JP2007186429A - Method for producing alkylene oxide adduct - Google Patents
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- JP2007186429A JP2007186429A JP2006003552A JP2006003552A JP2007186429A JP 2007186429 A JP2007186429 A JP 2007186429A JP 2006003552 A JP2006003552 A JP 2006003552A JP 2006003552 A JP2006003552 A JP 2006003552A JP 2007186429 A JP2007186429 A JP 2007186429A
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- 125000002947 alkylene group Chemical group 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- 238000012644 addition polymerization Methods 0.000 claims abstract description 4
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000005702 oxyalkylene group Chemical group 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 abstract description 11
- 238000006116 polymerization reaction Methods 0.000 abstract description 11
- 238000009826 distribution Methods 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 2
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- 239000003480 eluent Substances 0.000 description 3
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- 230000000052 comparative effect Effects 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
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- SFNALCNOMXIBKG-UHFFFAOYSA-N ethylene glycol monododecyl ether Chemical compound CCCCCCCCCCCCOCCO SFNALCNOMXIBKG-UHFFFAOYSA-N 0.000 description 2
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- BXVSAYBZSGIURM-UHFFFAOYSA-N 2-phenoxy-4h-1,3,2$l^{5}-benzodioxaphosphinine 2-oxide Chemical compound O1CC2=CC=CC=C2OP1(=O)OC1=CC=CC=C1 BXVSAYBZSGIURM-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- CUZKCNWZBXLAJX-UHFFFAOYSA-N 2-phenylmethoxyethanol Chemical compound OCCOCC1=CC=CC=C1 CUZKCNWZBXLAJX-UHFFFAOYSA-N 0.000 description 1
- GCYHRYNSUGLLMA-UHFFFAOYSA-N 2-prop-2-enoxyethanol Chemical compound OCCOCC=C GCYHRYNSUGLLMA-UHFFFAOYSA-N 0.000 description 1
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
- LVHMTXVUVRPRHE-UHFFFAOYSA-N C(CCC)C1=C(C=CC(=C1)OCCO)C Chemical compound C(CCC)C1=C(C=CC(=C1)OCCO)C LVHMTXVUVRPRHE-UHFFFAOYSA-N 0.000 description 1
- HFIIEBAQOSQGLN-UHFFFAOYSA-N C(CCC)C1=C(C=CC=C1OCCO)C Chemical compound C(CCC)C1=C(C=CC=C1OCCO)C HFIIEBAQOSQGLN-UHFFFAOYSA-N 0.000 description 1
- LPZGYSIREJQEDL-UHFFFAOYSA-N C(CCC)C=1C(=C(C=CC1)C)OCCO Chemical compound C(CCC)C=1C(=C(C=CC1)C)OCCO LPZGYSIREJQEDL-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- -1 ethylene glycol monoalkyl ether Chemical class 0.000 description 1
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
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- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000199 molecular distillation Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
本発明は、アルキレンオキサイド付加物の製造方法に関する。 The present invention relates to a method for producing an alkylene oxide adduct.
活性水素含有有機化合物とアルキレンオキサイドを反応させることを特徴とするアルキレンオキサイド付加物の製造方法が従来より知られている（例えば、非特許文献１）。しかしながら、従来の製造方法には以下のような問題点があった。 A method for producing an alkylene oxide adduct characterized by reacting an active hydrogen-containing organic compound with an alkylene oxide has been known (for example, Non-Patent Document 1). However, the conventional manufacturing method has the following problems.
例えば、高級アルコールを原料としたアルキレンオキサイドで、塩基性触媒を用いた場合、副生成物が少なく重合度が高い付加物が容易に得られるが、重合度分布が広くなり、未反応物である高級アルコールからアルキレンオキサイド重合度の高いものまで含む混合物になるという問題がある。未反応物が多いと重合物の臭気が強く、重合物の石油エーテル可溶分などの値が高くなるので、洗浄用の界面活性剤として使用するには問題があり、また、アルキレンオキサイドの重合度が高いものが多いと、疎水性と親水性のバランスが崩れるので界面活性剤としての性能低下などが問題となる。 For example, when a basic catalyst is used with an alkylene oxide made of a higher alcohol as a raw material, an adduct having a small amount of by-products and a high degree of polymerization can be easily obtained, but the degree of polymerization is widened and the product is unreacted. There is a problem that it becomes a mixture containing a higher alcohol to a polymer having a high degree of polymerization of alkylene oxide. If there are many unreacted substances, the odor of the polymer is strong and the value of the petroleum ether soluble matter of the polymer is high, so there is a problem in using it as a surfactant for washing, and the polymerization of alkylene oxide If the degree is high, the balance between the hydrophobicity and the hydrophilicity is lost, so that the performance as a surfactant deteriorates.
一方、酸性触媒を用いた場合は、未反応物である高級アルコールの含有量は少なくなるが、ポリエチレングリコールやジオキサンなど望ましくない副生成物が多く生成する。また、酸性触媒は金属に対する腐食性が強いので、使用する装置が限定され、工業用触媒として不具合な点を有する。 On the other hand, when an acidic catalyst is used, the content of unreacted higher alcohol is decreased, but many undesirable by-products such as polyethylene glycol and dioxane are generated. Moreover, since an acidic catalyst has strong corrosiveness with respect to a metal, the apparatus to be used is limited and has a fault as an industrial catalyst.
また重合度分布が狭い付加物が得られる触媒として多くのものが提案されているが、触媒の除去などに複雑な工程が必要であった（特許文献１，非特許文献２）。
本発明は、上記に鑑みてなされたものであり、ポリエチレングリコールやジオキサン等の副生物を多く生成してしまうといった従来の酸性触媒使用時の問題がなく、またハイドロタルサイトのような特殊な触媒を使用したときに必要である複雑な触媒の調整、除去の工程も要さずに、得られるアルキレンオキサイド付加物の重合度分布を十分に狭くすることができるアルキレンオキサイド付加物の製造方法を提供することを目的とする。 The present invention has been made in view of the above, and there is no problem when using a conventional acidic catalyst such as producing a large amount of by-products such as polyethylene glycol and dioxane, and a special catalyst such as hydrotalcite. Provided is a method for producing an alkylene oxide adduct capable of sufficiently narrowing the polymerization degree distribution of the resulting alkylene oxide adduct without requiring the steps of adjusting and removing the complicated catalyst required when using The purpose is to do.
本発明の製造方法は、活性水素含有化合物に対し、触媒を利用してアルキレンオキサイドを付加重合させることからなるアルキレンオキサイド付加物の製造方法であって、活性水素含有化合物として下記化学式（１）で示される化合物を使用するものとする。 The production method of the present invention is a production method of an alkylene oxide adduct comprising addition polymerization of an alkylene oxide to an active hydrogen-containing compound using a catalyst, wherein the active hydrogen-containing compound is represented by the following chemical formula (1). The indicated compound shall be used.
Ｒ｛（ＡＯ）ｎ−ＯＨ｝ｍ …（１）
Ｒはアルキル基、アルケニル基、又はアリール基を表し、ＡＯは炭素数２〜４のオキシアルキレン基を表す。ｎは１〜３の整数を示し、ｍは１〜８の整数を示す。
R {(AO) n-OH} m (1)
R represents an alkyl group, an alkenyl group, or an aryl group, and AO represents an oxyalkylene group having 2 to 4 carbon atoms. n represents an integer of 1 to 3, and m represents an integer of 1 to 8.
上記において、式（１）で示される活性水素含有化合物は、多分散度が１．０００〜１．１００であることが好ましい。 In the above, the active hydrogen-containing compound represented by the formula (1) preferably has a polydispersity of 1.000 to 1.100.
触媒としては塩基性触媒を用いることができる。 A basic catalyst can be used as the catalyst.
本発明の製造方法によれば、従来のものより重合度分布が狭いアルキレンオキサイド付加物が容易に製造可能となる。このため、重合物の臭気が弱く、アルキレンオキサイドの重合度が高いものも少ないので、疎水性と親水性のバランスが崩れることなく、界面活性剤としての性能低下などが生じない。 According to the production method of the present invention, an alkylene oxide adduct having a narrower polymerization degree distribution than conventional ones can be easily produced. For this reason, since the odor of the polymer is weak and few of the alkylene oxides have a high degree of polymerization, the balance between hydrophobicity and hydrophilicity is not lost, and performance as a surfactant does not deteriorate.
また本発明では、特殊な触媒ではなく、一般的に使用されている触媒が使用可能であるため、副生物も少なく、狭い重合度分布を持つアルキレンオキサイド付加物を製造できる。 In the present invention, not a special catalyst but a commonly used catalyst can be used, so that an by-product alkylene oxide adduct having a narrow polymerization degree distribution can be produced.
本発明の製造方法で用いる活性水素含有化合物は、上記の通り化学式（１）で表される化合物である。 The active hydrogen-containing compound used in the production method of the present invention is a compound represented by the chemical formula (1) as described above.
Ｒ｛（ＡＯ）ｎ−ＯＨ｝ｍ …（１）
式（１）におけるＲは、好ましくは、炭素数１〜３０の飽和又は不飽和の直鎖もしくは分枝構造のアルキル基、アルケニル基である。また、それらの中に芳香環やアリール基を含むものも含まれる。
R {(AO) n-OH} m (1)
R in Formula (1) is preferably a saturated or unsaturated linear or branched alkyl group or alkenyl group having 1 to 30 carbon atoms. Moreover, the thing containing an aromatic ring and an aryl group is also contained in them.
ＡＯは炭素数２〜４のオキシアルキレン基を表し、中でも炭素数２のエチレンオキサイドが好ましい。 AO represents an oxyalkylene group having 2 to 4 carbon atoms, and ethylene oxide having 2 carbon atoms is particularly preferable.
ｎは１〜３の整数を示し、中でもｎ＝１が好ましい。ｍは１〜８の整数を示し、中でもｍ＝１が好ましい。 n represents an integer of 1 to 3, and preferably n = 1. m shows the integer of 1-8, and m = 1 is especially preferable.
化学式（１）で表される化合物の具体例としては、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノ−ｎ−プロピルエーテル、エチレングリコールモノ−ｉｓｏ−プロピルエーテル、エチレングリコールモノ−ｎ−ブチルエーテル、エチレングリコールモノ−ｉｓｏ−ブチルエーテル、エチレングリコールモノ−ｔｅｒｔ−ブチルエーテル、エチレングリコールモノ−ｎ−ペンチルエーテル、エチレングリコールモノ−ｉｓｏ−ペンチルエーテル、エチレングリコールモノ−ｔｅｒｔ−ペンチルエーテル、エチレングリコールモノ−ｎ−ヘキシルエーテル、エチレングリコールモノ−２−エチルヘキシルエーテル、エチレングリコールモノ−ｎ−ドデシルエーテル、エチレングリコールモノフェニルエーテル、エチレングリコールモノ−ｏ−トリルエーテル、エチレングリコールモノ−ｍ−トリルエーテル、エチレングリコールモノ−ｐ−トリルエーテル、エチレングリコールモノベンジルエーテル、エチレングリコールモノアリルエーテルが挙げられる。また、エチレンオキシド付加物を分子蒸留することによって得られるエチレングリコールモノアルキルエーテル等も使用できる。 Specific examples of the compound represented by the chemical formula (1) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-iso-propyl ether, ethylene glycol mono-n- Butyl ether, ethylene glycol mono-iso-butyl ether, ethylene glycol mono-tert-butyl ether, ethylene glycol mono-n-pentyl ether, ethylene glycol mono-iso-pentyl ether, ethylene glycol mono-tert-pentyl ether, ethylene glycol mono-n -Hexyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol mono-n-dodecyl ether, ethylene glycol Mono phenyl ether, ethylene glycol monobutyl -o- tolyl ether, ethylene glycol monobutyl -m- tolyl ether, ethylene glycol monobutyl -p- tolyl ether, ethylene glycol monobenzyl ether, ethylene glycol monoallyl ether. In addition, ethylene glycol monoalkyl ether obtained by molecular distillation of an ethylene oxide adduct can also be used.
上記において、式（１）で示される活性水素含有化合物は、多分散度が１．０００〜１．１００であることが好ましい。 In the above, the active hydrogen-containing compound represented by the formula (1) preferably has a polydispersity of 1.000 to 1.100.
上記活性水素含有化合物に対し、アルキレンオキサイドを付加重合させることによりアルキレンオキサイド付加物を製造するに際において、触媒としては塩基性触媒を好適に用いることができ、その例としては、ＫＯＨ、ＮａＯＨ、ＬｉＯＨ、Ｋ２ＣＯ３、Ｎａ２ＣＯ３、Ｌｉ２ＣＯ３、ＣＨ３ＯＮａ、Ｃ２Ｈ５ＯＮａ、ＣＨ３ＯＬｉ、Ｃ２Ｈ５ＯＬｉ、ＣＨ３ＯＫ、Ｃ２Ｈ５ＯＫ等のアルコキシル化用触媒が挙げられ、１種を使用してもよく、２種以上を使用することもできる。 When an alkylene oxide adduct is produced by addition polymerization of alkylene oxide to the active hydrogen-containing compound, a basic catalyst can be suitably used as the catalyst. Examples thereof include KOH, NaOH, LiOH, K 2 CO 3, Na 2 CO 3, Li 2 CO 3, CH 3 ONa, C 2 H 5 ONa, CH 3 OLi, C 2 H 5 OLi, CH 3 OK, alkoxylated, such as C 2 H 5 OK 1 type may be used and 2 or more types can also be used.
本発明で用いられるアルキレンオキサイドは、活性水素を持つ化合物と反応して付加物を生成し得るものであればどのようなものでも良いが、エチレンオキサイドやプロピレンオキサイド、ブチレンオキサイド等のオキシラン環を持つものが好ましく、特に好ましいのはエチレンオキサイドである。 The alkylene oxide used in the present invention may be any alkylene oxide that can react with a compound having active hydrogen to form an adduct, but has an oxirane ring such as ethylene oxide, propylene oxide, and butylene oxide. Of these, ethylene oxide is particularly preferable.
本発明の製造方法によるアルキレンオキサイド付加物の製造は、オートクレーブ等の圧力反応器で、通常の操作手順および反応条件で容易に行うことができる。その際、反応温度は、８０〜１５０℃であることが好ましく、より好ましくは１００〜１３０℃である。 Production of the alkylene oxide adduct by the production method of the present invention can be easily carried out in a pressure reactor such as an autoclave, under ordinary operating procedures and reaction conditions. In that case, it is preferable that reaction temperature is 80-150 degreeC, More preferably, it is 100-130 degreeC.
触媒の使用量は、特に限定されないが、活性水素含有化合物に対して、０．１〜５．０重量％であることが好ましい。 Although the usage-amount of a catalyst is not specifically limited, It is preferable that it is 0.1 to 5.0 weight% with respect to an active hydrogen containing compound.
以下、本発明を実施例によってさらに具体的に示すが、本発明は以下の実施例によって限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples.
なお、以下におけるＥＯ付加モル数の測定はＧＰＣ（ゲル濾過クロマトグラフィー）で行い、副生ポリエチレングリコール含量の測定はＨＰＬＣ（液体クロマトグラフィー）で行った。測定条件はそれぞれ以下の通りである。 In the following, the number of moles of EO added was measured by GPC (gel filtration chromatography), and the content of by-product polyethylene glycol was measured by HPLC (liquid chromatography). The measurement conditions are as follows.
〈ＧＰＣ測定条件〉
カラム：Ｍｅｇａｐａｋ ＧＥＬ ２０１Ｆ（日本分光（株）製）
溶離液：テトラヒドロフラン（ＴＨＦ）
カラム温度：２５℃
検出器：示差屈折計（ＲＩ）
〈ＨＰＬＣ測定条件〉
溶離液：アセトニトリル／水
カラム：ＯＤＳ−Ｈ、２５℃
検出器：示差屈折計（ＲＩ）
<GPC measurement conditions>
Column: Megapak GEL 201F (manufactured by JASCO Corporation)
Eluent: Tetrahydrofuran (THF)
Column temperature: 25 ° C
Detector: Differential refractometer (RI)
<HPLC measurement conditions>
Eluent: Acetonitrile / water Column: ODS-H, 25 ° C
Detector: Differential refractometer (RI)
また、多分散度の測定は、次の条件によるＧＰＣ測定を行うことにより、分子量分布の広狭の程度であるＭｗ／Ｍｎを求めた。 The polydispersity was measured by GPC measurement under the following conditions to obtain Mw / Mn, which is the degree of molecular weight distribution.
カラム：Ｍｅｇａｐａｋ ＧＥＬ ２０１ＦＰ×１、
Ｍｅｇａｐａｋ ＧＥＬ ２０１Ｆ×２（日本分光（株）製）
溶離液：ＴＨＦ（３ｍＬ／分）
カラム温度：４０℃
検出器：ＲＩ
サンプル注入：５重量％溶液１００μＬ
Column: Megapak GEL 201FP × 1,
Megapak GEL 201F × 2 (manufactured by JASCO Corporation)
Eluent: THF (3 mL / min)
Column temperature: 40 ° C
Detector: RI
Sample injection: 5% by weight solution 100 μL
［実施例１］
ステンレス製オートクレーブに、化学式（１）で示される化合物としてエチレングリコールモノドデシルエーテル（多分散度：１．００）を２３０ｇ（１モル）と、触媒としてＫＯＨを０．３３ｇ（０．００６モル）を添加後、オートクレーブ内を窒素で置換した。次に、温度を１３０℃、圧力０．２ＭＰａに維持しながらエチレンオキサイド（以下、ＥＯと表記する場合もある）を１７６ｇ（４モル）導入し、反応を行った。引き続き、同温で１時間熟成した後、６０℃に冷却した。
[Example 1]
In a stainless steel autoclave, 230 g (1 mol) of ethylene glycol monododecyl ether (polydispersity: 1.00) as a compound represented by the chemical formula (1) and 0.33 g (0.006 mol) of KOH as a catalyst After the addition, the inside of the autoclave was replaced with nitrogen. Next, while maintaining the temperature at 130 ° C. and the pressure of 0.2 MPa, 176 g (4 mol) of ethylene oxide (hereinafter sometimes referred to as EO) was introduced to carry out the reaction. Subsequently, after aging at the same temperature for 1 hour, it was cooled to 60 ° C.
得られたアルキレンオキサイド付加物は、平均ＥＯ付加モル数が５．０モルであり、多分散度は１．０４であり、副生ポリエチレングリコールは０．５％であった。 The obtained alkylene oxide adduct had an average EO addition mole number of 5.0 mol, a polydispersity of 1.04, and a by-product polyethylene glycol of 0.5%.
［実施例２］
ステンレス製オートクレーブに、化学式（１）で示される化合物としてエチレングリコールモノヘキシルエーテル（多分散度：１．００）を１５１ｇ（１モル）と、触媒としてＫＯＨを０．３３ｇ（０．００６モル）を添加後、オートクレーブ内を窒素で置換した。次に、温度を１３０℃、圧力０．２ＭＰａに維持しながらエチレンオキサイドを１８１ｇ（４モル）導入し、反応を行った。引き続き、同温で１時間熟成した後、６０℃に冷却した。
[Example 2]
In a stainless steel autoclave, 151 g (1 mol) of ethylene glycol monohexyl ether (polydispersity: 1.00) as a compound represented by the chemical formula (1) and 0.33 g (0.006 mol) of KOH as a catalyst After the addition, the inside of the autoclave was replaced with nitrogen. Next, while maintaining the temperature at 130 ° C. and the pressure at 0.2 MPa, 181 g (4 mol) of ethylene oxide was introduced to carry out the reaction. Subsequently, after aging at the same temperature for 1 hour, it was cooled to 60 ° C.
得られたアルキレンオキサイド付加物は、平均ＥＯ付加モル数が５．０モルであり、多分散度は１．０５であり、副生ポリエチレングリコールは０．５％であった。 The obtained alkylene oxide adduct had an average EO addition mole number of 5.0 moles, a polydispersity of 1.05, and a by-product polyethylene glycol of 0.5%.
［比較例１］
ステンレス製オートクレーブに、ドデシルアルコールを１８６ｇ（１モル）と、ＫＯＨを０．３３ｇ（０．００６モル）を添加後、オートクレーブ内を窒素で置換した。次に、温度を１３０℃、圧力０．２ＭＰａに維持しながらエチレンオキサイドを２２０ｇ（５モル）導入し、反応を行った。引き続き、同温で１時間熟成した後、６０℃に冷却した。
[Comparative Example 1]
After adding 186 g (1 mol) of dodecyl alcohol and 0.33 g (0.006 mol) of KOH to a stainless steel autoclave, the inside of the autoclave was replaced with nitrogen. Next, while maintaining the temperature at 130 ° C. and the pressure at 0.2 MPa, 220 g (5 mol) of ethylene oxide was introduced to carry out the reaction. Subsequently, after aging at the same temperature for 1 hour, it was cooled to 60 ° C.
得られたアルキレンオキサイド付加物は、平均ＥＯ付加モル数が５．０モルであり、多分散度は１．１４であり、副生ポリエチレングリコールは０．５％であった。 The obtained alkylene oxide adduct had an average EO addition mole number of 5.0 moles, a polydispersity of 1.14, and a by-product polyethylene glycol of 0.5%.
［比較例２］
ステンレス製オートクレーブに、１−ヘキシルアルコールを１０２ｇ（１モル）と、ＫＯＨを０．３３ｇ（０．００６モル）を添加後、オートクレーブ内を窒素で置換した。次に、温度を１３０℃、圧力０．２ＭＰａに維持しながらエチレンオキサイドを２２０ｇ（５モル）導入し、反応を行った。引き続き、同温で１時間熟成した後、６０℃に冷却した。
[Comparative Example 2]
After adding 102 g (1 mol) of 1-hexyl alcohol and 0.33 g (0.006 mol) of KOH to a stainless steel autoclave, the inside of the autoclave was replaced with nitrogen. Next, while maintaining the temperature at 130 ° C. and the pressure at 0.2 MPa, 220 g (5 mol) of ethylene oxide was introduced to carry out the reaction. Subsequently, after aging at the same temperature for 1 hour, it was cooled to 60 ° C.
得られたアルキレンオキサイド付加物は、平均ＥＯ付加モル数が５．０モルであり、多分散度は１．１９であり、副生ポリエチレングリコールは０．５％であった。 The resulting alkylene oxide adduct had an average EO addition mole number of 5.0 moles, a polydispersity of 1.19, and by-product polyethylene glycol of 0.5%.
本発明によって得られたアルキレンオキサイド付加物は、重合度分布が狭く、また未反応原料や副生成物が少ないので、家庭用洗剤や工業用界面活性剤、更にはアニオン・カチオン・両性界面活性剤の原料などとして広範な用途に利用することができる。
The alkylene oxide adduct obtained by the present invention has a narrow polymerization degree distribution, and since there are few unreacted raw materials and by-products, household detergents and industrial surfactants, and further anionic / cationic / amphoteric surfactants It can be used in a wide range of applications as a raw material of
Claims (3)
活性水素含有化合物として下記化学式（１）で示される化合物を使用することを特徴とするアルキレンオキサイド付加物の製造方法。
Ｒ｛（ＡＯ）ｎ−ＯＨ｝ｍ …（１）
（Ｒはアルキル基、アルケニル基、又はアリール基を表し、ＡＯは炭素数２〜４のオキシアルキレン基を表す。ｎは１〜３の整数を示し、ｍは１〜８の整数を示す。） A method for producing an alkylene oxide adduct comprising addition polymerization of an alkylene oxide using a catalyst to an active hydrogen-containing compound,
The manufacturing method of the alkylene oxide adduct characterized by using the compound shown by following Chemical formula (1) as an active hydrogen containing compound.
R {(AO) n-OH} m (1)
(R represents an alkyl group, an alkenyl group, or an aryl group, AO represents an oxyalkylene group having 2 to 4 carbon atoms, n represents an integer of 1 to 3, and m represents an integer of 1 to 8.)
The method for producing an alkylene oxide adduct according to claim 1 or 2, wherein the catalyst is a basic catalyst.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08268919A (en) * | 1995-03-28 | 1996-10-15 | Lion Corp | Production of alkylene oxide adduct to active hydrogen-containing compound |
| JPH10168014A (en) * | 1996-12-06 | 1998-06-23 | Nippon Shokubai Co Ltd | Higher secondary alcohol alkoxylate adduct and its production, and cleansing agent and emulsifier containing the same |
| JP2001342156A (en) * | 2000-03-27 | 2001-12-11 | Sanyo Chem Ind Ltd | Method for producing aliphatic alcohol alkylene oxide adduct |
| JP2002308811A (en) * | 1998-09-29 | 2002-10-23 | Sanyo Chem Ind Ltd | Method for producing nonionic surfactant |
| JP2005350402A (en) * | 2004-06-11 | 2005-12-22 | Sanyo Chem Ind Ltd | Monohydric alcohol alkylene oxide adduct and method for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08268919A (en) * | 1995-03-28 | 1996-10-15 | Lion Corp | Production of alkylene oxide adduct to active hydrogen-containing compound |
| JPH10168014A (en) * | 1996-12-06 | 1998-06-23 | Nippon Shokubai Co Ltd | Higher secondary alcohol alkoxylate adduct and its production, and cleansing agent and emulsifier containing the same |
| JP2002308811A (en) * | 1998-09-29 | 2002-10-23 | Sanyo Chem Ind Ltd | Method for producing nonionic surfactant |
| JP2001342156A (en) * | 2000-03-27 | 2001-12-11 | Sanyo Chem Ind Ltd | Method for producing aliphatic alcohol alkylene oxide adduct |
| JP2005350402A (en) * | 2004-06-11 | 2005-12-22 | Sanyo Chem Ind Ltd | Monohydric alcohol alkylene oxide adduct and method for producing the same |
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