JP2007176893A - Method for producing alkylgalactoside - Google Patents
Method for producing alkylgalactoside Download PDFInfo
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- JP2007176893A JP2007176893A JP2005379805A JP2005379805A JP2007176893A JP 2007176893 A JP2007176893 A JP 2007176893A JP 2005379805 A JP2005379805 A JP 2005379805A JP 2005379805 A JP2005379805 A JP 2005379805A JP 2007176893 A JP2007176893 A JP 2007176893A
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- galactose
- galactoside
- alkyl
- alkyl galactoside
- alcohol
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 229930182830 galactose Natural products 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
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- 239000000203 mixture Substances 0.000 claims abstract description 18
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 8
- -1 alkyl galactoside Chemical class 0.000 claims description 81
- 235000000346 sugar Nutrition 0.000 claims description 25
- 238000009833 condensation Methods 0.000 claims description 19
- 230000005494 condensation Effects 0.000 claims description 19
- 238000005227 gel permeation chromatography Methods 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 150000001241 acetals Chemical group 0.000 claims description 7
- 239000003377 acid catalyst Substances 0.000 claims description 7
- 238000005858 glycosidation reaction Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 abstract description 25
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 20
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000007795 chemical reaction product Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
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- 238000004458 analytical method Methods 0.000 description 8
- 229930182470 glycoside Natural products 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- GOQYKNQRPGWPLP-UHFFFAOYSA-N heptadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- 230000000774 hypoallergenic effect Effects 0.000 description 2
- BTFJIXJJCSYFAL-UHFFFAOYSA-N icosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCO BTFJIXJJCSYFAL-UHFFFAOYSA-N 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- REIUXOLGHVXAEO-UHFFFAOYSA-N pentadecan-1-ol Chemical compound CCCCCCCCCCCCCCCO REIUXOLGHVXAEO-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- WYUFTYLVLQZQNH-UHFFFAOYSA-N 1-Ethyl-D-galactoside Natural products CCOC1OC(CO)C(O)C(O)C1O WYUFTYLVLQZQNH-UHFFFAOYSA-N 0.000 description 1
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 1
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical class CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 1
- WCASXYBKJHWFMY-NSCUHMNNSA-N 2-Buten-1-ol Chemical compound C\C=C\CO WCASXYBKJHWFMY-NSCUHMNNSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004435 Oxo alcohol Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229940096386 coconut alcohol Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000004872 foam stabilizing agent Substances 0.000 description 1
- 150000008195 galaktosides Chemical class 0.000 description 1
- WCASXYBKJHWFMY-UHFFFAOYSA-N gamma-methylallyl alcohol Natural products CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical class CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- HOVAGTYPODGVJG-VOQCIKJUSA-N methyl beta-D-galactoside Chemical compound CO[C@@H]1O[C@H](CO)[C@H](O)[C@H](O)[C@H]1O HOVAGTYPODGVJG-VOQCIKJUSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 229940087291 tridecyl alcohol Drugs 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、高縮合物の含有量が少ないアルキルガラクトシドの製造方法、及びアルキルガラクトシド組成物に関する。 The present invention relates to a method for producing an alkyl galactoside having a low content of a high condensate, and an alkyl galactoside composition.
糖誘導体であるアルキルグリコシドは低刺激性界面活性剤であり、他の陰イオン界面活性剤に対しては泡安定剤として作用することが知られている。
アルキルグリコシドの一般的な製造方法の一つに、糖と高級アルコールを酸触媒下で直接反応させる方法（以下「直接法」という）があり、多数の提案がなされている（例えば、特許文献１参照）。また、糖と低級アルコールを酸触媒下で反応させて低級アルキルグリコシドを調製し、その後高級アルコールとアセタール交換させることで目的とするアルキル鎖を有するアルキルグリコシドを得る方法（以下「間接法」という）が知られている（例えば、特許文献２参照）。
Alkyl glycosides, which are sugar derivatives, are hypoallergenic surfactants and are known to act as foam stabilizers for other anionic surfactants.
One common method for producing alkyl glycosides is a method in which a sugar and a higher alcohol are directly reacted in the presence of an acid catalyst (hereinafter referred to as “direct method”), and many proposals have been made (for example, Patent Document 1). reference). Also, a method in which a sugar and a lower alcohol are reacted in the presence of an acid catalyst to prepare a lower alkyl glycoside, and then an acetal exchange with a higher alcohol is performed to obtain an alkyl glycoside having a target alkyl chain (hereinafter referred to as “indirect method”). Is known (see, for example, Patent Document 2).
しかしながら、従来法によるアルキルグリコシドの製造には多くの困難が伴う。その中で重要な課題の一つとして、糖同士又は糖と生成したアルキルグリコシド、及び生成したアルキルグリコシド同士の縮合（以下「糖縮合」という）によって高縮合物が生成し、収率が低下することが挙げられる。
例えば、特許文献３や特許文献４に開示されたアルキルグリコシドの製造方法により、ガラクトースを原料糖として用いてアルキルガラクトシドの製造を試みると、高縮合物の生成が顕著であり、収率が著しく低下してしまう。
また、高縮合物が生成することによって反応終了物含有溶液は固液二相系となるため、過剰に用いた高級アルコールを除去する等の精製工程において、多くの困難が伴う。
However, many difficulties are associated with the production of alkyl glycosides by conventional methods. One of the important issues among them is that a high-condensate is produced due to condensation between sugars or sugar-produced alkylglycoside and between the produced alkylglycosides (hereinafter referred to as “sugar condensation”), resulting in a decrease in yield. Can be mentioned.
For example, when an attempt to produce an alkyl galactoside using galactose as a raw sugar by the method for producing an alkyl glycoside disclosed in Patent Document 3 and Patent Document 4, the production of a high condensate is remarkable and the yield is significantly reduced. Resulting in.
Moreover, since the reaction condensate-containing solution becomes a solid-liquid two-phase system due to the formation of the high condensate, many difficulties are involved in the purification step such as removal of the higher alcohol used in excess.
このように、アルキルグリコシドの製造方法に関する多くの提案がなされているが、これらの提案はグルコースを原料糖として用いるものが大半を占めており、ガラクトースのアルキルグリコシド化に関しては殆ど開示されていない。したがって、ガラクトースを出発原料とするアルキルガラクトシドの製造方法に伴う技術的課題も知られていない。 As described above, many proposals relating to a method for producing alkyl glycosides have been made, but most of these proposals use glucose as a raw sugar, and little is disclosed regarding alkyl glycosidation of galactose. Therefore, the technical problem accompanying the manufacturing method of the alkyl galactoside which uses galactose as a starting material is not known.
本発明は、ガラクトースと炭素数８〜２２の高級脂肪族アルコールとの反応（直接法）、又はガラクトースと炭素数１〜７の低級脂肪族アルコールとの反応物を経由して、前記高級アルコールとアセタール交換反応させる方法（間接法）により、アルキルガラクトシドを製造するに当たり、高縮合物の生成を抑制してアルキルガラクトシドを高収率で製造する方法、及び高縮合物の含有量が少ないアルキルガラクトシド組成物を提供することを課題とする。 The present invention provides a reaction between a galactose and a higher aliphatic alcohol having 8 to 22 carbon atoms (direct method) or a reaction product of a galactose and a lower aliphatic alcohol having 1 to 7 carbon atoms with the higher alcohol. In the production of alkyl galactoside by the acetal exchange reaction method (indirect method), the production of alkyl galactoside in a high yield by suppressing the formation of high condensate, and the composition of alkyl galactoside with low content of high condensate The issue is to provide goods.
本発明者らは、直接法、間接法にかかわらず、ガラクトースに対して、前記高級脂肪族アルコールを８倍モル以上の過剰量を用いることにより、高縮合物の生成を抑制し収率の向上したアルキルガラクトシドが得られることを見出した。
すなわち、本発明は次の（１）〜（３）を提供する。
（１）ガラクトースを炭素数８〜２２の高級脂肪族アルコールを用いてグリコシド化するアルキルガラクトシドの製造方法であって、ガラクトースに対して、該高級脂肪族アルコールを８〜２５倍モルの割合で用いるアルキルガラクトシドの製造方法（直接法）。
（２）ガラクトースを炭素数１〜７の低級脂肪族アルコールを用いてグリコシド化した後、炭素数８〜２２の高級脂肪族アルコールとアセタール交換反応させるアルキルガラクトシドの製造方法であって、ガラクトースに対して、該高級脂肪族アルコールを８〜２５倍モルの割合で用いるアルキルガラクトシドの製造方法（間接法）。
（３）糖縮合度４未満のアルキルガラクトシド（ａ）と糖縮合度４以上のアルキルガラクトシド（ｂ）を含有するアルキルガラクトシド組成物であって、アルキルガラクトシド（ａ）とアルキルガラクトシド（ｂ）のゲル浸透クロマトグラフィーによって測定されるモル比〔（ａ）：（ｂ）〕が、７０：３０〜１００：０であるアルキルガラクトシド組成物。
Regardless of the direct method or the indirect method, the present inventors have suppressed the production of high condensate and improved the yield by using an excess amount of the higher aliphatic alcohol of 8 times mol or more with respect to galactose. It was found that the obtained alkyl galactoside was obtained.
That is, the present invention provides the following (1) to (3).
(1) A method for producing an alkyl galactoside in which galactose is glycosidated using a higher aliphatic alcohol having 8 to 22 carbon atoms, and the higher aliphatic alcohol is used at a ratio of 8 to 25-fold mol with respect to galactose. Production method of alkyl galactoside (direct method).
(2) A method for producing an alkyl galactoside in which galactose is glycosidated using a lower aliphatic alcohol having 1 to 7 carbon atoms and then acetal exchange reaction with a higher aliphatic alcohol having 8 to 22 carbon atoms, In addition, a method for producing an alkyl galactoside using the higher aliphatic alcohol in a proportion of 8 to 25 moles (indirect method).
(3) An alkyl galactoside composition comprising an alkyl galactoside (a) having a degree of sugar condensation of less than 4 and an alkyl galactoside (b) having a degree of sugar condensation of 4 or more, comprising an alkyl galactoside (a) and an alkyl galactoside (b) gel An alkyl galactoside composition having a molar ratio [(a) :( b)] of 70:30 to 100: 0 as measured by permeation chromatography.
本発明方法によれば、糖の高縮合物の含有量が少ないアルキルガラクトシドを高収率で得ることができる。また、高縮合物が少ないアルキルガラクトシド組成物を提供することができる。 According to the method of the present invention, an alkyl galactoside having a low content of a high sugar condensate can be obtained in a high yield. Moreover, the alkyl galactoside composition with few high condensates can be provided.
本発明のアルキルガラクトシドの製造方法においては、アルキルガラクトシドは、ガラクトースと炭素数８〜２２の高級脂肪族アルコールを使用してグリコシド化することによって製造される。
本発明においては、（１）ガラクトースと前記高級アルコールとを直接反応させる直接法、又は、（２）炭素数１〜７の低級脂肪族アルコールを用いてガラクトースをグリコシド化した後、前記高級アルコールとアセタール交換反応させる間接法のいずれも実施可能である。
In the method for producing an alkyl galactoside of the present invention, the alkyl galactoside is produced by glycosidation using galactose and a higher aliphatic alcohol having 8 to 22 carbon atoms.
In the present invention, (1) a direct method in which galactose and the higher alcohol are directly reacted, or (2) glycosidation of galactose using a lower aliphatic alcohol having 1 to 7 carbon atoms, Any of the indirect methods of acetal exchange reaction can be carried out.
本発明において、原料として用いられる炭素数１〜７の低級脂肪族アルコール（以下、単に「低級アルコール」ということがある）としては特に制限はなく、例えば、メタノール、エタノール、プロパノール、イソプロパノール、各種ブタノール、各種ヘキサノール、各種ヘプタノール等の直鎖又は分岐鎖の飽和アルコール、アリルアルコール、クロチルアルコール等の直鎖又は分岐鎖の不飽和アルコールが挙げられる。
また、炭素数８〜２２の高級脂肪族アルコール（以下、単に「高級アルコール」ということがある）としては特に制限はなく、例えば、２−エチルヘキサノール、デシルアルコール、ドデシルアルコール、トリデシルアルコール、テトラデシルアルコール、ペンタデシルアルコール、ヘキサデシルアルコール、ヘプタデシルアルコール、オクタデシルアルコール、エイコシルアルコール、オレイルアルコール、ヤシアルコール、オキソアルコール、ゲルベアルコール等の直鎖又は分岐鎖の飽和又は不飽和アルコール、そのアルキレンオキサイド付加物及びその混合物等が挙げられる。
In the present invention, the lower aliphatic alcohol having 1 to 7 carbon atoms (hereinafter sometimes simply referred to as “lower alcohol”) used as a raw material is not particularly limited, and examples thereof include methanol, ethanol, propanol, isopropanol, and various butanols. , Linear or branched saturated alcohols such as various hexanols and various heptanols, and linear or branched unsaturated alcohols such as allyl alcohol and crotyl alcohol.
Moreover, there is no restriction | limiting in particular as a C8-C22 higher aliphatic alcohol (henceforth only a "higher alcohol"), For example, 2-ethylhexanol, decyl alcohol, dodecyl alcohol, tridecyl alcohol, tetra Linear or branched saturated or unsaturated alcohols such as decyl alcohol, pentadecyl alcohol, hexadecyl alcohol, heptadecyl alcohol, octadecyl alcohol, eicosyl alcohol, oleyl alcohol, coconut alcohol, oxo alcohol, gerve alcohol, alkylene oxides thereof Examples include adducts and mixtures thereof.
本発明においては、前記高級アルコールの使用量は、ガラクトースに対して８〜２５倍モルの範囲である。高級アルコールの使用量が８倍モル以上であれば、高縮合物の生成を充分に抑制することができ、また２５倍モル以下であれば、技術的及び経済的なメリットがある。高級アルコールの好ましい使用量は、ガラクトースに対して９〜２２倍モルであり、より好ましくは１０〜２０倍モルである。 In this invention, the usage-amount of the said higher alcohol is the range of 8-25 times mole with respect to galactose. If the amount of the higher alcohol used is 8 times mol or more, the formation of a high condensate can be sufficiently suppressed, and if it is 25 times mol or less, there are technical and economic advantages. The preferred amount of higher alcohol used is 9 to 22-fold mol, more preferably 10 to 20-fold mol based on galactose.
グリコシド化工程において使用される酸触媒としては、通常脱水反応に用いられるものであれば特に制限されず公知のものが用いられる。例えば、パラトルエンスルホン酸、メタンスルホン酸、硫酸、塩酸、硝酸、リン酸、スチレン−ジビニルベンゼン共重合体等を母体とする強酸性イオン交換樹脂等から選ばれる少なくとも一種が挙げられる。これらの中では、該高級アルコールへの溶解性の観点から、パラトルエンスルホン酸が好ましい。
使用される酸触媒の量は、ガラクトース又はガラクトースと低級アルコールとの反応物１モルあたり０．００１〜０．１０モルであることが好ましい。酸触媒の使用量がこの範囲にあれば、反応速度及び得られるアルキルガラクトシドの色相が共に良好となる。該酸触媒の量は、ガラクトース又はガラクトースと低級アルコールとの反応物１モルあたり、より好ましくは０．００２〜０．０８モル、さらに好ましくは０．００３〜０．０５モルである。
The acid catalyst used in the glycosidation step is not particularly limited as long as it is usually used in a dehydration reaction, and a known one is used. Examples thereof include at least one selected from strongly acidic ion exchange resins based on paratoluenesulfonic acid, methanesulfonic acid, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, styrene-divinylbenzene copolymer, and the like. Among these, paratoluenesulfonic acid is preferable from the viewpoint of solubility in the higher alcohol.
The amount of the acid catalyst used is preferably 0.001 to 0.10 mole per mole of galactose or a reaction product of galactose and a lower alcohol. If the usage-amount of an acid catalyst exists in this range, both the reaction rate and the hue of the alkyl galactoside obtained will become favorable. The amount of the acid catalyst is more preferably 0.002 to 0.08 mol, and still more preferably 0.003 to 0.05 mol, per mol of the reaction product of galactose or galactose and a lower alcohol.
本発明の間接法において、ガラクトースと低級アルコールとの反応物としては、メチルガラクトシド、エチルガラクトシド、プロピルガラクトシド、ブチルガラクトシド等が挙げられる。ガラクトースと低級アルコールとの反応を短時間で完結させるためには高温条件下で反応を行うことが好ましく、この観点からブチルガラクトシドが好ましい。 In the indirect method of the present invention, examples of the reaction product of galactose and lower alcohol include methyl galactoside, ethyl galactoside, propyl galactoside, and butyl galactoside. In order to complete the reaction between galactose and lower alcohol in a short time, the reaction is preferably carried out under high temperature conditions, and butyl galactoside is preferred from this viewpoint.
本発明においては、直接法によるガラクトースと高級アルコールとの反応、間接法によるガラクトースと低級アルコールとの反応及びその反応物と高級アルコールとのアセタール交換反応におけるそれぞれの反応温度は、通常８０〜１５０℃、好ましくは９０〜１２０℃、より好ましくは１１５〜１２０℃である。反応速度の観点から、反応温度は８０℃以上が好ましく、得られるアルキルガラクトシドの色相劣化を抑制するためには１５０℃以下とするのがよい。
また、直接法におけるグリコシド化反応、及び間接法におけるアセタール交換反応においては、減圧の程度は好ましくは０．６７〜１３．３ｋＰａ、より好ましくは２．７〜８．０ｋＰａである。脱水及び低級アルコールの除去の観点から、減圧度は１３．３ｋＰａ以下が好ましい。
In the present invention, each reaction temperature in the reaction of galactose with a higher alcohol by the direct method, the reaction of galactose with a lower alcohol by the indirect method and the acetal exchange reaction between the reaction product and the higher alcohol is usually 80 to 150 ° C. , Preferably it is 90-120 degreeC, More preferably, it is 115-120 degreeC. From the viewpoint of the reaction rate, the reaction temperature is preferably 80 ° C. or higher, and is preferably 150 ° C. or lower in order to suppress the hue deterioration of the resulting alkyl galactoside.
In the glycosidation reaction in the direct method and the acetal exchange reaction in the indirect method, the degree of reduced pressure is preferably 0.67 to 13.3 kPa, more preferably 2.7 to 8.0 kPa. From the viewpoint of dehydration and removal of the lower alcohol, the degree of vacuum is preferably 13.3 kPa or less.
ここで副生する水又は低級アルコ−ルを効率よく除去するために窒素を吹込んでもよい。窒素の吹込み量は原料の仕込み量によって異なるため一概には言えないが、例えば、ガラクトース０．１０モルの仕込み量に対して１０〜５０ｍｌ／ｍｉｎ程度の窒素を吹き込むことが好ましい。
反応時間は反応条件によって左右されるため、一概には決定できないが、原料の消費量や生成物の生成量を適宣追跡し、反応終了時点で反応を打ち切ることが好ましい。
なお、間接法におけるガラクトースと低級アルコールとの反応においても、副生する水を除去するために、前記と同様に窒素を吹き込むことができる。
Here, nitrogen may be blown in order to efficiently remove the by-product water or lower alcohol. Although the amount of nitrogen blown differs depending on the amount of raw material charged, it cannot be generally stated. For example, it is preferable to blow nitrogen of about 10 to 50 ml / min with respect to the amount of galactose 0.10 mol.
Since the reaction time depends on the reaction conditions, it cannot be determined unconditionally. However, it is preferable to appropriately monitor the consumption of raw materials and the amount of product produced, and to terminate the reaction at the end of the reaction.
In the reaction of galactose and lower alcohol in the indirect method, nitrogen can be blown in the same manner as described above in order to remove the by-product water.
本発明においては、アルキルガラクトシドの原料となるアルコールを反応溶媒として用いることができるが、反応系の濃度を調整するために補助溶媒を用いてもよい。ただし、用いる補助溶媒は、アルキルガラクトシド製造の反応条件下であっても沸騰しない程度の高い沸点を有しており、かつ、反応に全く影響を与えないものであることが好ましい。 In the present invention, alcohol as a raw material for alkylgalactoside can be used as a reaction solvent, but an auxiliary solvent may be used to adjust the concentration of the reaction system. However, it is preferable that the auxiliary solvent to be used has a boiling point high enough not to boil even under the reaction conditions for producing the alkylgalactoside and does not affect the reaction at all.
反応終了後、反応器を常圧に戻した段階で糖縮合の進行を抑制するため、塩基性物質を添加して触媒を中和するのが好ましい。中和に用いられる塩基性物質としては特に制限はないが、例えばＮａＯＨ、ＫＯＨ、Ｎａ2ＣＯ3、ＮａＨＣＯ3、ＮＨ3、強塩基性イオン交換樹脂等が挙げられる。これらの中では、経済性、溶解性、取扱い性の観点から、ＮａＯＨ、ＫＯＨの使用が好ましい。 After completion of the reaction, it is preferable to neutralize the catalyst by adding a basic substance in order to suppress the progress of sugar condensation at the stage where the reactor is returned to normal pressure. The basic substance used for neutralization is not particularly limited, and examples thereof include NaOH, KOH, Na 2 CO 3 , NaHCO 3 , NH 3 , and strongly basic ion exchange resins. Among these, NaOH and KOH are preferably used from the viewpoints of economy, solubility, and handleability.
反応終了物の平均糖縮合度を算出する手法は特に限定されない。本発明においては、反応終了物をアセチル化処理後、ゲル浸透クロマトグラフィー法（以下「ＧＰＣ」という）による分析を行い、各成分の面積比から平均糖縮合度を算出することができる。
ＧＰＣによる分析は、例えば、東ソー株式会社製の商品名、ＬＣ−８０２０ 高圧グラジエントシステムを使用し、カラムとして、東ソー株式会社製の商品名、ＴＳＫ−ＧＥＬ Ｇ２０００ＨＸＬ７．８＊３００と、ＴＳＫ−ＧＥＬ Ｇ１０００ＨＸＬ７．８＊３００を直列使用し、展開溶媒として、テトラヒドロフランを用いることによって行うことができる。また、検出器として、東ソー株式会社製の商品名、ＲＩ８０２０を用いた。
なお、「高縮合物」の一般的な意味は特に限定されるものではないが、本発明においては、反応終了物のＧＰＣ分析の結果、糖縮合度が４以上のアルキルガラクトシドを意味する。
The method for calculating the average degree of sugar condensation of the reaction end product is not particularly limited. In the present invention, after the reaction end product is acetylated, it is analyzed by gel permeation chromatography (hereinafter referred to as “GPC”), and the average sugar condensation degree can be calculated from the area ratio of each component.
The analysis by GPC uses, for example, a product name manufactured by Tosoh Corporation, LC-8020 high-pressure gradient system, and as a column, product names manufactured by Tosoh Corporation, TSK-GEL G2000HXL7.8 * 300, and TSK-GEL G1000HXL7. .8 * 300 can be used in series, and tetrahydrofuran can be used as a developing solvent. Further, as a detector, a trade name, RI8020, manufactured by Tosoh Corporation was used.
The general meaning of the “high condensate” is not particularly limited, but in the present invention, it means an alkyl galactoside having a sugar condensation degree of 4 or more as a result of GPC analysis of the reaction end product.
本発明はまた、アルキルガラクトシド組成物をも提供する。
本発明のアルキルガラクトシド組成物は、糖縮合度４未満のアルキルガラクトシド（ａ）と糖縮合度４以上のアルキルガラクトシド（ｂ）を含有するアルキルガラクトシド組成物であって、アルキルガラクトシド（ａ）とアルキルガラクトシド（ｂ）のＧＰＣによって測定されるモル比〔（ａ）：（ｂ）〕が、７０：３０〜１００：０である。
ＧＰＣによって測定されるモル比〔（ａ）：（ｂ）〕は、アルキルガラクトシド組成物の組成比（含有比）を表す。このように、本発明のアルキルガラクトシド組成物においては、アルキルガラクトシド中の糖縮合度４以上の高縮合物（ｂ）の前記モル比が０．５〜３０％、好ましくは０〜１０％と低いことが特徴である。
このような本発明のアルキルガラクトシド組成物は、前記した本発明のアルキルガラクトシドの製造方法により得ることができる。
本発明のアルキルガラクトシド組成物は、低刺激性界面活性剤として有用であり、他の陰イオン界面活性剤に対する泡安定剤としても利用することができる。
The present invention also provides alkyl galactoside compositions.
The alkyl galactoside composition of the present invention is an alkyl galactoside composition containing an alkyl galactoside (a) having a sugar condensation degree of less than 4 and an alkyl galactoside (b) having a sugar condensation degree of 4 or more, wherein the alkyl galactoside (a) and alkyl The molar ratio [(a) :( b)] measured by GPC of galactoside (b) is 70:30 to 100: 0.
The molar ratio [(a) :( b)] measured by GPC represents the composition ratio (content ratio) of the alkylgalactoside composition. Thus, in the alkyl galactoside composition of the present invention, the molar ratio of the high condensate (b) having a sugar condensation degree of 4 or more in the alkyl galactoside is as low as 0.5 to 30%, preferably 0 to 10%. It is a feature.
Such an alkyl galactoside composition of the present invention can be obtained by the above-described method for producing an alkyl galactoside of the present invention.
The alkyl galactoside composition of the present invention is useful as a hypoallergenic surfactant and can also be used as a foam stabilizer for other anionic surfactants.
実施例１
５００ｍｌの５ッ口フラスコにパラトルエンスルホン酸一水和物０．１１ｇ（５．６×１０-4ｍｏｌ）、ガラクトース２０．００ｇ（０．１１ｍｏｌ）、ｎ−ドデシルアルコール３１０．２７ｇ（１．６７ｍｏｌ）を秤量し、窒素吹き込み口とリービッヒ冷却管を取り付け、１１５℃まで昇温した。昇温後、系内圧力を５．３ｋＰａ（４０ｍｍＨｇ）にして脱水反応を開始した。この際、反応混合溶液中に窒素を２５〜５０ｍｌ／ｍｉｎで吹き込み、生成する水を効率よく除去するようにして、４時間反応させアルキルガラクトシドを得た。
反応終了後常圧に戻し、反応終了物溶液が８０℃程度になった状態で、４８質量％水酸化ナトリウム水溶液０．０５ｇ（６．０×１０-4ｍｏｌ）を加えて中和した。また、得られたアルキルガラクトシドをＧＰＣ分析（装置：東ソー株式会社製、商品名、ＬＣ−８０２０ 高圧グラジエントシステム、カラム：東ソー株式会社製、商品名、ＴＳＫ−ＧＥＬ Ｇ２０００ＨＸＬ７．８＊３００とＴＳＫ−ＧＥＬ Ｇ１０００ＨＸＬ７．８＊３００の直列使用、展開溶媒：テトラヒドロフラン）した結果、ガラクトースの平均糖縮合度は１．２４であり、高縮合物のモル比は１．７％であった。
Example 1
In a 500 ml five-necked flask, 0.11 g (5.6 × 10 −4 mol) of paratoluenesulfonic acid monohydrate, 20.00 g (0.11 mol) of galactose, 310.27 g (1.67 mol) of n-dodecyl alcohol ) Were weighed, a nitrogen inlet and a Liebig condenser were attached, and the temperature was raised to 115 ° C. After the temperature increase, the pressure inside the system was set to 5.3 kPa (40 mmHg) to start the dehydration reaction. At this time, nitrogen was blown into the reaction mixture solution at 25 to 50 ml / min, and the reaction was carried out for 4 hours so as to efficiently remove the generated water to obtain alkyl galactoside.
After completion of the reaction, the pressure was returned to normal pressure, and with the reaction product solution at about 80 ° C., 0.05 g (6.0 × 10 −4 mol) of a 48 mass% sodium hydroxide aqueous solution was added for neutralization. The obtained alkyl galactoside was subjected to GPC analysis (apparatus: manufactured by Tosoh Corporation, trade name, LC-8020 high pressure gradient system, column: manufactured by Tosoh Corporation, trade name, TSK-GEL G2000HXL7.8 * 300 and TSK-GEL. As a result of using G1000HXL7.8 * 300 in series, developing solvent: tetrahydrofuran, the average sugar condensation degree of galactose was 1.24, and the molar ratio of the high condensate was 1.7%.
比較例１
実施例１におけるパラトルエンスルホン酸一水和物を０．３２ｇ（１．７×１０-3ｍｏｌ）、ガラクトースを６０．００ｇ（０．３３ｍｏｌ）、ｎ−ドデシルアルコールを３１０．２７ｇ（１．６７ｍｏｌ）とした以外は実施例１の操作を行い、反応時間８時間でアルキルガラクトシドを得た。
得られたアルキルガラクトシドを実施例１と同様にしてＧＰＣ分析した結果、ガラクトースの平均糖縮合度は２．０７であり、高縮合物のモル比は２９．４％であった。
Comparative Example 1
0.32 g (1.7 × 10 −3 mol) of paratoluenesulfonic acid monohydrate, 60.00 g (0.33 mol) of galactose, and 310.27 g (1.67 mol) of n-dodecyl alcohol in Example 1. Except for the above, the procedure of Example 1 was performed to obtain alkyl galactoside in a reaction time of 8 hours.
The obtained alkyl galactoside was subjected to GPC analysis in the same manner as in Example 1. As a result, the average sugar condensation degree of galactose was 2.07, and the molar ratio of the high condensate was 29.4%.
実施例２
３００ｍｌの４ッ口フラスコにパラトルエンスルホン酸一水和物０．０９９ｇ（５．２×１０-4ｍｏｌ）、ガラクトース１８．０５（０．１０ｍｏｌ）、ｎ−ブタノール７４．１８ｇ（１．００ｍｏｌ）を秤量し、窒素吹き込み口とリービッヒ冷却管を取り付け、１１５℃に昇温した。昇温後、還流が確認できた段階を反応開始とした。この際、反応混合溶液中に窒素を５０ｍｌ／ｍｉｎで吹き込み、生成する水を効率よく除去するようにして、３時間反応させ、ブチルガラクトシドのブタノール溶液を得た。
５００ｍｌの５ッ口フラスコにパラトルエンスルホン酸一水和物０．１０ｇ（５．３×１０-4ｍｏｌ）、ｎ−ドデシルアルコール２７９．９８ｇ（１．５０ｍｏｌ）を秤量し、そこにブチルガラクトシドのブタノール溶液を加えた。反応容器に窒素吹き込み口とリービッヒ冷却管を取り付け、１１５℃に昇温した。昇温後、系内圧力を５．３ｋＰａとするとともに窒素を５０ｍｌ／ｍｉｎで吹き込むことでブタノールを効率よく除去するようにして、６時間反応させ、アルキルガラクトシドを得た。反応終了後常圧に戻し、反応終了物溶液が８０℃程度になった状態で、４８質量％水酸化ナトリウム水溶液０．０４ｇ（４．８×１０-4ｍｏｌ）を加えて中和した。
得られたアルキルガラクトシドを実施例１と同様にしてＧＰＣ分析した結果、ガラクトースの平均糖縮合度は１．１６であり、高縮合物のモル比は０．１％であった。
Example 2
In a 300 ml four-necked flask, 0.099 g (5.2 × 10 −4 mol) of paratoluenesulfonic acid monohydrate, 18.05 (0.10 mol) of galactose, 74.18 g (1.00 mol) of n-butanol Were weighed, a nitrogen inlet and a Liebig condenser were attached, and the temperature was raised to 115 ° C. The reaction was started when the reflux was confirmed after the temperature was raised. At this time, nitrogen was blown into the reaction mixture solution at 50 ml / min, and the reaction was performed for 3 hours so as to efficiently remove generated water to obtain a butanol solution of butyl galactoside.
In a 500 ml five-necked flask, 0.10 g (5.3 × 10 −4 mol) of paratoluenesulfonic acid monohydrate and 279.98 g (1.50 mol) of n-dodecyl alcohol were weighed, and butyl galactoside was added thereto. Butanol solution was added. A nitrogen inlet and a Liebig condenser were attached to the reaction vessel, and the temperature was raised to 115 ° C. After raising the temperature, the system pressure was set to 5.3 kPa, and nitrogen was blown at 50 ml / min to efficiently remove butanol, and the reaction was performed for 6 hours to obtain alkyl galactoside. After the completion of the reaction, the pressure was returned to normal pressure, and in the state where the reaction product solution was about 80 ° C., a 48% by mass aqueous sodium hydroxide solution (0.04 g, 4.8 × 10 −4 mol) was added for neutralization.
The obtained alkyl galactoside was subjected to GPC analysis in the same manner as in Example 1. As a result, the average sugar condensation degree of galactose was 1.16, and the molar ratio of the high condensate was 0.1%.
実施例３
実施例２におけるｎ−ドデシルアルコールを１８９．５０ｇ（１．０２ｍｏｌ）とし、ブチルガラクトシドのブタノール溶液をｎ−ドデシルアルコール内に４時間かけて滴下した以外は、実施例２と同様の操作を行い、アルキルガラクトシドを得た。
得られたアルキルガラクトシドを実施例１と同様にしてＧＰＣ分析した結果、ガラクトースの平均糖縮合度は１．３８であり、高縮合物のモル比は４．７％であった。
Example 3
The same operation as in Example 2 was performed except that n-dodecyl alcohol in Example 2 was 189.50 g (1.02 mol), and a butanol solution of butyl galactoside was dropped into n-dodecyl alcohol over 4 hours, An alkyl galactoside was obtained.
The obtained alkyl galactoside was subjected to GPC analysis in the same manner as in Example 1. As a result, the average sugar condensation degree of galactose was 1.38, and the molar ratio of the high condensate was 4.7%.
実施例４
実施例２におけるｎ−ドデシルアルコールを３７２．７５ｇ（２．００ｍｏｌ）とし、ブチルガラクトシドのブタノール溶液をｎ−ドデシルアルコール内に４時間かけて滴下した以外は、実施例２と同様の操作を行い、アルキルガラクトシドを得た。
得られたアルキルガラクトシドを実施例１と同様にしてＧＰＣ分析した結果、ガラクトースの平均糖縮合度は１．１3であり、高縮合物のモル比は０．３％であった。
Example 4
Except that n-dodecyl alcohol in Example 2 was 372.75 g (2.00 mol) and a butanol solution of butyl galactoside was dropped into n-dodecyl alcohol over 4 hours, the same operation as in Example 2 was performed, An alkyl galactoside was obtained.
The obtained alkyl galactoside was subjected to GPC analysis in the same manner as in Example 1. As a result, the average sugar condensation degree of galactose was 1.13, and the molar ratio of the high condensate was 0.3%.
比較例２
実施例２におけるパラトルエンスルホン酸一水和物を０．１４ｇ（７．４×１０-4ｍｏｌ）、ガラクトースを２７．０４ｇ（０．１５ｍｏｌ）、ｎ−ブタノール１１１．１６ｇ（１．５０ｍｏｌ）、ｎ−ドデシルアルコールを１３９．６８ｇ（０．７５ｍｏｌ）とした以外は実施例２と同様の操作を行い、反応時間５時間でアルキルガラクトシドを得た。
得られたアルキルガラクトシドを実施例１と同様にしてＧＰＣ分析した結果、ガラクトースの平均糖縮合度は２．０２であり、高縮合物のモル比は２７．６％であった。
実施例１〜４及び比較例１、２に記載した反応において、得られたアルキルガラクトシド中の高縮合物のモル比を第１図に示した。
Comparative Example 2
0.14 g (7.4 × 10 −4 mol) of paratoluenesulfonic acid monohydrate in Example 2, 27.04 g (0.15 mol) of galactose, 111.16 g (1.50 mol) of n-butanol, The same operation as in Example 2 was performed except that n-dodecyl alcohol was changed to 139.68 g (0.75 mol), and an alkyl galactoside was obtained in a reaction time of 5 hours.
The obtained alkyl galactoside was subjected to GPC analysis in the same manner as in Example 1. As a result, the average sugar condensation degree of galactose was 2.02, and the molar ratio of the high condensate was 27.6%.
In the reactions described in Examples 1 to 4 and Comparative Examples 1 and 2, the molar ratio of the high condensate in the obtained alkyl galactoside is shown in FIG.
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| JP2008297290A (en) * | 2007-06-04 | 2008-12-11 | Kao Corp | Method for producing alkylgalactoside |
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