JP2008156263A - Method for stabilizing ethylene glycol - Google Patents
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- JP2008156263A JP2008156263A JP2006345702A JP2006345702A JP2008156263A JP 2008156263 A JP2008156263 A JP 2008156263A JP 2006345702 A JP2006345702 A JP 2006345702A JP 2006345702 A JP2006345702 A JP 2006345702A JP 2008156263 A JP2008156263 A JP 2008156263A
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- ethylene glycol
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- antifreeze
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 238000000034 method Methods 0.000 title claims abstract description 21
- 230000000087 stabilizing effect Effects 0.000 title claims abstract description 15
- 150000003549 thiazolines Chemical class 0.000 claims abstract description 16
- 230000003647 oxidation Effects 0.000 claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 15
- 230000002265 prevention Effects 0.000 claims abstract 3
- 239000000126 substance Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 9
- 230000002528 anti-freeze Effects 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000002826 coolant Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000000110 cooling liquid Substances 0.000 claims description 2
- 230000006641 stabilisation Effects 0.000 claims description 2
- 238000011105 stabilization Methods 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 claims 1
- 238000006731 degradation reaction Methods 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 3
- WGJCBBASTRWVJL-UHFFFAOYSA-N 1,3-thiazolidine-2-thione Chemical compound SC1=NCCS1 WGJCBBASTRWVJL-UHFFFAOYSA-N 0.000 abstract description 2
- 230000003064 anti-oxidating effect Effects 0.000 abstract 1
- 230000006866 deterioration Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000003203 everyday effect Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- -1 triazole compound Chemical class 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OUIAITHYQOIRPM-UHFFFAOYSA-N 4-methyl-1,3-thiazolidine-2-thione Chemical compound CC1CSC(=S)N1 OUIAITHYQOIRPM-UHFFFAOYSA-N 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Abstract
Description
本発明は、主として有機合成用の反応剤や溶剤、自動車などの内燃機関などにおいて不凍液および/または冷却液、あるいは化学プラントにおける熱媒や冷媒として使用されるエチレングリコールに関し、詳細にはエチレングリコールの劣化防止方法に関する。 The present invention relates to ethylene glycol used mainly as an antifreeze and / or cooling liquid in an organic synthesis reactant or solvent, an internal combustion engine such as an automobile, or a heating medium or refrigerant in a chemical plant. The present invention relates to a method for preventing deterioration.
エチレングリコールをはじめアルコール類は、特に加熱時に熱劣化や空気酸化を受けやすく、劣化することが知られている。従来、エチレングリコール類の酸化を防止する方法としては、特許文献１にトリアゾール化合物を添加する方法が、特許文献２には特定のカルボン酸塩による方法が開示されている。また、下記化２に記載の化合物とエチレングリコール類との組み合わせは、金属除去剤の比較例として、特許文献３に開示があるに過ぎない。 It is known that alcohols such as ethylene glycol are susceptible to thermal deterioration and air oxidation especially during heating, and deteriorate. Conventionally, as a method for preventing the oxidation of ethylene glycols, Patent Document 1 discloses a method of adding a triazole compound, and Patent Document 2 discloses a method using a specific carboxylate. Further, the combination of the compound described in Chemical Formula 2 and ethylene glycols is merely disclosed in Patent Document 3 as a comparative example of the metal remover.
本発明の目的は、エチレングリコールの安定化方法を提供することにある。この目的を達成するために、本発明のとった手段について、以下に説明する。 An object of the present invention is to provide a method for stabilizing ethylene glycol. In order to achieve this object, means taken by the present invention will be described below.
すなわち本発明にかかるエチレングリコールの安定化方法の構成は、含水状態であってもよいエチレングリコールおよび下記化２で表されるチアゾリン誘導体からなり、当該チアゾリン誘導体を１種または２種以上添加することによる、エチレングリコールの酸化に対する安定化方法である。 That is, the composition of the method for stabilizing ethylene glycol according to the present invention comprises ethylene glycol which may be in a water-containing state and a thiazoline derivative represented by the following chemical formula 2, and one or more of the thiazoline derivatives are added. To stabilize ethylene glycol against oxidation.
（ただし、Ｒ1〜R4は独立して水素、Ｃ1〜Ｃ4のアルキル基を表す。） (Wherein, R 1 to R 4 are independently represents hydrogen, an alkyl group of C 1 ~C 4.)
本発明のチアゾリン誘導体には２−メルカプトチアゾリン、２−メルカプト−４−メチルチアゾリンが例示される。 Examples of the thiazoline derivative of the present invention include 2-mercaptothiazoline and 2-mercapto-4-methylthiazoline.
安定化されたエチレングリコール組成物中の、化２で表されるチアゾリン誘導体のエチレングリコールに対する添加量は、重量比で０．００１〜５％、好ましくは ０．０１〜２％、さらに好ましくは０．１〜１％である。この割合で当該チアゾリン誘導体を存在させたエチレングリコールは、空気酸化に対して極めて良好な抵抗性を示す。むろん、５％を越える添加量であっても、熱劣化を始め、空気酸化に対して極めて良好な抵抗性を示す。しかしながら、添加の費用を考慮すれば、上記の添加量程度が好ましい。 The added amount of the thiazoline derivative represented by Chemical formula 2 with respect to ethylene glycol in the stabilized ethylene glycol composition is 0.001 to 5% by weight, preferably 0.01 to 2%, more preferably 0. .1 to 1%. Ethylene glycol in which the thiazoline derivative is present at this ratio exhibits extremely good resistance to air oxidation. Of course, even if the addition amount exceeds 5%, thermal deterioration starts and extremely good resistance to air oxidation is exhibited. However, considering the cost of addition, the above addition amount is preferable.
エチレングリコールの自動酸化の機構は、過酸化物中間体を通じてアルデヒドを生じ、最終的にギ酸になると言われている。本発明の組成物は、エチレングリコールに化２で表されるチアゾリン誘導体を添加することにより調整されるものである。本発明を実施することにより、化２で示されるチアゾリン誘導体は、エチレングリコールの過酸化物生成を抑制するものと推定している。上記、化２に示される化合物は、金属用防錆剤や腐食抑制剤としては公知であるものの、エチレングリコールにおける酸化防止剤としての効果は知られていない。本発明は、この点に着目してなされたものであり、新規なエチレングリコールの安定化方法として極めて有用である。 The mechanism of ethylene glycol autoxidation is said to produce aldehydes through peroxide intermediates and eventually to formic acid. The composition of the present invention is prepared by adding a thiazoline derivative represented by Chemical Formula 2 to ethylene glycol. By carrying out the present invention, it is presumed that the thiazoline derivative represented by Chemical formula 2 suppresses the formation of ethylene glycol peroxide. Although the compound shown in Chemical Formula 2 is known as a metal rust inhibitor and corrosion inhibitor, its effect as an antioxidant in ethylene glycol is not known. The present invention has been made paying attention to this point, and is extremely useful as a novel method for stabilizing ethylene glycol.
以上説明したとおり、本発明にかかるエチレングリコールの安定化方法によれば、以下の効果を奏する。即ち、エチレングリコールに本発明にかかるチアゾリン誘導体を添加又は含有してなるエチレングリコールは、その酸化防止効果がきわめて良好となる。また、本発明は、エチレングリコールの、特に加熱時の、空気酸化防止方法として有効である。よって、本発明の安定化方法によれば、酸化防止効果の高いエチレングリコールを得ることができる。具体的には化学プラントの熱媒や冷媒、自動車エンジンの冷却液、不凍液などに適用が可能である。
As described above, the method for stabilizing ethylene glycol according to the present invention has the following effects. That is, ethylene glycol obtained by adding or containing the thiazoline derivative according to the present invention to ethylene glycol has a very good antioxidant effect. The present invention is also effective as a method for preventing air oxidation of ethylene glycol, particularly during heating. Therefore, according to the stabilization method of the present invention, ethylene glycol having a high antioxidant effect can be obtained. Specifically, the present invention can be applied to a heat medium and a refrigerant of a chemical plant, a coolant of an automobile engine, an antifreeze solution, and the like.
以下、本実施例を詳細に説明するが、これは代表的なものを示したものであり、本実施例によって本発明が限定されるものではない。
試験例１
空気酸化によるエチレングリコールの劣化試験を次の操作で行い、その結果を下記にまとめた。エチレングリコール５０ｇに、上記化２で表されるチアゾリン誘導体を重量比で所定量加えた。その後に酸化促進剤として銅粉を５ｇ加え、エアレーションしながら１００℃で３０日間経時変化させた。そしてガスクロマトグラフィーによりエチレングリコールの残存量を測定した。ただし、下記実施例において、化２記載のＲ2〜Ｒ4は それぞれ水素である。
Hereinafter, although a present Example is described in detail, this shows a typical thing and this invention is not limited by this Example.
Test example 1
The deterioration test of ethylene glycol by air oxidation was performed as follows, and the results are summarized below. A predetermined amount of the thiazoline derivative represented by the above chemical formula 2 was added to 50 g of ethylene glycol in a weight ratio. Thereafter, 5 g of copper powder was added as an oxidation accelerator, and the mixture was aged for 30 days at 100 ° C. while aeration. The residual amount of ethylene glycol was measured by gas chromatography. However, in the following Examples, R 2 to R 4 described in Chemical Formula 2 are each hydrogen.
Ｒ1 添加量（％） 残存率（％）
Ｈ ０．５ ９８．３
Ｈ １．０ ９９．２
ＣＨ3 ０．５ ９７．５
ＣＨ3 １．０ ９８．７
比較例 無添加 ７６．３
R 1 addition amount (%) Residual rate (%)
H 0.5 98.3
H 1.0 99.2
CH 3 0.5 97.5
CH 3 1.0 98.7
Comparative Example No addition 76.3
試験例２
空気酸化による含水エチレングリコールの劣化試験を次の操作で行い、その結果を下記にまとめた。エチレングリコール２５ｇと水２５ｇからなる溶液に、上記化２で表されるチアゾリン誘導体をそれぞれ０．１２５ｇ、０．２５ｇ（エチレングリコールに対して重量比で０．５％、１．０％）加えた。その後、試験例１と同様に酸化促進剤として銅粉を５ｇ加え、エアレーションしながら１００℃で３０日間経時変化させた。なお、試験中に蒸発する水は、毎日、試験開始の状態になるように補充した。３０日後、ガスクロマトグラフィーによりエチレングリコールの残存量を測定した。ただし、下記実施例において、化２記載のＲ1〜Ｒ4は それぞれ水素である。
Test example 2
The deterioration test of water-containing ethylene glycol by air oxidation was performed by the following operation, and the results are summarized below. 0.125 g and 0.25 g of the thiazoline derivative represented by the above chemical formula 2 were added to a solution consisting of 25 g of ethylene glycol and 25 g of water, respectively (0.5% and 1.0% by weight with respect to ethylene glycol). . Thereafter, 5 g of copper powder was added as an oxidation accelerator in the same manner as in Test Example 1, and the mixture was aged for 30 days at 100 ° C. with aeration. The water evaporated during the test was replenished every day so that the test was started. After 30 days, the residual amount of ethylene glycol was measured by gas chromatography. However, in the following Examples, R 1 to R 4 described in Chemical Formula 2 are each hydrogen.
添加量（％） 残存率（％）
０．５ ９６．７
１．０ ９８．３
比較例 無添加 ７６．３
Amount added (%) Residual rate (%)
0.5 96.7
1.0 98.3
Comparative Example No addition 76.3
試験例３
空気酸化による自動車用不凍液の劣化試験を次の操作で行い、その結果を下記にまとめた。自動車用不凍液の例として、以下の配合で不凍液の類似液を調製した。エチレングリコール８８ｇ、水３．５ｇ、セバシン酸３ｇ、安息香酸ナトリウム３ｇ、ベンゾトリアゾール０．２ｇ、トリルトリアゾール０．２ｇ、２−メルカプトベンゾチアゾールのナトリウム塩０．１ｇ、硝酸ナトリウム０．１ｇ、モリブデン酸ナトリウム０．１ｇ、水酸化カリウム１．８ｇ。以上からなる溶液に、上記化２で表されるチアゾリン誘導体をそれぞれ０．４４ｇ、０．８８ｇ（エチレングリコールに対して重量比で０．５％、１．０％）加えた。
Test example 3
Deterioration test of automobile antifreeze due to air oxidation was performed as follows, and the results are summarized below. As an example of an antifreeze for automobiles, an antifreeze similar liquid was prepared with the following composition. 88 g of ethylene glycol, 3.5 g of water, 3 g of sebacic acid, 3 g of sodium benzoate, 0.2 g of benzotriazole, 0.2 g of tolyltriazole, 0.1 g of sodium salt of 2-mercaptobenzothiazole, 0.1 g of sodium nitrate, molybdic acid Sodium 0.1g, potassium hydroxide 1.8g. 0.44 g and 0.88 g (0.5% and 1.0% by weight with respect to ethylene glycol) of the thiazoline derivative represented by the chemical formula 2 were added to the above solution.
その後、試験例２と同様に酸化促進剤として銅粉を１０ｇ加え、３０日間経時変化させた。なお、試験中に蒸発する水は、毎日、試験開始の状態になるように補充した。３０日後、ガスクロマトグラフィーによりエチレングリコールの残存量を測定した。ただし、下記実施例において、化２記載のＲ1〜Ｒ4は それぞれ水素である。 Thereafter, 10 g of copper powder was added as an oxidation accelerator in the same manner as in Test Example 2, and the time was changed for 30 days. The water evaporated during the test was replenished every day so that the test was started. After 30 days, the residual amount of ethylene glycol was measured by gas chromatography. However, in the following Examples, R 1 to R 4 described in Chemical Formula 2 are each hydrogen.
添加量（％） 残存率（％）
０．５ ９８．５
１．０ ９９．４
比較例 無添加 ８３．７
Amount added (%) Residual rate (%)
0.5 98.5
1.0 99.4
Comparative Example No addition 83.7
Claims (9)
（ただし、Ｒ1〜R4は独立して水素、Ｃ1〜Ｃ4のアルキル基を表す。） A method for stabilizing ethylene glycol, comprising adding one or more thiazoline derivatives represented by Chemical Formula 1 to ethylene glycol.
(Wherein, R 1 to R 4 are independently represents hydrogen, an alkyl group of C 1 ~C 4.)
The method for stabilizing ethylene glycol according to any one of claims 1 to 7, wherein the object of stabilization is prevention of thermal degradation and / or prevention of air oxidation.
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|---|---|---|---|
| JP2006345702A JP5448018B2 (en) | 2006-12-22 | 2006-12-22 | Method for preventing ethylene glycol oxidation |
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| JP2006345702A JP5448018B2 (en) | 2006-12-22 | 2006-12-22 | Method for preventing ethylene glycol oxidation |
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| JP2008156263A5 JP2008156263A5 (en) | 2010-02-12 |
| JP5448018B2 JP5448018B2 (en) | 2014-03-19 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014167985A1 (en) | 2013-04-11 | 2014-10-16 | 大阪有機化学工業株式会社 | 1,2-alkane polyol-containing composition |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53108909A (en) * | 1977-03-01 | 1978-09-22 | Mitsui Petrochem Ind Ltd | Purification of ethylene glycol |
| JPS5783550A (en) * | 1980-11-12 | 1982-05-25 | Matsushita Electric Ind Co Ltd | High polymeric temperature-sensitive material |
| JPH01163142A (en) * | 1987-12-21 | 1989-06-27 | Mitsui Toatsu Chem Inc | Production of high-purity monoethylene glycol |
| EP0352120B1 (en) * | 1988-07-20 | 1992-04-08 | The British Petroleum Company p.l.c. | Antifreeze agent for liquid coolants |
| JPH0625655A (en) * | 1992-03-09 | 1994-02-01 | Showa Kk | Method for regeneration of brine and equipment therefor |
| JPH07278100A (en) * | 1994-04-04 | 1995-10-24 | Sanshin Chem Ind Co Ltd | Method for producing 2-aminothiophenols |
| JPH09227425A (en) * | 1996-02-15 | 1997-09-02 | Sanshin Chem Ind Co Ltd | Stabilization of ethylene glycol |
| JP2007502870A (en) * | 2003-08-15 | 2007-02-15 | ケムチュア コーポレイション | Reaction products of mercaptobenzothiazole, mercaptothiazoline and mercaptobenzimidazole with epoxides as lubricant additives |
-
2006
- 2006-12-22 JP JP2006345702A patent/JP5448018B2/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53108909A (en) * | 1977-03-01 | 1978-09-22 | Mitsui Petrochem Ind Ltd | Purification of ethylene glycol |
| JPS5783550A (en) * | 1980-11-12 | 1982-05-25 | Matsushita Electric Ind Co Ltd | High polymeric temperature-sensitive material |
| JPH01163142A (en) * | 1987-12-21 | 1989-06-27 | Mitsui Toatsu Chem Inc | Production of high-purity monoethylene glycol |
| EP0352120B1 (en) * | 1988-07-20 | 1992-04-08 | The British Petroleum Company p.l.c. | Antifreeze agent for liquid coolants |
| JPH0625655A (en) * | 1992-03-09 | 1994-02-01 | Showa Kk | Method for regeneration of brine and equipment therefor |
| JPH07278100A (en) * | 1994-04-04 | 1995-10-24 | Sanshin Chem Ind Co Ltd | Method for producing 2-aminothiophenols |
| JPH09227425A (en) * | 1996-02-15 | 1997-09-02 | Sanshin Chem Ind Co Ltd | Stabilization of ethylene glycol |
| JP2007502870A (en) * | 2003-08-15 | 2007-02-15 | ケムチュア コーポレイション | Reaction products of mercaptobenzothiazole, mercaptothiazoline and mercaptobenzimidazole with epoxides as lubricant additives |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014167985A1 (en) | 2013-04-11 | 2014-10-16 | 大阪有機化学工業株式会社 | 1,2-alkane polyol-containing composition |
| KR20150142679A (en) | 2013-04-11 | 2015-12-22 | 오사카 유키가가쿠고교 가부시키가이샤 | 1,2-alkane polyol-containing composition |
| US9795549B2 (en) | 2013-04-11 | 2017-10-24 | Osaka Organic Chemical Industry Ltd. | 1,2-alkane polyol-containing composition |
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