JP2007009173A - Process for producing aliphatic primary amine alkylene oxide adduct and emulsifier - Google Patents
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Abstract
【課題】反応時間が短く、かつ色調が良好で、例えば、乳化剤として用いた場合に良好な乳化性能を示す脂肪族第１級アミンアルキレンオキサイド付加物の製造方法、及びこれにより得られる脂肪族第１級アミンのアルキレンオキサイド付加物を含有する乳化剤の提供。
【解決手段】脂肪族第１級アミン１モルに対してアルキレンオキサイド０．５〜１．８モルを無触媒で付加させる無触媒付加工程と、該脂肪族第１級アミンに残部のアルキレンオキサイドをアルカリ触媒の存在下で付加させるアルカリ触媒下付加工程とを含むことを特徴とする脂肪族第１級アミンアルキレンオキサイド付加物の製造方法である。
【選択図】なし
A method for producing an aliphatic primary amine alkylene oxide adduct having a short reaction time and good color tone, for example, exhibiting good emulsification performance when used as an emulsifier, and an aliphatic compound obtained thereby. Providing an emulsifier containing an alkylene oxide adduct of a primary amine.
A non-catalytic addition step in which 0.5 to 1.8 mol of alkylene oxide is added without catalyst to 1 mol of an aliphatic primary amine, and the remaining alkylene oxide is added to the aliphatic primary amine. And an addition step in the presence of an alkali catalyst under an alkali catalyst. A method for producing an aliphatic primary amine alkylene oxide adduct.
[Selection figure] None
Description
本発明は、反応時間が短く、かつ色調が良好で、例えば、乳化剤として用いた場合に良好な乳化性能を示す脂肪族第１級アミンのアルキレンオキサイド付加物の製造方法、及びこれにより得られる脂肪族第１級アミンアルキレンオキサイド付加物を含有する乳化剤に関する。 The present invention relates to a method for producing an alkylene oxide adduct of an aliphatic primary amine that has a short reaction time and a good color tone, and exhibits good emulsifying performance when used as an emulsifier, and a fat obtained thereby. The present invention relates to an emulsifier containing an aromatic primary amine alkylene oxide adduct.
脂肪族第１級アミンのエチレンオキサイド付加体は、通常、脂肪族第１級アミンにアルカリ触媒、アミン触媒、金属触媒等の触媒を用いて、エチレンオキサイドを付加させて得られる（特許文献１参照）。しかし、反応当初から触媒を用いてエチレンオキサイドを付加反応させると、１モルのエチレンオキサイドが付加して２級アミンとなった後、２級アミンのままＯＨ基末端の付加反応が進行する。その結果、２級アミンのままエチレンオキサイド付加反応が進行した成分、及び３級アミンでエチレンオキサイド付加反応が進行した成分のそれぞれが幅広い付加モル分布を持ち、最終生成物の外観や形態が悪化する。また、乳化剤として用いた場合、乳化性能が不良となる。 An ethylene oxide adduct of an aliphatic primary amine is usually obtained by adding ethylene oxide to an aliphatic primary amine using a catalyst such as an alkali catalyst, an amine catalyst, or a metal catalyst (see Patent Document 1). ). However, when ethylene oxide is subjected to addition reaction using a catalyst from the beginning of the reaction, 1 mol of ethylene oxide is added to form a secondary amine, and then the addition reaction of the OH group terminal proceeds with the secondary amine remaining. As a result, each of the component in which the ethylene oxide addition reaction proceeds with the secondary amine and the component in which the ethylene oxide addition reaction proceeds with the tertiary amine each have a wide addition molar distribution, and the appearance and form of the final product deteriorate. . Moreover, when used as an emulsifier, the emulsification performance becomes poor.
無触媒でエチレンオキサイドを付加させて３級アミンの含有率を高める技術も提案されているが（特許文献２参照）、分岐構造をもつ３級アルキル基とアミンとが結合した、高度に分岐した脂肪族第１級アミンの場合、エチレンオキサイドの付加モル数が２モルに近づくにつれ付加反応が著しく遅くなり、製品色調が劣化するという問題や、反応時間が長時間を要して製造コストが高くなるという問題があった。色調の劣化に対しては、原料アミンを蒸留処理した後にエチレンオキサイドを付加する方法も提案されているが、工程数が増えることによりコストが高くなるという問題があった（特許文献３及び４参照）。更に、１００℃以下の低温でエチレンオキサイドを付加させることにより色調を改善する方法も提案されているが（特許文献５参照）、分岐構造をもつ３級アルキル基とアミンの結合した高度に分岐した脂肪族第１級アミンの場合、１００℃以下の低温ではエチレンオキサイド付加反応は非常に進行しにくいという問題があった。 A technology for increasing the content of tertiary amines by adding ethylene oxide without catalyst has also been proposed (see Patent Document 2), but a highly branched structure in which a tertiary alkyl group having a branched structure and an amine are combined. In the case of aliphatic primary amines, as the number of moles of ethylene oxide approaching 2 moles, the addition reaction becomes extremely slow and the product color tone deteriorates. There was a problem of becoming. For the deterioration of the color tone, a method of adding ethylene oxide after distillation of the raw material amine has also been proposed, but there is a problem that the cost increases due to an increase in the number of steps (see Patent Documents 3 and 4). ). Furthermore, although a method for improving the color tone by adding ethylene oxide at a low temperature of 100 ° C. or lower has been proposed (see Patent Document 5), it is highly branched in which a tertiary alkyl group having a branched structure and an amine are bonded. In the case of an aliphatic primary amine, there is a problem that the ethylene oxide addition reaction hardly proceeds at a low temperature of 100 ° C. or lower.
本発明は従来における前記問題を解決し、以下の目的を達成することを課題とする。
即ち、本発明は、反応時間が短く、かつ色調が良好で、例えば、乳化剤として用いた場合に良好な乳化性能を示す脂肪族第１級アミンアルキレンオキサイド付加物の製造方法、及びこれにより得られる脂肪族第１級アミンのアルキレンオキサイド付加物を含有する乳化剤を提供することを目的とする。
An object of the present invention is to solve the above-described problems and achieve the following objects.
That is, the present invention provides a method for producing an aliphatic primary amine alkylene oxide adduct having a short reaction time and good color tone, and exhibiting good emulsifying performance when used as an emulsifier, and the like. An object of the present invention is to provide an emulsifier containing an alkylene oxide adduct of an aliphatic primary amine.
前記課題を解決するための手段としては、以下の通りである。即ち、
＜１＞ 下記構造式（１）で表される脂肪族第１級アミン１モルに対してアルキレンオキサイド０．５〜１．８モルを無触媒で付加させる無触媒付加工程と、該脂肪族第１級アミンに残部のアルキレンオキサイドをアルカリ触媒の存在下で付加させるアルカリ触媒下付加工程とを含むことを特徴とする脂肪族第１級アミンアルキレンオキサイド付加物の製造方法である。
該＜１＞に記載の脂肪族第１級アミンアルキレンオキサイド付加物の製造方法によれば、分岐脂肪族第１級アミンのアルキレンオキサイドの付加に際し、まず該アルキレンオキサイドを無触媒で付加させることで３級アミンの含有率を高め、かつ、その付加を該アミン１モルに対して０．５〜１．８モルで止めることにより、反応時間が短く、かつ色調が良好で、例えば、乳化剤として用いた場合に良好な乳化性能を示す脂肪族第１級アミンアルキレンオキサイド付加物を得ることができる。
＜２＞ 無触媒工程で付加されるアルキレンオキサイドのモル数、及びアルカリ触媒下付加工程で付加させるアルキレンオキサイドのモル数の合計が、前記脂肪族第１級アミン１モルに対して２〜５０モルである前記＜１＞に記載の脂肪族第１級アミンアルキレンオキサイド付加物の製造方法である。
＜３＞ 無触媒工程で付加されるアルキレンオキサイドのモル数、及びアルカリ触媒下付加工程で付加させるアルキレンオキサイドのモル数の合計が、前記脂肪族第１級アミン１モルに対して３〜２０モルである前記＜１＞から＜２＞のいずれかに記載の脂肪族第１級アミンアルキレンオキサイド付加物の製造方法である。
＜４＞ アルキレンオキサイドがエチレンオキサイドである請求項１から３のいずれかに記載の脂肪族第１級アミンアルキレンオキサイド付加物の製造方法である。
Means for solving the problems are as follows. That is,
<1> Non-catalytic addition step in which 0.5 to 1.8 mol of alkylene oxide is added non-catalytically to 1 mol of an aliphatic primary amine represented by the following structural formula (1); And an addition step under an alkali catalyst in which the remaining alkylene oxide is added to a primary amine in the presence of an alkali catalyst. This is a method for producing an aliphatic primary amine alkylene oxide adduct.
According to the method for producing an aliphatic primary amine alkylene oxide adduct described in <1>, when adding an alkylene oxide of a branched aliphatic primary amine, first, the alkylene oxide is added without a catalyst. By increasing the content of the tertiary amine and stopping the addition at 0.5 to 1.8 mol per mol of the amine, the reaction time is short and the color tone is good, for example, as an emulsifier. An aliphatic primary amine alkylene oxide adduct exhibiting good emulsifying performance.
<2> The total number of moles of alkylene oxide added in the non-catalytic process and the number of moles of alkylene oxide added in the addition process under an alkali catalyst is 2 to 50 moles per mole of the aliphatic primary amine. It is a manufacturing method of the aliphatic primary amine alkylene oxide adduct as described in said <1> which is.
<3> The total number of moles of alkylene oxide added in the non-catalytic step and the number of moles of alkylene oxide added in the addition step under an alkali catalyst is 3 to 20 moles relative to 1 mole of the aliphatic primary amine. The method for producing an aliphatic primary amine alkylene oxide adduct according to any one of <1> to <2>.
<4> The method for producing an aliphatic primary amine alkylene oxide adduct according to any one of claims 1 to 3, wherein the alkylene oxide is ethylene oxide.
＜５＞ 前記＜１＞から＜４＞のいずれかに記載の脂肪族第１級アミンアルキレンオキサイド付加物の製造方法により得られた脂肪族第１級アミンアルキレンオキサイド付加物を含有することを特徴とする乳化剤である。
該＜５＞に記載の乳化剤は、本発明の脂肪族第１級アミンアルキレンオキサイド付加物の製造方法により得られた脂肪族第１級アミンアルキレンオキサイド付加物を含有するため、良好な乳化性能を示すことができる。
＜６＞ 金属加工油に用いられる前記＜５＞に記載の乳化剤である。
＜７＞ 金属加工油が金属圧延油である前記＜６＞に記載の乳化剤である。
＜８＞ 金属加工油が金属切削油である前記＜６＞に記載の乳化剤である。
<5> An aliphatic primary amine alkylene oxide adduct obtained by the method for producing an aliphatic primary amine alkylene oxide adduct according to any one of <1> to <4>. It is an emulsifier.
The emulsifier according to <5> contains an aliphatic primary amine alkylene oxide adduct obtained by the method for producing an aliphatic primary amine alkylene oxide adduct of the present invention, and therefore has good emulsification performance. Can show.
<6> The emulsifier according to <5>, which is used for metalworking oil.
<7> The emulsifier according to <6>, wherein the metal processing oil is a metal rolling oil.
<8> The emulsifier according to <6>, wherein the metal processing oil is a metal cutting oil.
＜９＞ 前記＜５＞に記載の乳化剤を含むことを特徴とする金属加工油である。
＜１０＞ 金属圧延油である前記＜９＞に記載の金属加工油である。
＜１１＞ 金属切削油である前記＜９＞に記載の金属加工油である。
<9> A metalworking oil comprising the emulsifier according to <5>.
<10> The metal working oil according to <9>, which is a metal rolling oil.
<11> The metal working oil according to <9>, which is a metal cutting oil.
本発明によると、反応時間が短く、かつ色調が良好で、例えば、乳化剤として用いた場合に良好な乳化性能を示す脂肪族第１級アミンアルキレンオキサイド付加物の製造方法、及びこれにより得られる脂肪族第１級アミンアルキレンオキサイド付加物を含有する乳化剤を提供することができる。 According to the present invention, the reaction time is short and the color tone is good, for example, a method for producing an aliphatic primary amine alkylene oxide adduct that exhibits good emulsifying performance when used as an emulsifier, and the fat obtained thereby An emulsifier containing a group primary amine alkylene oxide adduct can be provided.
（脂肪族第１級アミンアルキレンオキサイド付加物の製造方法）
本発明の脂肪族第１級アミンアルキレンオキサイド付加物の製造方法は、脂肪族第１級アミン１モルに対してアルキレンオキサイド０．５〜１．８モルを無触媒で付加させる無触媒付加工程と、該脂肪族第１級アミンに残部のアルキレンオキサイドをアルカリ触媒の存在下で付加させるアルカリ触媒下付加工程とを含み、更に必要に応じてその他の工程を含む。
(Method for producing an aliphatic primary amine alkylene oxide adduct)
The method for producing an aliphatic primary amine alkylene oxide adduct according to the present invention comprises a non-catalytic addition step in which 0.5 to 1.8 mol of alkylene oxide is added non-catalyst to 1 mol of an aliphatic primary amine. And an addition step under an alkali catalyst in which the remaining alkylene oxide is added to the aliphatic primary amine in the presence of an alkali catalyst, and further includes other steps as necessary.
−脂肪族第１級アミン−
前記脂肪族第１級アミンは、下記構造式（１）で表される。
-Aliphatic primary amine-
The aliphatic primary amine is represented by the following structural formula (1).
具体的には、ｎ-ペンチル、ｎ-オクチル、ｎ-ドデシル、ｎ-テトラデシル、ｎ-ヘキサデシル、ｎ-ステアリル、ｎ-オレイル、などが好適に挙げられる。
前記Ｒ２、Ｒ３は、いずれも炭素原子数が１〜５のアルキル基であることが必要であり、前記炭素原子数は１〜３であることが好ましい。前記炭素原子数が５を超えると立体障害が大きくなるためアミノ基へのアルキレンオキサイド付加反応が進行しにくくなる。
前記構造式（１）で表される脂肪族第１級アミンとしては、特に制限はなく、目的に応じて適宜選択することができるが、ターシャリーオクチルアミン、ターシャリードデシルアミン、ターシャリーステアリルアミン、などが好適に挙げられる。
Specific examples include n-pentyl, n-octyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-stearyl, and n-oleyl.
R 2 and R 3 both need to be alkyl groups having 1 to 5 carbon atoms, and the number of carbon atoms is preferably 1 to 3. When the number of carbon atoms exceeds 5, the steric hindrance increases, so that the alkylene oxide addition reaction to the amino group does not proceed easily.
The aliphatic primary amine represented by the structural formula (1) is not particularly limited and may be appropriately selected depending on the intended purpose. Tertiary octylamine, tertiary lead decylamine, tertiary stearylamine And the like.
−アルキレンオキサイド−
前記アルキレンオキサイドとしては、特に制限はなく、目的に応じて適宜選択することができ、例えば、エチレンオキサイド、プロピレンオキシド、ブチレンオキシド、などが挙げられる。これらは、１種単独で使用してもよいし、２種以上を組み合わせて使用してもよい。これらの中でもエチレンオキサイドが好ましい。
-Alkylene oxide-
There is no restriction | limiting in particular as said alkylene oxide, According to the objective, it can select suitably, For example, ethylene oxide, propylene oxide, butylene oxide, etc. are mentioned. These may be used individually by 1 type and may be used in combination of 2 or more type. Among these, ethylene oxide is preferable.
−アルカリ触媒−
前記アルカリ触媒としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム、水酸化マグネシウム、ナトリウム金属、などが挙げられる。これらの中でも、水酸化ナトリウム、水酸化カリウムが好ましい。
-Alkaline catalyst-
There is no restriction | limiting in particular as said alkali catalyst, According to the objective, it can select suitably, For example, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium metal etc. are mentioned. Among these, sodium hydroxide and potassium hydroxide are preferable.
−無触媒付加工程−
前記無触媒付加工程において、脂肪族第１級アミン１モルに付加させるアルキレンオキサイドの量は、上述のように、該脂肪族第１級アミン１モルに対してアルキレンオキサイド０．５〜１．８モルであることが必要であり、１．２〜１．８モルが好ましい。前記アルキレンオキサイドの量が０．５モル未満であると、最終的に得られた脂肪族第１級アミンアルキレンオキサイド付加物の外観や形態、乳化性能が劣るなど品質面で問題を生じる。前記アルキレンオキサイドの量が１．８モルを超えると、前記脂肪族第１級アミンに結合した分岐構造をもつ３級アルキル基の立体障害により付加反応速度が著しく遅くなり、製品色調の劣化が生じたり、反応時間が長時間を要して製造コストが高くなる弊害がある。
-Catalytic-free addition process-
In the noncatalytic addition step, the amount of alkylene oxide added to 1 mol of the aliphatic primary amine is 0.5 to 1.8 alkylene oxide per mol of the aliphatic primary amine as described above. It is necessary to be a mol, and 1.2 to 1.8 mol is preferable. When the amount of the alkylene oxide is less than 0.5 mol, there is a problem in quality such that the finally obtained aliphatic primary amine alkylene oxide adduct has poor appearance and form and poor emulsification performance. When the amount of the alkylene oxide exceeds 1.8 mol, the addition reaction rate is remarkably slowed by the steric hindrance of the tertiary alkyl group having a branched structure bonded to the aliphatic primary amine, resulting in deterioration of the product color tone. Or the reaction time takes a long time and the production cost increases.
前記無触媒付加工程において、脂肪族第１級アミン１モルにアルキレンオキサイドを付加させる方法としては、アルキレンオキサイドの量以外は特に制限はなく、目的に応じて適宜選択することができるが、該脂肪族第１級アミンをオートクレーブに仕込み、該オートクレーブの釜内を窒素で置換した後、攪拌しながら昇温して、アルキレンオキサイドを徐々に添加して系内に仕込みながら付加反応させることが好ましい。
前記昇温時の温度は、１００〜２００℃が好ましく、１２０〜１８０℃がより好ましい。
前記付加反応させる際の圧力は、特に制限はなく、常圧であってもよいし、加圧下であってもよいが、例えば、０．６ＭＰａ以下が好ましい。
In the non-catalyst addition step, the method of adding alkylene oxide to 1 mol of aliphatic primary amine is not particularly limited except the amount of alkylene oxide, and can be appropriately selected according to the purpose. It is preferable to add the group primary amine to the autoclave and replace the inside of the autoclave with nitrogen, then raise the temperature while stirring, and gradually add the alkylene oxide to carry out the addition reaction while charging the system.
100-200 degreeC is preferable and the temperature at the time of the said temperature rising has more preferable 120-180 degreeC.
The pressure at the time of the addition reaction is not particularly limited and may be normal pressure or under pressure, but for example, 0.6 MPa or less is preferable.
−アルカリ触媒下付加工程−
前記アルカリ触媒下付加工程において、脂肪族第１級アミンに付加させるアルキレンオキサイドの量は、特に制限はなく、目的に応じて適宜選択することができるが、前記無触媒工程で付加されるアルキレンオキサイドのモル数、及びアルカリ触媒下付加工程で付加させるアルキレンオキサイドのモル数の合計が、前記脂肪族第１級アミン１モルに対して２〜５０モルであることが好ましく、乳化性能とハンドリング性の両立の観点から、３〜２０モルであることがより好ましい。該モル数が２モル未満であると、乳化性能が十分に発現されないことがあり、５０モルを超えると、ハンドリング性が悪化してワックス状の固体になることがある。
-Addition step under alkali catalyst-
The amount of alkylene oxide added to the aliphatic primary amine in the addition step under the alkali catalyst is not particularly limited and may be appropriately selected depending on the intended purpose, but the alkylene oxide added in the non-catalytic step And the total number of moles of alkylene oxide to be added in the addition step under an alkali catalyst is preferably 2 to 50 moles per mole of the aliphatic primary amine. From the viewpoint of compatibility, it is more preferably 3 to 20 mol. When the number of moles is less than 2 moles, the emulsification performance may not be sufficiently exhibited, and when the number exceeds 50 moles, handling properties may be deteriorated to form a waxy solid.
前記アルカリ触媒下付加工程において、脂肪族第１級アミンにアルキレンオキサイドを付加させる方法としては、特に制限はなく、目的に応じて適宜選択することができるが、例えば、上述した無触媒付加工程の昇温時の温度により、所定時間熟成してから、冷却した後、アルカリ触媒を添加して、必要に応じて減圧脱水を行い、昇温して、アルキレンオキサイドを付加反応させることが好ましい。
前記熟成させる時間は、３０分〜２時間が好ましい。前記冷却した際の温度は、１００℃以下が好ましい。
前記アルカリ触媒の添加量は、特に制限はなく、目的に応じて適宜選択することができるが、前記脂肪族第１級アミン１モルに対して１００〜２，０００ｐｐｍが好ましい。
前記昇温時の温度は、１００〜２００℃が好ましく、１２０〜１８０℃がより好ましい。
In the addition step under the alkali catalyst, the method for adding the alkylene oxide to the aliphatic primary amine is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferable that after aging for a predetermined time depending on the temperature at the time of temperature increase, after cooling, an alkali catalyst is added, dehydration under reduced pressure is performed as necessary, the temperature is increased, and the alkylene oxide is subjected to an addition reaction.
The aging time is preferably 30 minutes to 2 hours. The cooling temperature is preferably 100 ° C. or lower.
There is no restriction | limiting in particular in the addition amount of the said alkali catalyst, Although it can select suitably according to the objective, 100-2,000 ppm is preferable with respect to 1 mol of said aliphatic primary amines.
100-200 degreeC is preferable and the temperature at the time of the said temperature rising has more preferable 120-180 degreeC.
−その他の工程−
本発明の脂肪族第１級アミンアルキレンオキサイド付加物の製造方法は、前記無触媒付加工程及びアルカリ触媒下付加工程以外に、必要に応じて適宜その他の工程を含んでいてもよい。
前記その他の工程としては、例えば、前記アルカリ触媒下付加工程における昇温時の温度で３０分〜２時間熟成した後、５０〜１００℃で未反応のアルキレンオキサイドを２〜２０ｋＰａの圧力で蒸留後、１００℃以下に冷却して付加させる工程などが挙げられる。
また、前記脂肪族第１級アミンアルキレンオキサイド付加物は、後処理として、例えば、酢酸、硫酸、等の酸による中和処理や、無機系吸着剤により吸着をした後、濾過を行う吸着濾過処理、などを行ってもよい。
前記無機系吸着剤としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、シリカ・アルミナ系吸着剤などが挙げられる。前記シリカ・アルミナ系吸着剤の、具体的な市販品としては、例えば、キヨーワードシリーズ（協和化学製）が好適に挙げられる。
また、本発明の効果を阻害しない範囲で酸化防止剤、抗菌剤等の添加剤を必要に応じて配合することもできる。
-Other processes-
The method for producing an aliphatic primary amine alkylene oxide adduct of the present invention may optionally include other steps as needed in addition to the non-catalyst addition step and the alkali-catalyzed addition step.
As said other process, for example, after aging 30 minutes-2 hours at the temperature at the time of temperature increase in the said addition process under an alkali catalyst, after distilling unreacted alkylene oxide at a pressure of 2-20 kPa at 50-100 degreeC. And a step of cooling to 100 ° C. or lower and the like.
The aliphatic primary amine alkylene oxide adduct is a post-treatment, for example, a neutralization treatment with an acid such as acetic acid or sulfuric acid, or an adsorption filtration treatment in which adsorption is performed with an inorganic adsorbent followed by filtration. , Etc. may be performed.
There is no restriction | limiting in particular as said inorganic type adsorption agent, According to the objective, it can select suitably, For example, a silica * alumina type adsorption agent etc. are mentioned. As a specific commercial product of the silica-alumina-based adsorbent, for example, Kyoward series (manufactured by Kyowa Chemical) is preferably mentioned.
In addition, additives such as antioxidants and antibacterial agents can be blended as necessary within a range not impairing the effects of the present invention.
−用途−
本発明の脂肪族第１級アミンアルキレンオキサイド付加物の製造方法は、反応時間が短く、また、得られる脂肪族第１級アミンアルキレンオキサイド付加物が、色調が良好で、かつ各種天然油・合成油と水との乳化性に優れるので、例えば、金属加工時の加工油用乳化剤等に好適に用いられ、中でも、圧延油用乳化剤、切削油用乳化剤に特に好適に用いられる。また、その他の工業用各種乳化剤、家庭品化粧品の各種乳化剤としても有用である。
-Application-
The production method of the aliphatic primary amine alkylene oxide adduct of the present invention has a short reaction time, the resulting aliphatic primary amine alkylene oxide adduct has a good color tone, and various natural oils and synthetics. Since it is excellent in emulsifying property between oil and water, it is preferably used, for example, as an emulsifier for processing oil during metal processing, and particularly preferably used as an emulsifier for rolling oil and an emulsifier for cutting oil. It is also useful as various industrial emulsifiers and various emulsifiers in household cosmetics.
以下、本発明の実施例について説明するが、本発明はこの実施例に何ら限定されるものではない。
（実施例１）
−脂肪族第１級アミンアルキレンオキサイド付加物の調製−
内容積４ｌのオートクレーブに、脂肪族第１級アミン（以下、単に「原料アミン」ともいう。）としての下記構造式（１）で表されるターシャリードデシルアミン（ローム＆ハース（株）製、プライメン８１−Ｒ、平均分子量１９０）１，６３０ｇを仕込み、窒素置換後、１６０℃まで昇温した。その後、同温度でエチレンオキサイド６３５ｇ（原料アミン１モルに対して１．６７モル）を圧力０．２〜０．５ＭＰａに保ちながら導入して無触媒でエチレンオキサイド付加反応を行なった（無触媒付加工程）。
Hereinafter, although the Example of this invention is described, this invention is not limited to this Example at all.
Example 1
-Preparation of aliphatic primary amine alkylene oxide adduct-
In an autoclave with an internal volume of 4 l, a tertiary lead decylamine (produced by Rohm & Haas Co., Ltd.) represented by the following structural formula (1) as an aliphatic primary amine (hereinafter also simply referred to as “raw material amine”), Primer 81-R, average molecular weight 190) 1,630 g were charged, and after nitrogen substitution, the temperature was raised to 160 ° C. Thereafter, 635 g of ethylene oxide (1.67 mol with respect to 1 mol of raw material amine) was introduced at the same temperature while maintaining the pressure at 0.2 to 0.5 MPa, and an ethylene oxide addition reaction was carried out without catalyst (no catalyst addition). Process).
エチレンオキサイドの導入終了後、前記無触媒付加工程の昇温時の温度で１時間熟成した後、６０℃に冷却した。次いで、アルカリ触媒としての３０％水酸化ナトリウム水溶液６ｇ（原料アミン１モルに対して５００ｐｐｍ）を添加した。窒素置換後、１１０℃まで昇温し、圧力３ｋＰａ以下に１時間保って水分を系内より除去した。次いで１６０℃まで昇温した後、エチレンオキサイド１，３３５ｇ（原料アミン１モルに対して３．５３モル)を圧力０．２〜０．５ＭＰａに保ちながら導入してエチレンオキサイド付加反応を行なった（アルカリ触媒下付加工程）。
エチレンオキサイドの導入終了後、同温度で３０分熟成した後、８０℃で未反応エチレンオキサイドを３ｋＰａの圧力で蒸留後、６０℃に冷却して付加させ、原料アミン１モル当たりエチレンオキサイド５．２モルの脂肪族第１級アミンエチレンオキサイド付加物３６００ｇを得た。
After completion of the introduction of ethylene oxide, the mixture was aged at the temperature at the time of temperature increase in the non-catalyst addition step, and then cooled to 60 ° C. Subsequently, 6 g of a 30% aqueous sodium hydroxide solution as an alkali catalyst (500 ppm relative to 1 mol of the raw material amine) was added. After nitrogen substitution, the temperature was raised to 110 ° C., and the pressure was kept at 3 kPa or less for 1 hour to remove moisture from the system. Subsequently, after heating up to 160 degreeC, ethylene oxide 1,335g (3.53 mol with respect to 1 mol of raw material amines) was introduce | transduced keeping the pressure 0.2-0.5 MPa, and ethylene oxide addition reaction was performed ( Addition step under alkali catalyst).
After completion of the introduction of ethylene oxide, after aging at the same temperature for 30 minutes, unreacted ethylene oxide was distilled at 80 ° C. at a pressure of 3 kPa and then added by cooling to 60 ° C. to give 5.2 ethylene oxide per mole of starting amine. 3600 g of a molar aliphatic primary amine ethylene oxide adduct was obtained.
（実施例２）
実施例１において、無触媒付加工程のエチレンオキサイド導入量を５１３ｇ（原料アミン１モルに対して１．３５モル）に、アルカリ触媒下付加工程のエチレンオキサイド導入量を５１６２ｇ（原料アミン１モルに対して１３．６５モル）にした以外は実施例１と同様にして、エチレンオキサイド付加反応を行ない、原料アミン１モル当たりエチレンオキサイド１５モルの脂肪族第１級アミンエチレンオキサイド付加物７，３０５ｇを得た。
(Example 2)
In Example 1, the amount of ethylene oxide introduced in the uncatalyzed addition step was 513 g (1.35 mol relative to 1 mol of raw material amine), and the amount of ethylene oxide introduced in the addition step under an alkali catalyst was 5162 g (per mol of raw material amine). The ethylene oxide addition reaction was carried out in the same manner as in Example 1 except that the total amount was 13.65 mol), to obtain 7,305 g of an aliphatic primary amine ethylene oxide adduct having 15 mol of ethylene oxide per mol of raw material amine. It was.
（実施例３）
実施例１において、無触媒付加工程のエチレンオキサイド導入量を６３５ｇ（原料アミン１モルに対して１．６７モル）に、アルカリ触媒下付加工程のエチレンオキサイド導入量を３８０ｇ（原料アミン１モルに対して１モル）にした以外は実施例１と同様にして、エチレンオキサイド付加反応を行ない、原料アミン１モル当たりエチレンオキサイド２．６７モルの脂肪族第１級アミンエチレンオキサイド付加物２，６４５ｇを得た。
(Example 3)
In Example 1, the amount of ethylene oxide introduced in the non-catalyst addition step was 635 g (1.67 mol relative to 1 mol of raw material amine), and the amount of ethylene oxide introduced in the addition step under an alkali catalyst was 380 g (per mol of raw material amine). The ethylene oxide addition reaction was carried out in the same manner as in Example 1 except that it was changed to 1 mol) to obtain 2.645 g of an aliphatic primary amine ethylene oxide adduct having 2.67 mol of ethylene oxide per mol of the raw material amine. It was.
（実施例４）
実施例１において、無触媒付加工程のエチレンオキサイド導入量を６３５ｇ（原料アミン１モルに対して１．６７モル）に、アルカリ触媒下付加工程のエチレンオキサイド導入量を１０，７７２ｇ（原料アミン１モルに対して２８．３３モル）にした以外は実施例１と同様にして、エチレンオキサイド付加反応を行ない、原料アミン１モル当たりエチレンオキサイド３０モルの脂肪族第１級アミンエチレンオキサイド付加物１３，０３７ｇを得た。
Example 4
In Example 1, the amount of ethylene oxide introduced in the non-catalyst addition step was 635 g (1.67 mol relative to 1 mol of raw material amine), and the amount of ethylene oxide introduced in the addition step under an alkali catalyst was 10,772 g (1 mol of raw material amine). In the same manner as in Example 1 except that the amount was 28.33 mol), an ethylene oxide addition reaction was carried out to produce 13,037 g of an aliphatic primary amine ethylene oxide adduct of 30 mol of ethylene oxide per mol of raw material amine. Got.
（実施例５）
実施例１において、無触媒付加工程のエチレンオキサイド導入量を６３５ｇ（原料アミン１モルに対して１．６７モル）に、アルカリ触媒下付加工程のエチレンオキサイド導入量を５０ｇ（原料アミン１モルに対して０．１３モル）にした以外は実施例１と同様にして、エチレンオキサイド付加反応を行ない、原料アミン１モル当たりエチレンオキサイド１．８モルの脂肪族第１級アミンエチレンオキサイド付加物２，３１５ｇを得た。
(Example 5)
In Example 1, the amount of ethylene oxide introduced in the catalyst-free addition step was 635 g (1.67 mol relative to 1 mol of raw material amine), and the amount of ethylene oxide introduced in the addition step under an alkali catalyst was 50 g (per mol of raw material amine). The ethylene oxide addition reaction was carried out in the same manner as in Example 1 except that the amount was 0.13 mol), and 2,315 g of an aliphatic primary amine ethylene oxide adduct of 1.8 mol of ethylene oxide per mol of raw material amine was used. Got.
（実施例６）
実施例１において、無触媒付加工程のエチレンオキサイド導入量を６３５ｇ（原料アミン１モルに対して１．６７モル）に、アルカリ触媒下付加工程のエチレンオキサイド導入量を２２，１７９ｇ（原料アミン１モルに対して５８．３３モル）にした以外は実施例１と同様にして、エチレンオキサイド付加反応を行ない、原料アミン１モル当たりエチレンオキサイド６０モルの脂肪族第１級アミンエチレンオキサイド付加物２４，４４４ｇを得た。
(Example 6)
In Example 1, the amount of ethylene oxide introduced in the catalyst-free addition step was 635 g (1.67 mol relative to 1 mol of raw material amine), and the amount of ethylene oxide introduced in the addition step under an alkali catalyst was 22,179 g (1 mol of raw material amine). The ethylene oxide addition reaction was carried out in the same manner as in Example 1 except that the amount was 58.33 mol), and 24,444 g of an aliphatic primary amine ethylene oxide adduct having 60 mol of ethylene oxide per mol of raw material amine was used. Got.
（実施例７）
実施例１において、アルキレンオキサイドとして、エチレンオキサイドの代わりに、プロピレンオキサイドを使用し、該プロピレンオキサイドを、無触媒付加工程において８３７ｇ導入（原料アミン１モルに対して１．６７モル）し、更に、アルカリ触媒下付加工程において１，７６０ｇ（原料アミン１モルに対して３．５３モル）導入した以外は実施例１と同様にして、プロピレンオキサイド付加反応を行ない、原料アミン１モル当たりプロピレンオキサイド５．２モルの脂肪族第１級アミンプロピレンオキサイド付加物４，２２７ｇを得た。
(Example 7)
In Example 1, propylene oxide was used as alkylene oxide instead of ethylene oxide, and 837 g of the propylene oxide was introduced in the catalyst-free addition step (1.67 mol with respect to 1 mol of the raw material amine). A propylene oxide addition reaction was carried out in the same manner as in Example 1 except that 1,760 g (3.53 mol with respect to 1 mol of raw material amine) was introduced in the addition step under an alkali catalyst. As a result, 4,227 g of 2 mol of aliphatic primary amine propylene oxide adduct was obtained.
（比較例１）
実施例１において、無触媒付加工程を行わず、かつエチレンオキサイド導入量を１，９７０ｇ（原料アミン１モルに対して５．２モル）にした以外は、実施例１と同様にして、エチレンオキサイド付加反応を行ない、原料アミン１モル当たりエチレンオキサイド５．２モルの脂肪族第１級アミンエチレンオキサイド付加物３，６００ｇを得た。
(Comparative Example 1)
In Example 1, ethylene oxide was obtained in the same manner as in Example 1 except that the catalyst-free addition step was not performed and the amount of ethylene oxide introduced was 1,970 g (5.2 moles per mole of raw material amine). The addition reaction was performed to obtain 3,600 g of an aliphatic primary amine ethylene oxide adduct of 5.2 mol of ethylene oxide per 1 mol of the raw material amine.
（比較例２）
実施例１において、無触媒付加工程のエチレンオキサイド導入量を１１３ｇ（原料アミン１モルに対して０．３モル)に、アルカリ触媒下付加工程のエチレンオキサイド導入量を１，８５７ｇ（原料アミン１モルに対して４．９モル）にした以外は実施例１と同様にして、エチレンオキサイド付加反応を行ない、原料アミン１モル当たりエチレンオキサイド５．２モルの脂肪族第１級アミンエチレンオキサイド付加物３，６００ｇを得た。
(Comparative Example 2)
In Example 1, the amount of ethylene oxide introduced in the catalyst-free addition step was 113 g (0.3 mol relative to 1 mol of raw material amine), and the amount of ethylene oxide introduced in the addition step under an alkali catalyst was 1,857 g (1 mol of raw material amine). The reaction was conducted in the same manner as in Example 1 except that the amount was changed to 4.9 mol), and an aliphatic primary amine ethylene oxide adduct 3 of 5.2 mol of ethylene oxide per 1 mol of the raw material amine was conducted. , 600 g was obtained.
（比較例３）
実施例１において、無触媒付加工程のエチレンオキサイド導入量を７５０ｇ（原料アミン１モルに対して１．９６モル）に、アルカリ触媒下付加工程のエチレンオキサイド導入量を１，９４５ｇ（原料アミン１モルに対して５．０４モル）にした以外は実施例１と同様にして、エチレンオキサイド付加反応を行ない、原料アミン１モル当たりエチレンオキサイド７モルの脂肪族第１級アミンエチレンオキサイド付加物４，３２５ｇを得た。
(Comparative Example 3)
In Example 1, the introduction amount of ethylene oxide in the non-catalyst addition step was 750 g (1.96 mol with respect to 1 mol of raw material amine), and the amount of ethylene oxide introduction in the addition step under alkali catalyst was 1,945 g (1 mol of raw material amine). The ethylene oxide addition reaction was carried out in the same manner as in Example 1 except that the amount was 5.04 mol), and 4,325 g of an aliphatic primary amine ethylene oxide adduct of 7 mol of ethylene oxide per 1 mol of the raw material amine. Got.
〔評価〕
実施例１〜７及び比較例１〜３の、脂肪族第１級アミンエチレンオキサイド付加物又は脂肪族第１級プロピレンオキサイド付加物（以下、アルキレンオキサイド付加物ともいう。）について、無触媒付加工程及びアルカリ触媒下付加工程で要した時間（反応所要時間）を測定すると共に、以下に示す方法で、各例で得られた脂肪族第１級アミンエチレンオキサイド付加物の乳化性及び色調を評価した。その結果を表１に示す。
[Evaluation]
About the aliphatic primary amine ethylene oxide adduct or the aliphatic primary propylene oxide adduct (hereinafter also referred to as alkylene oxide adduct) of Examples 1 to 7 and Comparative Examples 1 to 3, a non-catalytic addition step In addition, the time required for the addition step under an alkali catalyst (required reaction time) was measured, and the emulsifiability and color tone of the aliphatic primary amine ethylene oxide adduct obtained in each example were evaluated by the following methods. . The results are shown in Table 1.
＜乳化性の評価方法＞
−圧延油乳化性−
各実施例及び比較例で得られたアルキレンオキサイド付加物を１ｍｌ、水９３ｍｌ、及びトリメチロールプロパントリカプリレート（ライオン（株）製、加工油ルビノールＦ−３１０Ｎ）６ｍｌを１００ｍｌトールビーカー内に配合した。ホモミキサーに取りつけたタービン羽にてこの液を５００ｒｐｍで３分間攪拌した。攪拌後、混合液を２４時間静置し、外観を観察した。該外観は、白濁した乳化層が底部に生成した状態を乳化状態とみなし、「◎：均一な乳化状態」、「○：上層部に一部、不均一な箇所がある乳化状態」、「×：２層が分離し、乳化していない状態」の３段階に分けて評価を行った。
<Emulsifying evaluation method>
-Rolling oil emulsification-
1 ml of the alkylene oxide adduct obtained in each Example and Comparative Example, 93 ml of water, and 6 ml of trimethylolpropane tricaprylate (manufactured by Lion Corporation, processed oil rubinol F-310N) were blended in a 100 ml tall beaker. . This liquid was stirred at 500 rpm for 3 minutes with a turbine blade attached to a homomixer. After stirring, the mixture was allowed to stand for 24 hours and the appearance was observed. As for the appearance, a state in which a cloudy emulsified layer is formed at the bottom is regarded as an emulsified state, and “◎: uniform emulsified state”, “◯: emulsified state having a part of the upper layer part and uneven portions”, “× : Two layers were separated and evaluated without being emulsified.
−切削油乳化性−
ＪＩＳＫ２２４１に基づき調製した硬水（塩化カルシウム２水塩０．７５７ｇを蒸留水１Ｌに溶解させた水）に、流動性パラフィン（関東化学製）と、各実施例及び比較例で得られたアルキレンオキサイド付加物とを、各１質量％ずつ配合し、混合液１００ｍｌを、１００ｍｌトールビーカー内に調製した。得られた混合液を、ホモミキサーに取りつけたタービン羽にて、５００ｒｐｍで３分間、攪拌した。攪拌後、混合液を２４時間静置して、ビーカーの背後に印刷物を置いた時の混合液の透明性を観察し、下記の３段階に分けて評価を行った。
「◎：印刷物の文字が判読できる」
「○：印刷物の文字は判読できないが、色は判断できる」
「×：乳白色に濁り、印刷物が全く見えない」
-Cutting oil emulsification-
Addition of fluid paraffin (manufactured by Kanto Chemical) and alkylene oxide obtained in each of Examples and Comparative Examples to hard water (water in which 0.757 g of calcium chloride dihydrate was dissolved in 1 L of distilled water) prepared based on JISK2241 1% by mass of each product, and 100 ml of the mixed solution was prepared in a 100 ml tall beaker. The obtained mixed liquid was stirred at 500 rpm for 3 minutes with a turbine blade attached to a homomixer. After stirring, the mixed solution was allowed to stand for 24 hours, and the transparency of the mixed solution was observed when the printed material was placed behind the beaker, and evaluation was performed in the following three stages.
“◎: The characters on the printed material can be read”
“○: The letters on the printed material cannot be read, but the color can be determined.”
"X: Milky white and turbid, no printed material visible"
＜色調の評価方法＞
各例で得られたアルキレンオキサイド付加物の試料をガードナー・ホルト試料管（内径１０．６５ｍｍ、外径１２．３ｍｍ、長さ１１４ｍｍの平底硬質ガラス管）に入れ、測定用器具にセットして、試料と標準色を比較し、試料に最も近似したガードナー標準色番号を色調の値とする、いわゆるガードナー・ヘーリゲ法により、２０℃における色調（Ｇ／Ｈ）を評価した。
<Evaluation method of color tone>
Put the sample of alkylene oxide adduct obtained in each example into a Gardner-Holt sample tube (inner diameter 10.65 mm, outer diameter 12.3 mm, length 114 mm flat bottom hard glass tube), set in a measuring instrument, The sample and the standard color were compared, and the color tone (G / H) at 20 ° C. was evaluated by the so-called Gardner-Heligue method in which the Gardner standard color number closest to the sample was used as the color value.
表１から明らかなように、本発明の製造方法によって製造された実施例１〜７の脂肪族第１級アミンエチレンオキサイド付加物は、比較例１〜３の脂肪族第１級アミンエチレンオキサイド付加物に比して、短い反応時間で、良好な色調、及び良好な乳化性が得られた。特に、無触媒工程で付加されるエチレンオキサイドのモル数、及びアルカリ触媒下付加工程で付加させるエチレンオキサイドのモル数の合計が、前記脂肪族第１級アミン１モルに対して３〜２０モルである実施例１及び２では非常に優れた乳化性が得られた。
本発明の製造方法により、乳化性能が良好となる原因は定かではないが、実施例１〜６では、無触媒付加工程のエチレンオキサイド付加において、アミンの２個の水素にエチレンオキサイドが各々１モルずつ付加した３級アミンが大部分を占めるため、アルカリ触媒下付加工程のエチレンオキサイド付加において、この３級アミンの末端の、２つのオキシエチレン基の水酸基にほぼ均等に付加した構造の化合物が得られ、良好な乳化性能を示すものと思われる。一方、比較例１及び２では、２級アミンのままエチレンオキサイド付加反応が進行した成分が多く生成したものと考えられ、その結果、最終生成物はワックス状の固体となった。また、比較例３の場合は、無触媒付加工程のエチレンオキサイド導入量が１.９６モルと多いため、無触媒付加工程において付加反応を完結するのに要する時間が長すぎてしまい、乳化性能は良好であるが色調が劣化してしまう結果となった。
As is clear from Table 1, the aliphatic primary amine ethylene oxide adducts of Examples 1 to 7 produced by the production method of the present invention were the aliphatic primary amine ethylene oxide additions of Comparative Examples 1 to 3. Good color tone and good emulsifiability were obtained in a short reaction time as compared with the product. In particular, the total number of moles of ethylene oxide added in the non-catalytic step and the number of moles of ethylene oxide added in the addition step under the alkali catalyst is 3 to 20 moles per mole of the aliphatic primary amine. In some Examples 1 and 2, a very good emulsifying property was obtained.
The reason why the emulsification performance is improved by the production method of the present invention is not clear, but in Examples 1 to 6, in the addition of ethylene oxide in the catalyst-free addition step, 1 mol of ethylene oxide is added to each of two hydrogens of the amine. Since the added tertiary amine occupies the majority, ethylene oxide addition in the addition step under an alkali catalyst gives a compound having a structure in which the tertiary amine ends are added almost equally to the hydroxyl groups of the two oxyethylene groups. And seems to show good emulsification performance. On the other hand, in Comparative Examples 1 and 2, it was considered that many components in which the ethylene oxide addition reaction proceeded as a secondary amine were produced, and as a result, the final product became a waxy solid. In the case of Comparative Example 3, the amount of ethylene oxide introduced in the non-catalyst addition step is as large as 1.96 mol, so that the time required to complete the addition reaction in the non-catalyst addition step is too long, and the emulsification performance is Although it was good, the color tone was deteriorated.
本発明の脂肪族第１級アミンアルキレンオキサイド付加物の製造方法は、反応時間が短く、また、得られる脂肪族第１級アミンアルキレンオキサイド付加物が、色調が良好で、かつ各種天然油・合成油と水との乳化性に優れるので、例えば、金属加工時の加工油用乳化剤等に好適に用いられ、中でも、圧延油用乳化剤、切削油用乳化剤に特に好適に用いられる。また、その他の工業用各種乳化剤、家庭品化粧品の各種乳化剤としても有用である。
The production method of the aliphatic primary amine alkylene oxide adduct of the present invention has a short reaction time, the resulting aliphatic primary amine alkylene oxide adduct has a good color tone, and various natural oils and synthetics. Since it is excellent in emulsifying property between oil and water, it is preferably used, for example, as an emulsifier for processing oil during metal processing, and particularly preferably used as an emulsifier for rolling oil and an emulsifier for cutting oil. It is also useful as various industrial emulsifiers and various emulsifiers in household cosmetics.
Claims (8)
The emulsifier according to claim 6, wherein the metal working oil is a metal cutting oil.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007262251A (en) * | 2006-03-29 | 2007-10-11 | Sanyo Chem Ind Ltd | Method for producing aliphatic amine-alkylene oxide adduct |
| JP2007262250A (en) * | 2006-03-29 | 2007-10-11 | Sanyo Chem Ind Ltd | Method for producing aliphatic amine-alkylene oxide adduct |
| JP2008013465A (en) * | 2006-07-04 | 2008-01-24 | Sanyo Chem Ind Ltd | Manufacturing method of aliphatic amine alkylene oxide adduct |
| JP2010168348A (en) * | 2008-12-26 | 2010-08-05 | Sanyo Chem Ind Ltd | Method for producing aliphatic amine alkylene oxide adduct |
| JP2013181000A (en) * | 2012-03-02 | 2013-09-12 | Matsumoto Yushi Seiyaku Co Ltd | Aliphatic amine alkylene oxide adduct and method for producing the same |
| CN116731306A (en) * | 2023-06-14 | 2023-09-12 | 深圳飞扬骏研新材料股份有限公司 | Secondary amine resin and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2809159A (en) * | 1954-11-18 | 1957-10-08 | Dexter Chemical Corp | Antistatic and rewetting treatment of textile material |
| JPS58147566A (en) * | 1982-02-24 | 1983-09-02 | Kurita Water Ind Ltd | Steam-based corrosion inhibitor composition |
| JPH05179074A (en) * | 1991-12-26 | 1993-07-20 | Lion Corp | Antistatic polyolefin resin composition for molding |
| JPH11228509A (en) * | 1998-02-10 | 1999-08-24 | Kao Corp | Method for producing primary amine derivative |
| JP2000044505A (en) * | 1998-07-30 | 2000-02-15 | Asahi Denka Kogyo Kk | Polyether and method for producing the same |
| JP2003096186A (en) * | 2001-09-27 | 2003-04-03 | Nof Corp | Method for producing aliphatic primary amine alkylene oxide adduct |
| WO2004076529A1 (en) * | 2003-02-21 | 2004-09-10 | Bayer Materialscience Llc | Amine-initiated polyether polyols and a process for their production |
-
2005
- 2005-12-21 JP JP2005368222A patent/JP4813894B2/en not_active Expired - Lifetime
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2809159A (en) * | 1954-11-18 | 1957-10-08 | Dexter Chemical Corp | Antistatic and rewetting treatment of textile material |
| JPS58147566A (en) * | 1982-02-24 | 1983-09-02 | Kurita Water Ind Ltd | Steam-based corrosion inhibitor composition |
| JPH05179074A (en) * | 1991-12-26 | 1993-07-20 | Lion Corp | Antistatic polyolefin resin composition for molding |
| JPH11228509A (en) * | 1998-02-10 | 1999-08-24 | Kao Corp | Method for producing primary amine derivative |
| JP2000044505A (en) * | 1998-07-30 | 2000-02-15 | Asahi Denka Kogyo Kk | Polyether and method for producing the same |
| JP2003096186A (en) * | 2001-09-27 | 2003-04-03 | Nof Corp | Method for producing aliphatic primary amine alkylene oxide adduct |
| WO2004076529A1 (en) * | 2003-02-21 | 2004-09-10 | Bayer Materialscience Llc | Amine-initiated polyether polyols and a process for their production |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007262251A (en) * | 2006-03-29 | 2007-10-11 | Sanyo Chem Ind Ltd | Method for producing aliphatic amine-alkylene oxide adduct |
| JP2007262250A (en) * | 2006-03-29 | 2007-10-11 | Sanyo Chem Ind Ltd | Method for producing aliphatic amine-alkylene oxide adduct |
| JP2008013465A (en) * | 2006-07-04 | 2008-01-24 | Sanyo Chem Ind Ltd | Manufacturing method of aliphatic amine alkylene oxide adduct |
| JP2010168348A (en) * | 2008-12-26 | 2010-08-05 | Sanyo Chem Ind Ltd | Method for producing aliphatic amine alkylene oxide adduct |
| JP2013181000A (en) * | 2012-03-02 | 2013-09-12 | Matsumoto Yushi Seiyaku Co Ltd | Aliphatic amine alkylene oxide adduct and method for producing the same |
| CN116731306A (en) * | 2023-06-14 | 2023-09-12 | 深圳飞扬骏研新材料股份有限公司 | Secondary amine resin and preparation method and application thereof |
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