JP2009091530A - Freezing-point depressant for straight-chain alcohol - Google Patents
Freezing-point depressant for straight-chain alcohol Download PDFInfo
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 230000000994 depressogenic effect Effects 0.000 title claims abstract description 24
- 230000008014 freezing Effects 0.000 claims abstract description 52
- 238000007710 freezing Methods 0.000 claims abstract description 52
- 239000000203 mixture Substances 0.000 claims abstract description 52
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- -1 ethyleneoxy group Chemical group 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims description 18
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 description 16
- 239000002994 raw material Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- 239000004094 surface-active agent Substances 0.000 description 9
- 239000002736 nonionic surfactant Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000003945 anionic surfactant Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000003240 coconut oil Substances 0.000 description 6
- 235000019864 coconut oil Nutrition 0.000 description 6
- 239000003925 fat Substances 0.000 description 5
- 235000019197 fats Nutrition 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 239000000701 coagulant Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 241000894007 species Species 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 235000019482 Palm oil Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229930182478 glucoside Natural products 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本発明は、直鎖アルコールの凝固点降下剤及び凝固点を降下させた直鎖アルコール含有組成物に関する。 The present invention relates to a linear alcohol freezing point depressant and a linear alcohol-containing composition having a reduced freezing point.
各種の非イオン性界面活性剤や陰イオン性界面活性剤として、工業的に石化原料由来のアルコール又は油脂原料由来のアルコールから誘導されたものが知られている。 As various nonionic surfactants and anionic surfactants, those industrially derived from alcohols derived from petrochemical raw materials or alcohols derived from fat and oil raw materials are known.
いわゆる合成アルコールと呼ばれている石化原料由来のアルコールは、通常、エチレンを経由してオリゴメリゼーション化反応により内部オレフィンを有する化合物に誘導された後に、オキソ反応によりアルコールに誘導される。その結果得られた合成アルコールは、約８０重量％の直鎖アルコールの他に、２０重量％の分岐アルコールを含む混合物となることが知られている。合成アルコールから誘導された各種の非イオン性界面活性剤や陰イオン性界面活性剤は、直鎖アルコールからの誘導体に比べて、低融点、低凝固点であることから、低温安定性に優れるといった特徴を有することが知られている。 Alcohol derived from a petrochemical raw material called so-called synthetic alcohol is usually derived into a compound having an internal olefin through an oligomerization reaction via ethylene and then into an alcohol through an oxo reaction. The resultant synthetic alcohol is known to be a mixture containing 20% by weight of branched alcohol in addition to about 80% by weight of linear alcohol. Various nonionic surfactants and anionic surfactants derived from synthetic alcohols have a low melting point and a low freezing point compared to derivatives from linear alcohols. It is known to have
一方、天然アルコールの一種である油脂原料由来のアルコールから誘導された各種の非イオン性界面活性剤や陰イオン性界面活性剤は、合成アルコールからの誘導体に比べて、高起泡性、低ｃｍｃ、高曇点、高乳化力といった特徴を有することが知られている。 On the other hand, various nonionic surfactants and anionic surfactants derived from alcohols derived from fats and oils, which are a kind of natural alcohol, have higher foaming properties and lower cmc than derivatives derived from synthetic alcohols. It is known to have characteristics such as high cloud point and high emulsifying power.
また、アルコールそれ自体に着目した場合には、合成アルコール（分岐アルコールを含むアルコール組成物）は、低温安定性の点で天然アルコールよりも優れるものの、環境適合性の点で天然アルコールよりも劣る。一方、天然アルコールは、環境適合性の点で優れるものの、同じ分子量の合成アルコールと比較した場合、凝固点がやや高く、アルコールとしての取扱い性に劣るという課題があった。 Further, when focusing on the alcohol itself, the synthetic alcohol (alcohol composition containing a branched alcohol) is superior to natural alcohol in terms of low-temperature stability, but is inferior to natural alcohol in terms of environmental compatibility. On the other hand, natural alcohol is excellent in terms of environmental compatibility, but has a problem that it has a slightly higher freezing point and is inferior in handleability as alcohol when compared with synthetic alcohol having the same molecular weight.
また、直鎖アルコールの凝固点が合成アルコールに比較してやや高いということは、そのアルコール種から誘導される各種の界面活性剤等の誘導体を含む製品においても、低温時の保存安定性の点に少なからず悪影響を与える虞があった。 In addition, the freezing point of linear alcohols is somewhat higher than that of synthetic alcohols, even in products containing derivatives such as various surfactants derived from the alcohol species, because of low storage stability at low temperatures. There was a risk of adverse effects.
従って、天然アルコールの優れた性能を損なうことなく、合成アルコールの低温安定性を付与することができれば、目的・用途に応じてアルコール種を使い分けできることが大いに期待される。 Therefore, if the low temperature stability of the synthetic alcohol can be imparted without impairing the excellent performance of the natural alcohol, it is highly expected that the alcohol species can be selectively used according to the purpose and application.
そこで、本発明者等は、直鎖アルコール主体のアルコール組成物である天然アルコールの凝固点を低下させることができる、凝固点降下剤の探索を開始した。 Accordingly, the present inventors have started searching for freezing point depressants that can lower the freezing point of natural alcohol, which is an alcohol composition mainly composed of linear alcohol.
既存の凝固点降下剤としては、メタノール、エタノール、エチレングリコール、グリセリン等が知られている（特許文献１〜３）。しかしながら、これらの既知の凝固点降下剤は、水溶性を有する液体アルコールであるが故に、疎水性を有するアルコール、例えば炭素数６〜２２の直鎖アルコールに添加した場合には、その凝固点は降下するものの、アルコールそれ自体の界面活性剤としての特性、又は、これから誘導して得られる非イオン性界面活性剤や陰イオン性界面活性剤の特性が損なわれてしまう為に、そのままでは使用できない虞があった。 As existing freezing point depressants, methanol, ethanol, ethylene glycol, glycerin and the like are known (Patent Documents 1 to 3). However, since these known freezing point depressants are liquid alcohols having water solubility, their freezing point lowers when added to hydrophobic alcohols such as linear alcohols having 6 to 22 carbon atoms. However, since the properties of the alcohol itself as a surfactant or the properties of nonionic surfactants and anionic surfactants derived therefrom are impaired, there is a possibility that they cannot be used as they are. there were.
その上、メタノール、エタノールは長鎖アルコールよりも揮発性が高く、引火点が低く、取り扱いが困難となる。エチレングリコール、グリセリンは多価アルコールの為、水溶性が高く、長鎖アルコールと混合しても分離するため、好ましくない。
石化原料由来のアルコールと油脂原料由来のアルコールのそれぞれが有する有利な効果を併せ持つアルコール及びそれから誘導される各種の界面活性剤の開発を行う中で、直鎖アルコールの凝固点を降下させることができる凝固点降下剤が得られれば、石化原料由来のアルコールと油脂原料由来のアルコールのそれぞれが有する有利な効果を併せ持ったアルコール及びそれから誘導される各種の界面活性剤、アルコール非イオン性界面活性剤や陰イオン性界面活性剤等といった界面活性剤をはじめ各種製品の原料としての用途を拡大することができると考えられる。 Freezing point that can lower the freezing point of linear alcohol in the development of alcohols that have both advantageous effects of alcohols derived from petrochemical raw materials and alcohols derived from fat raw materials and various surfactants derived therefrom. If a depressant is obtained, an alcohol having the advantageous effects of both an alcohol derived from a petrochemical raw material and an alcohol derived from a fat and oil raw material, and various surfactants derived therefrom, alcohol nonionic surfactants and anions It is thought that the use as a raw material of various products including surfactants such as surfactants can be expanded.
本発明者等は、鋭意に検討を行った結果、驚くべきことに、天然アルコールのような直鎖型のアルコールに対して、特定のプロピレングリコールエチレングリコールモノ長鎖アルキルエーテル系化合物が凝固点降下作用をもたらし、当該化合物を含む直鎖アルコール含有組成物の物性や作用効果が合成アルコール組成物の物性や作用効果と同等か又はそれ以上に優れること、更にはその有利な効果が当該直鎖アルコール含有組成物から誘導した種々の製品（例えば非イオン性界面活性剤や陰イオン性界面活性剤）においても有利な作用効果を発現することを見出した。 As a result of intensive studies, the present inventors have surprisingly found that a specific propylene glycol ethylene glycol monolong chain alkyl ether compound has a freezing point lowering action on a linear alcohol such as natural alcohol. The physical properties and action effects of the linear alcohol-containing composition containing the compound are equal to or better than the physical properties and action effects of the synthetic alcohol composition. It has been found that advantageous effects are also exhibited in various products derived from the composition (for example, nonionic surfactants and anionic surfactants).
本発明は、下記一般式（１）で表される化合物からなる直鎖アルコールの凝固点降下剤に関する。
Ｒ1−Ｏ−（ＰＯ）m（ＥＯ）n−Ｈ （１）
（式中、Ｒ1は炭素数が６〜２２である直鎖アルキル基であり、ＥＯとＰＯは夫々エチレンオキシ基とプロピレンオキシ基を示し、ｍは平均で０．１〜２の数であり、ｎは平均で０．５〜５の数である。但しｍ≦ｎの条件を満たす。）
The present invention relates to a freezing point depressant for a linear alcohol comprising a compound represented by the following general formula (1).
R 1 —O— (PO) m (EO) n —H (1)
(In the formula, R 1 is a linear alkyl group having 6 to 22 carbon atoms, EO and PO are ethyleneoxy group and propyleneoxy group, respectively, and m is an average number of 0.1 to 2) , N is an average number of 0.5 to 5, provided that m ≦ n is satisfied.)
また、本発明は、直鎖アルコールと、下記一般式（１）で表される化合物からなる直鎖アルコールの凝固点降下剤５〜９５重量％とを含有する直鎖アルコール含有組成物に関する。
Ｒ1−Ｏ−（ＰＯ）m（ＥＯ）n−Ｈ （１）
（式中、Ｒ1は炭素数が６〜２２である直鎖アルキル基であり、ＥＯとＰＯは夫々エチレンオキシ基とプロピレンオキシ基を示し、ｍは平均で０．１〜２の数であり、ｎは平均で０．５〜５の数である。但しｍ≦ｎの条件を満たす。）
Moreover, this invention relates to the linear alcohol containing composition containing linear alcohol and the freezing point depressant 5 to 95 weight% of the linear alcohol which consists of a compound represented by following General formula (1).
R 1 —O— (PO) m (EO) n —H (1)
(In the formula, R 1 is a linear alkyl group having 6 to 22 carbon atoms, EO and PO are ethyleneoxy group and propyleneoxy group, respectively, and m is an average number of 0.1 to 2) , N is an average number of 0.5 to 5, provided that m ≦ n is satisfied.)
また、本発明は、（ａ）下記一般式（１）で表される化合物５〜９５重量％、及び（ｂ）下記一般式（２）で表される化合物５〜９５重量％を含有する、直鎖アルコール含有組成物に関する。
Ｒ1−Ｏ−（ＰＯ）m（ＥＯ）n−Ｈ （１）
Ｒ2−ＯＨ （２）
（式中、Ｒ1及びＲ2は、同一又は異なっていても良い炭素数が６〜２２である直鎖アルキル基であり、ＥＯとＰＯは夫々エチレンオキシ基とプロピレンオキシ基を示し、ｍは平均で０．１〜２の数であり、ｎは平均で０．５〜５の数である。但しｍ≦ｎの条件を満たす。）
The present invention also includes (a) 5 to 95% by weight of a compound represented by the following general formula (1), and (b) 5 to 95% by weight of a compound represented by the following general formula (2). The present invention relates to a linear alcohol-containing composition.
R 1 —O— (PO) m (EO) n —H (1)
R 2 —OH (2)
(In the formula, R 1 and R 2 are the same or different linear alkyl groups having 6 to 22 carbon atoms, EO and PO are ethyleneoxy group and propyleneoxy group, respectively, m is (The average is a number of 0.1 to 2, and n is an average of 0.5 to 5. However, the condition of m ≦ n is satisfied.)
また、本発明は、（ａ）下記一般式（１）で表される化合物５〜８０重量％、及び（ｂ）下記一般式（２）で表される化合物を含有し、且つ、成分（ａ）に対する成分（ｂ）の重量比が（ｂ）／（ａ）＝１／１５〜１０／１である、直鎖アルコール含有組成物に関する。
Ｒ1−Ｏ−（ＰＯ）m（ＥＯ）n−Ｈ （１）
Ｒ2−ＯＨ （２）
（式中、Ｒ1及びＲ2は、同一又は異なっていても良い炭素数が６〜２２である直鎖アルキル基であり、ＥＯとＰＯは夫々エチレンオキシ基とプロピレンオキシ基を示し、ｍは平均で０．１〜２の数であり、ｎは平均で０．５〜５の数である。但しｍ≦ｎの条件を満たす。）
Moreover, this invention contains the compound represented by (a) 5-80 weight% of compounds represented by the following general formula (1), and (b) the following general formula (2), and the component (a ) Is a linear alcohol-containing composition in which the weight ratio of component (b) to (b) / (a) = 1/15 to 10/1.
R 1 —O— (PO) m (EO) n —H (1)
R 2 —OH (2)
(In the formula, R 1 and R 2 are the same or different linear alkyl groups having 6 to 22 carbon atoms, EO and PO are ethyleneoxy group and propyleneoxy group, respectively, m is (The average is a number of 0.1 to 2, and n is an average of 0.5 to 5. However, the condition of m ≦ n is satisfied.)
また、本発明は、直鎖アルコールに、プロピレンオキサイドを平均で０．１〜２モル付加し、次いで、エチレンオキサイドを平均で０．５〜５モル付加することにより、該直鎖アルコールと、該アルコールのプロピレンオキサイドとエチレンオキサイドとの付加物とを含有し、且つ凝固点が前記直鎖アルコールよりも低い直鎖アルコール含有混合物を製造する方法に関する。 In addition, the present invention adds an average of 0.1 to 2 mol of propylene oxide to a linear alcohol, and then adds an average of 0.5 to 5 mol of ethylene oxide, The present invention relates to a method for producing a linear alcohol-containing mixture containing an alcohol adduct of propylene oxide and ethylene oxide and having a freezing point lower than that of the linear alcohol.
本発明によれば、直鎖アルコール主体のアルコール組成物である天然アルコールの凝固点を低下させることができる凝固点降下剤が提供される。本発明は、油脂原料由来の天然アルコールに着目し、直鎖アルコールを改質した新規な直鎖アルコール含有組成物を提供するものである。本発明の直鎖アルコール含有組成物は、石化原料由来のアルコールから誘導されたアルコール組成物の代替品として、この組成物から誘導された界面活性剤が同等又はそれ以上の優れた洗浄性及び低温安定性効果を奏し、食器、ガラス、プラスチック等の硬質表面用洗浄剤組成物、衣類用洗浄剤組成物、皮膚、毛髪等の身体用洗浄剤組成物に好適な界面活性剤等の出発原料として好適である。 ADVANTAGE OF THE INVENTION According to this invention, the freezing point depressant which can lower the freezing point of the natural alcohol which is a linear alcohol-based alcohol composition is provided. This invention pays attention to the natural alcohol derived from fats and oils raw materials, and provides the novel linear alcohol containing composition which modified | denatured linear alcohol. The linear alcohol-containing composition of the present invention is an alternative to an alcohol composition derived from a petrochemical raw material-derived alcohol, and the surfactant derived from this composition has the same or more excellent detergency and low temperature. As a starting material such as surfactants that have a stability effect and are suitable for detergent compositions for hard surfaces such as tableware, glass and plastic, detergent compositions for clothes, and detergents for the body such as skin and hair. Is preferred.
＜凝固点降下剤＞
本発明の凝固点降下剤となる成分（ａ）の一般式（１）の化合物は、特に限定されないが、炭素数６〜２２の直鎖アルコールにプロピレンオキサイド、次いで、エチレンオキサイドを反応させることで製造できる。また、成分（ｂ）の直鎖アルコールに極少量のプロピレンオキサイドを付加することで、本発明の成分（ａ）と成分（ｂ）とを含む直鎖アルコール含有組成物として同時に入手することもできる。
<Freezing point depressant>
The compound of the general formula (1) as the component (a) serving as the freezing point depressant of the present invention is not particularly limited, but is produced by reacting a straight-chain alcohol having 6 to 22 carbon atoms with propylene oxide and then ethylene oxide. it can. Moreover, it can also obtain simultaneously as a linear alcohol containing composition containing the component (a) and component (b) of this invention by adding a very small amount of propylene oxide to the linear alcohol of a component (b). .
一般式（１）中のＲ1は、界面活性能の観点から、炭素数が６〜２２の直鎖アルキル基が好ましく、８〜２０のアルキル基がより好ましく、特に１２〜１４のアルキル基が特に好ましい。また、ｍは、凝固剤降下能の観点から、０．１〜２であり、０．１〜１が好ましく、０．２〜０．９がより好ましい。また、ｎは凝固剤降下能の観点から、０．５〜５であり、０．５〜３が好ましく、０．５〜２がより好ましい。本発明の凝固点降下剤は、一般式（１）の化合物を１種以上含有することができる。 R 1 in the general formula (1) is preferably a linear alkyl group having 6 to 22 carbon atoms, more preferably an alkyl group having 8 to 20 carbon atoms, and particularly preferably an alkyl group having 12 to 14 carbon atoms from the viewpoint of surface activity. Particularly preferred. Moreover, m is 0.1-2 from a viewpoint of coagulant lowering ability, 0.1-1 are preferable and 0.2-0.9 are more preferable. Moreover, n is 0.5-5 from a viewpoint of coagulant lowering ability, 0.5-3 are preferable and 0.5-2 are more preferable. The freezing point depressant of the present invention can contain one or more compounds of the general formula (1).
＜直鎖アルコール含有組成物＞
本発明の直鎖アルコール含有組成物は、直鎖アルコールと、上記本発明の凝固点降下剤５〜９５重量％とを含有する。凝固点降下剤、すなわち成分（ａ）の含有量は、組成物中、５〜９５重量％、更に１０〜９５重量％、より更に１５〜９５重量％が好ましい。
<Linear alcohol-containing composition>
The linear alcohol-containing composition of the present invention contains a linear alcohol and 5 to 95% by weight of the freezing point depressant of the present invention. The content of the freezing point depressant, that is, the component (a) is preferably 5 to 95% by weight, more preferably 10 to 95% by weight, and still more preferably 15 to 95% by weight in the composition.
直鎖アルコールとしては、上記一般式（２）で表される成分（ｂ）の直鎖アルコールが好ましい。成分（ｂ）は、炭素数が６〜２２、より好ましくは８〜２０、特に好ましくは１２〜１４の直鎖アルキル基を有するアルコールである。天然油脂由来のアルコールを用いることもできる。直鎖アルコール、好ましくは成分（ｂ）の含有量は、組成物中、５〜９５重量％、更に５〜９０重量％、より更に５〜８５重量％が好ましい。 As a linear alcohol, the linear alcohol of the component (b) represented by the said General formula (2) is preferable. Component (b) is an alcohol having a linear alkyl group having 6 to 22, more preferably 8 to 20, and particularly preferably 12 to 14 carbon atoms. Natural alcohol-derived alcohol can also be used. The content of the linear alcohol, preferably component (b) is preferably 5 to 95% by weight, more preferably 5 to 90% by weight, and still more preferably 5 to 85% by weight in the composition.
また、成分（ａ）と成分（ｂ）の重量比は、（ｂ）／（ａ）＝１／１５〜１０／１、更に１／１０〜１０／１であることが、凝固点降下の観点から好ましい。 Further, the weight ratio of the component (a) to the component (b) is (b) / (a) = 1/15 to 10/1, more preferably 1/10 to 10/1, from the viewpoint of the freezing point depression. preferable.
本発明の直鎖アルコール含有組成物として、成分（ａ）５〜９５重量％、更に１０〜９５重量％、より更に１５〜９５重量％が好ましい。成分（ｂ）２０〜９５重量％、更に２０〜９０重量％、より更に２０〜８５重量％を含有する直鎖アルコール含有組成物が挙げられる。本発明の直鎖アルコール含有組成物の凝固点は直鎖アルコールの凝固点よりも５℃以上低いことが好ましい。 As the linear alcohol-containing composition of the present invention, the component (a) is preferably 5 to 95% by weight, more preferably 10 to 95% by weight, and still more preferably 15 to 95% by weight. Examples thereof include linear alcohol-containing compositions containing 20 to 95% by weight of component (b), further 20 to 90% by weight, and more preferably 20 to 85% by weight. The freezing point of the linear alcohol-containing composition of the present invention is preferably 5 ° C. or lower than the freezing point of the linear alcohol.
本発明の直鎖アルコール含有組成物を得る方法として、
〔１〕：成分（ａ）と成分（ｂ）とを混合する方法、
〔２〕：成分（ｂ）にプロピレンオキサイドを極少量付加し、更にエチレンオキサイドを付加する方法、
等が挙げられる。〔２〕の方法では、成分（ｂ）以外の直鎖アルコールのプロピレンオキサイド・エチレンオキサイド付加物を含む組成物として入手されるが、本発明の効果を損なわない限り、それらを含んでいても良い。また、〔２〕の方法では、成分（ａ）を高濃度で含むよう、プロピレンオキサイドの付加モル数は平均で０超２未満とすることが好ましい。〔２〕の方法により、直鎖アルコールに、プロピレンオキサイドを平均で０．１〜２モル付加し、次いでエチレンオキサイドを平均０．５〜５モル付加することにより、該直鎖アルコールと、該アルコールのプロピレンオキサイド・エチレンオキサイド付加物とを含有し、且つ凝固点が前記直鎖アルコールよりも低い直鎖アルコール含有混合物を製造する方法が提供される。この方法で得られた混合物は、直鎖アルコール含有組成物として用いることができる。また、この方法で得られた混合物の凝固点は、直鎖アルコールの凝固点よりも５℃以上低いことが好ましい。
As a method of obtaining the linear alcohol-containing composition of the present invention,
[1]: Method of mixing component (a) and component (b),
[2]: A method of adding a very small amount of propylene oxide to the component (b) and further adding ethylene oxide,
Etc. In the method [2], it is obtained as a composition containing a propylene oxide / ethylene oxide adduct of a linear alcohol other than the component (b), but may be contained as long as the effect of the present invention is not impaired. . In the method [2], the number of moles of propylene oxide added is preferably more than 0 and less than 2 so as to contain the component (a) at a high concentration. By adding 0.1 to 2 mol of propylene oxide on average to the linear alcohol by the method of [2], and then adding 0.5 to 5 mol of ethylene oxide on average, the linear alcohol and the alcohol And a propylene oxide / ethylene oxide adduct, and a method for producing a linear alcohol-containing mixture having a freezing point lower than that of the linear alcohol. The mixture obtained by this method can be used as a linear alcohol-containing composition. In addition, the freezing point of the mixture obtained by this method is preferably 5 ° C. or lower than the freezing point of the linear alcohol.
本発明の直鎖アルコール含有組成物は、界面活性剤、更に非イオン性界面活性剤、陰イオン性界面活性剤の製造原料として好適である。その他にも、アミノ化合物、アルキルグルコシド、脂肪酸エステル等の製造原料とすることができる。また、当該組成物をそのまま洗浄剤、乳化剤、分散剤として使用することもできる。本発明の直鎖アルコール含有組成物から製造する製品等の用途によっては、本発明の直鎖アルコール含有組成物は本発明の凝固点降下剤を含んだまま各種製品の製造原料として使用できる。 The linear alcohol-containing composition of the present invention is suitable as a raw material for producing a surfactant, further a nonionic surfactant and an anionic surfactant. In addition, it can be used as a raw material for producing amino compounds, alkyl glucosides, fatty acid esters and the like. Moreover, the said composition can also be used as a washing | cleaning agent, an emulsifier, and a dispersing agent as it is. Depending on the application of the product produced from the linear alcohol-containing composition of the present invention, the linear alcohol-containing composition of the present invention can be used as a raw material for producing various products while containing the freezing point depressant of the present invention.
＜製造例１：凝固点硬化剤１の製造＞
攪拌装置、温度制御装置、自動導入装置を備えたオートクレーブにヤシ油アルコール１９４ｇ（平均分子量１９４、１．０モル）、触媒として４８％水酸化カリウム０．６ｇ（０．００５モル）を投入し、混合系内を窒素で置換した後、減圧下（１．３ｋＰａ）、１１０℃にて０．５時間脱水を行った。ついでプロピレンオキシド（以下、ＰＯと表記する）５８．５ｇ（１．０モル）を１３０℃にて圧力０．１〜０．４ＭＰａとなるように導入しながら反応を行った。ＰＯ導入後１３０℃で１時間反応させた。次いでエチレンオキシド（以下、ＥＯと表記する）４４．１ｇ（１．０モル）を１５５℃にて圧力０．１〜０．４ＭＰａとなるように導入しながら反応を行った。ＥＯ導入後１５５℃で１時間反応させた。
<Production Example 1: Production of freezing point curing agent 1>
194 g (average molecular weight 194, 1.0 mol) of coconut oil alcohol and 0.6 g (0.005 mol) of 48% potassium hydroxide as a catalyst were charged into an autoclave equipped with a stirrer, a temperature controller, and an automatic introduction device. After the inside of the mixed system was replaced with nitrogen, dehydration was performed at 110 ° C. under reduced pressure (1.3 kPa) for 0.5 hour. Next, the reaction was carried out while introducing 58.5 g (1.0 mol) of propylene oxide (hereinafter referred to as PO) at 130 ° C. so that the pressure was 0.1 to 0.4 MPa. After introducing PO, the mixture was reacted at 130 ° C. for 1 hour. Next, the reaction was carried out while introducing 44.1 g (1.0 mol) of ethylene oxide (hereinafter referred to as EO) at 155 ° C. so that the pressure was 0.1 to 0.4 MPa. After introducing EO, the reaction was carried out at 155 ° C. for 1 hour.
反応終了混合物をガラス製４つ口フラスコに移した。反応終了混合物に対してキョーワード６００Ｓ（協和化学製）２．２ｇを添加し、８０℃、３時間で吸着処理を行い、８０℃条件でろ過を行いヤシ油アルコールのＰＯ平均１．０モル、ＥＯ平均１．０モル付加物を得た。この凝固点降下剤は、一般式（１）で表される化合物であってｍ、ｎがそれぞれ０、１、２、３、４である化合物の混合物である。なお、化合物の確認は、ガスクロマトグラフィーを用いて行った（以下同様）。 The reaction completed mixture was transferred to a glass four-necked flask. Kyoward 600S (manufactured by Kyowa Chemical Co., Ltd.) (2.2 g) was added to the reaction finished mixture, adsorbed at 80 ° C. for 3 hours, filtered under 80 ° C. condition, and PO average 1.0 mol of palm oil alcohol. An EO average of 1.0 mole adduct was obtained. This freezing point depressant is a mixture of compounds represented by the general formula (1), wherein m and n are 0, 1, 2, 3, 4 respectively. The compound was confirmed using gas chromatography (the same applies hereinafter).
＜製造例２：凝固点降下剤２の製造＞
製造例１においてＥＯを８８．１ｇ（２．０モル）を用いる以外は製造例１記載の通りに行い、ヤシ油アルコールのＰＯ平均１．０モル、ＥＯ平均２．０モル付加物を得た。
<Production Example 2: Production of freezing point depressant 2>
Except that 88.1 g (2.0 mol) of EO was used in Production Example 1, it was carried out as described in Production Example 1 to obtain an adduct of coconut oil alcohol with a PO average of 1.0 mol and an EO average of 2.0 mol. .
＜実施例１〜６＞
上記で得られた凝固点降下剤を表１に示す割合（見かけ重量比）で直鎖アルコールと混合し、得られた直鎖アルコール含有組成物の凝固点を測定した。また、直鎖アルコールの凝固点も測定した。結果を表１に示す。なお、凝固点は、凝固点測定装置（マイクロニクス株式会社製 ＫＦＰ−１０１）を用いて測定した。
<Examples 1-6>
The freezing point depressant obtained above was mixed with a linear alcohol in the ratio shown in Table 1 (apparent weight ratio), and the freezing point of the obtained linear alcohol-containing composition was measured. The freezing point of the linear alcohol was also measured. The results are shown in Table 1. The freezing point was measured using a freezing point measuring device (KFP-101 manufactured by Micronics Co., Ltd.).
＜実施例７＞
製造例１においてＰＯを２３．２ｇ（０．４モル）、ＥＯを４４．１ｇ（１．０モル）を用いる以外は製造例１記載の通りに行い、ヤシ油アルコールのＰＯ平均０．４モル、ＥＯ平均１．０モル付加物を得た。この付加物は、直鎖アルコールと、一般式（１）で表される化合物からなる凝固点降下剤とを含有する直鎖アルコール含有組成物である。その凝固点を表２に示した。
<Example 7>
Except for using 23.2 g (0.4 mol) of PO and 44.1 g (1.0 mol) of EO in Production Example 1, the procedure was as described in Production Example 1, and the average PO of coconut oil alcohol was 0.4 mol. An EO average of 1.0 mole adduct was obtained. This adduct is a linear alcohol-containing composition containing a linear alcohol and a freezing point depressant composed of the compound represented by the general formula (1). The freezing point is shown in Table 2.
＜実施例８＞
製造例１においてＰＯを１１．６ｇ（０．２モル）、ＥＯを６６．１ｇ（１．５モル）を用いる以外は製造例１記載の通りに行い、ヤシ油アルコールのＰＯ平均０．２モル、ＥＯ平均１．５モル付加物を得た。この付加物は、直鎖アルコールと、一般式（１）で表される化合物からなる凝固点降下剤とを含有する直鎖アルコール含有組成物である。その凝固点を表２に示した。
<Example 8>
Except for using 11.6 g (0.2 mol) of PO and 66.1 g (1.5 mol) of EO in Production Example 1, the procedure was as described in Production Example 1, and the average PO of coconut oil alcohol was 0.2 mol. The EO average 1.5 mol adduct was obtained. This adduct is a linear alcohol-containing composition containing a linear alcohol and a freezing point depressant composed of the compound represented by the general formula (1). The freezing point is shown in Table 2.
＜実施例９＞
製造例１においてＰＯを２３．２ｇ（０．４モル）、ＥＯを６６．１ｇ（１．５モル）を用いる以外は製造例１記載の通りに行い、ヤシ油アルコールのＰＯ平均０．４モル、ＥＯ平均１．５モル付加物を得た。この付加物は、直鎖アルコールと、一般式（１）で表される化合物からなる凝固点降下剤とを含有する直鎖アルコール含有組成物である。その凝固点を表２に示した。
<Example 9>
Except for using 23.2 g (0.4 mol) of PO and 66.1 g (1.5 mol) of EO in Production Example 1, the procedure was as described in Production Example 1, and the average PO of coconut oil alcohol was 0.4 mol. The EO average 1.5 mol adduct was obtained. This adduct is a linear alcohol-containing composition containing a linear alcohol and a freezing point depressant composed of the compound represented by the general formula (1). The freezing point is shown in Table 2.
＜実施例１０＞
製造例１においてＰＯを４０．７ｇ（０．７モル）、ＥＯを８８．１ｇ（２．０モル）を用いる以外は製造例１記載の通りに行い、ヤシ油アルコールのＰＯ平均０．７モル、ＥＯ平均２．０モル付加物を得た。この付加物は、直鎖アルコールと、一般式（１）で表される化合物からなる凝固点降下剤とを含有する直鎖アルコール含有組成物である。その凝固点を表２に示した。
<Example 10>
In Production Example 1, except that 40.7 g (0.7 mol) of PO and 88.1 g (2.0 mol) of EO were used, the production was performed as described in Production Example 1, and the average PO of coconut oil alcohol was 0.7 mol. The EO average 2.0 mol adduct was obtained. This adduct is a linear alcohol-containing composition containing a linear alcohol and a freezing point depressant composed of the compound represented by the general formula (1). The freezing point is shown in Table 2.
Claims (8)
Ｒ1−Ｏ−（ＰＯ）m（ＥＯ）n−Ｈ （１）
（式中、Ｒ1は炭素数が６〜２２である直鎖アルキル基であり、ＥＯとＰＯは夫々エチレンオキシ基とプロピレンオキシ基を示し、ｍは平均で０．１〜２の数であり、ｎは平均で０．５〜５の数である。但しｍ≦ｎの条件を満たす。） A freezing point depressant for a linear alcohol comprising a compound represented by the following general formula (1).
R 1 —O— (PO) m (EO) n —H (1)
(In the formula, R 1 is a linear alkyl group having 6 to 22 carbon atoms, EO and PO are ethyleneoxy group and propyleneoxy group, respectively, and m is an average number of 0.1 to 2) , N is an average number of 0.5 to 5, provided that m ≦ n is satisfied.)
Ｒ2−ＯＨ （２）
（式中、Ｒ2は、炭素数が６〜２２である直鎖アルキル基である。） The freezing point depressant for a linear alcohol according to claim 1, wherein the linear alcohol is a compound represented by the following general formula (2).
R 2 —OH (2)
(In the formula, R 2 is a linear alkyl group having 6 to 22 carbon atoms.)
Ｒ1−Ｏ−（ＰＯ）m（ＥＯ）n−Ｈ （１）
（式中、Ｒ1は炭素数が６〜２２である直鎖アルキル基であり、ＥＯとＰＯは夫々エチレンオキシ基とプロピレンオキシ基を示し、ｍとｎは夫々０．１〜２の平均の数と０．５〜５の平均の数である。但しｍ≦ｎの条件を満たす。） A linear alcohol-containing composition comprising a linear alcohol and a linear alcohol freezing point depressant of 5 to 95% by weight comprising a compound represented by the following general formula (1).
R 1 —O— (PO) m (EO) n —H (1)
(In the formula, R 1 is a linear alkyl group having 6 to 22 carbon atoms, EO and PO are ethyleneoxy group and propyleneoxy group, respectively, and m and n are each an average of 0.1 to 2. And the average number of 0.5 to 5, provided that m ≦ n is satisfied.)
Ｒ2−ＯＨ （２）
（式中、Ｒ2は、炭素数が６〜２２である直鎖アルキル基である。） The linear alcohol-containing composition according to claim 3, wherein the linear alcohol is a compound represented by the following general formula (2).
R 2 —OH (2)
(In the formula, R 2 is a linear alkyl group having 6 to 22 carbon atoms.)
Ｒ1−Ｏ−（ＰＯ）m（ＥＯ）n−Ｈ （１）
Ｒ2−ＯＨ （２）
（式中、Ｒ1及びＲ2は、同一又は異なっていても良い炭素数が６〜２２である直鎖アルキル基であり、ＥＯとＰＯは夫々エチレンオキシ基とプロピレンオキシ基を示し、ｍは平均で０．１〜２の数であり、ｎは平均で０．５〜５の数である。但しｍ≦ｎの条件を満たす。） A linear alcohol-containing composition containing (a) 5 to 95% by weight of a compound represented by the following general formula (1) and (b) 5 to 95% by weight of a compound represented by the following general formula (2) .
R 1 —O— (PO) m (EO) n —H (1)
R 2 —OH (2)
(In the formula, R 1 and R 2 are the same or different linear alkyl groups having 6 to 22 carbon atoms, EO and PO are ethyleneoxy group and propyleneoxy group, respectively, m is (The average is a number of 0.1 to 2, and n is an average of 0.5 to 5. However, the condition of m ≦ n is satisfied.)
Ｒ1−Ｏ−（ＰＯ）m（ＥＯ）n−Ｈ （１）
Ｒ2−ＯＨ （２）
（式中、Ｒ1及びＲ2は、同一又は異なっていても良い炭素数が６〜２２である直鎖アルキル基であり、ＥＯとＰＯは夫々エチレンオキシ基とプロピレンオキシ基を示し、ｍは平均で０．１〜２の数であり、ｎは平均で０．５〜５の数である。但しｍ≦ｎの条件を満たす。） (A) 5 to 95% by weight of a compound represented by the following general formula (1), and (b) a compound represented by the following general formula (2), and component (b) relative to component (a) The linear alcohol containing composition whose weight ratio is (b) / (a) = 1 / 15-10 / 1.
R 1 —O— (PO) m (EO) n —H (1)
R 2 —OH (2)
(In the formula, R 1 and R 2 are the same or different linear alkyl groups having 6 to 22 carbon atoms, EO and PO are ethyleneoxy group and propyleneoxy group, respectively, m is (The average is a number of 0.1 to 2, and n is an average of 0.5 to 5. However, the condition of m ≦ n is satisfied.)
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| JPS57167375A (en) * | 1981-04-08 | 1982-10-15 | Nippon Shokubai Kagaku Kogyo Co Ltd | Antifreezing agent |
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| JP2001011489A (en) * | 1998-09-29 | 2001-01-16 | Sanyo Chem Ind Ltd | Nonionic surfactant and its preparation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5236761B2 (en) * | 1974-01-04 | 1977-09-17 | ||
| JPS54155985A (en) * | 1978-05-31 | 1979-12-08 | Daihatsu Motor Co Ltd | Antiifreezing composition for water mixed in fuel tank |
| JPS57167375A (en) * | 1981-04-08 | 1982-10-15 | Nippon Shokubai Kagaku Kogyo Co Ltd | Antifreezing agent |
| JPH0331388A (en) * | 1989-06-27 | 1991-02-12 | Nippon Oil Co Ltd | Freezing-preventive composition |
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| CN113046026A (en) * | 2021-04-07 | 2021-06-29 | 山西大同大学 | Chlorine-free low-corrosivity coal antifreezing solution |
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