乃至周知の
化合物が例示されるが、通常はスチレン、ビニルトルエ
ン、α−メチルスチレン、ｐ−イソプロペニルトルエン
、ｐ−インプロペニル−０−キシレン、ｐ−イソプロペ
ニル−α−エチルスチレン等が好適に選ばれる。Compound (1) in the present invention is exemplified by known or well-known compounds, but usually styrene, vinyltoluene, α-methylstyrene, p-isopropenyltoluene, p-impropenyl-0-xylene, p- Isopropenyl-α-ethylstyrene and the like are preferably selected.
本発明における安定剤の含有割合は特に限定されないが
、Ｒ１２３に対しテｏ、００１ｗｔ％以上、好ましくは
、０．０１〜５ｗｔ％が適当である。又、本発明の安定
剤にさらに他の安定剤、例えば、フェノール類、エポキ
シ化合物やニトロ基を含有する炭化水素化合物等を０．
００１〜５ｗｔ％添加することも可能である。The content ratio of the stabilizer in the present invention is not particularly limited, but it is suitably at least 0.001 wt%, preferably from 0.01 to 5 wt%, based on R123. In addition, other stabilizers such as phenols, epoxy compounds, and hydrocarbon compounds containing nitro groups may be added to the stabilizer of the present invention.
It is also possible to add 0.001 to 5 wt%.
［実施例］
以下、本発明を実施例により具体的に説明するが、本発
明はこれらの実施例のみに限定されるものではない。[Examples] Hereinafter, the present invention will be specifically explained using Examples, but the present invention is not limited only to these Examples.
ポリウレタン発泡剤としての結果を表１に示す。試料と
して次に示す混合液を調製し、ボ’） 、ｔ −ルＥＬ
−７５０ＨＤ １００重量部（旭オーリン社製）
触 媒 Ｄａｂｃｏ ３３ＬＶ ２重量部
（三共エアープロダクト社製）
整 泡 剤 ５Ｈ−１９３２重量部（東しシリ
コーン社製）
純水 ４重量部Ｒ１２３（Ｃ
）ｌｃ１２ｃＦｓ） ４０重量部これに安定
剤の所定量を混合し、これを耐圧ガラス容器に封入し、
熱風循環型恒温槽中で温度９０℃に保持し、３日間加熱
試験を行う。加熱試験後に、分解生成物であるＲ１３３
ａの発生量をガスクロマトグラフィーを用い分析するこ
とにより、Ｒ１３３ａ発生抑制効果を測定できる。The results as a polyurethane blowing agent are shown in Table 1. Prepare the following mixture as a sample, and add
-750HD 100 parts by weight (manufactured by Asahi Olin Co., Ltd.) Catalyst Dabco 33LV 2 parts by weight (manufactured by Sankyo Air Products Co., Ltd.) Foam stabilizer 5H-1932 parts by weight (manufactured by Toshi Silicone Co., Ltd.) Pure water 4 parts by weight R123 (C
) lc12cFs) 40 parts by weight was mixed with a predetermined amount of stabilizer, and this was sealed in a pressure-resistant glass container.
The temperature is maintained at 90°C in a hot air circulation type constant temperature bath, and a heating test is performed for 3 days. After the heating test, the decomposition product R133
The effect of suppressing the generation of R133a can be measured by analyzing the amount of a generated using gas chromatography.
表１
一方、冷媒としての結果を表２に示す。試料として次に
示す混合液を調製し、
潤滑油 肛ソ４Ｇ３ ５０重量部（日本サン石
油社製）
Ｒ１２３（ＣＨＣｌｉＣＦｓ） １００重量部金属
（ＳＳ４１． Ｃｕ、 Ａｌ）
これに安定剤の所定量を混合し、これを耐圧金属容器に
封入し、熱風循環型恒温槽中で温度１３０℃に保持し、
１４日間加熱試験を行う。加熱試験後に、分解生成物で
あるＲ１３３ａの発生量をガスクロマトグラフィーを用
い分析することにより、Ｒ１３３ａ発生抑制効果を測定
できる。Table 1 On the other hand, Table 2 shows the results as a refrigerant. The following mixed liquid was prepared as a sample, and a predetermined amount of a stabilizer was mixed with this: 50 parts by weight of lubricating oil 4G3 (manufactured by Nippon Sun Oil Co., Ltd.), 100 parts by weight of R123 (CHCliCFs), metals (SS41. Cu, Al). This was then sealed in a pressure-resistant metal container and maintained at a temperature of 130°C in a hot air circulation type constant temperature bath.
A heating test is conducted for 14 days. After the heating test, the generation suppression effect of R133a can be measured by analyzing the amount of generated R133a, which is a decomposition product, using gas chromatography.
表２ ［発明の効果］ 本発明の方法に従って安定化されたＲTable 2 [Effect of the invention] R stabilized according to the method of the invention
Claims (2)
子数１〜３個の炭化水素基）で表される炭化水素化合物
を含有せしめることを特徴とする１，１−ジクロロ−２
，２，２−トリフルオロエタンを安定化する方法。(1) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼…(1) (R^1, R^2, R^3 and R^4 are hydrogen or hydrocarbon groups with 1 to 3 carbon atoms) 1,1-dichloro-2 characterized by containing a hydrocarbon compound represented by
, 2,2-trifluoroethane.
子数１〜３個の炭化水素基）で表される炭化水素化合物
を含有せしめ、１，１−ジクロロ−２，２，２−トリフ
ルオロエタンの分解生成物である１−クロロ−２，２，
２−トリフルオロエタンの発生を抑制することにより、
１，１−ジクロロ−２，２，２−トリフルオロエタンを
安定化する方法。(2) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼…(1) (R^1, R^2, R^3 and R^4 are hydrogen or hydrocarbon groups with 1 to 3 carbon atoms) 1-chloro-2,2, which is a decomposition product of 1,1-dichloro-2,2,2-trifluoroethane, contains a hydrocarbon compound represented by
By suppressing the generation of 2-trifluoroethane,
A method of stabilizing 1,1-dichloro-2,2,2-trifluoroethane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29972290A JPH04173751A (en) | 1990-11-07 | 1990-11-07 | Method for stabilizing 1,1-dichloro-2,2,2-trifluoroethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29972290A JPH04173751A (en) | 1990-11-07 | 1990-11-07 | Method for stabilizing 1,1-dichloro-2,2,2-trifluoroethane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04173751A true JPH04173751A (en) | 1992-06-22 |
Family
ID=17876176
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29972290A Pending JPH04173751A (en) | 1990-11-07 | 1990-11-07 | Method for stabilizing 1,1-dichloro-2,2,2-trifluoroethane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04173751A (en) |
-
1990
- 1990-11-07 JP JP29972290A patent/JPH04173751A/en active Pending
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