JPH07163381A - Production of diglycerin-1,2-diester - Google Patents
Production of diglycerin-1,2-diesterInfo
- Publication number
- JPH07163381A JPH07163381A JP5342344A JP34234493A JPH07163381A JP H07163381 A JPH07163381 A JP H07163381A JP 5342344 A JP5342344 A JP 5342344A JP 34234493 A JP34234493 A JP 34234493A JP H07163381 A JPH07163381 A JP H07163381A
- Authority
- JP
- Japan
- Prior art keywords
- diglycerin
- diester
- acid
- lipase
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title description 11
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 35
- 229930195729 fatty acid Natural products 0.000 claims abstract description 35
- 239000000194 fatty acid Substances 0.000 claims abstract description 35
- 108090001060 Lipase Proteins 0.000 claims abstract description 32
- 102000004882 Lipase Human genes 0.000 claims abstract description 32
- 239000004367 Lipase Substances 0.000 claims abstract description 32
- 235000019421 lipase Nutrition 0.000 claims abstract description 32
- 229940105990 diglycerin Drugs 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 26
- -1 diester compound Chemical class 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 125000005907 alkyl ester group Chemical group 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 6
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 abstract description 6
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 abstract description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 abstract description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 abstract description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 abstract description 5
- 150000005690 diesters Chemical class 0.000 abstract description 5
- 239000002736 nonionic surfactant Substances 0.000 abstract description 3
- 239000002537 cosmetic Substances 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 235000013305 food Nutrition 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 abstract 1
- 229940040461 lipase Drugs 0.000 description 27
- 238000000034 method Methods 0.000 description 13
- 239000007795 chemical reaction product Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 229960003656 ricinoleic acid Drugs 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 230000003834 intracellular effect Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 235000011837 pasties Nutrition 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical group C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 241000222120 Candida <Saccharomycetales> Species 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- UHPMCKVQTMMPCG-UHFFFAOYSA-N 5,8-dihydroxy-2-methoxy-6-methyl-7-(2-oxopropyl)naphthalene-1,4-dione Chemical compound CC1=C(CC(C)=O)C(O)=C2C(=O)C(OC)=CC(=O)C2=C1O UHPMCKVQTMMPCG-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- 241000588881 Chromobacterium Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- 241000223218 Fusarium Species 0.000 description 1
- 241000159512 Geotrichum Species 0.000 description 1
- 241000223198 Humicola Species 0.000 description 1
- 108010093096 Immobilized Enzymes Proteins 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- 241000235395 Mucor Species 0.000 description 1
- 241000187654 Nocardia Species 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 102000019280 Pancreatic lipases Human genes 0.000 description 1
- 108050006759 Pancreatic lipases Proteins 0.000 description 1
- 239000005643 Pelargonic acid Substances 0.000 description 1
- 241000228143 Penicillium Species 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 241000589516 Pseudomonas Species 0.000 description 1
- 241000235527 Rhizopus Species 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229940114079 arachidonic acid Drugs 0.000 description 1
- 235000021342 arachidonic acid Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 239000011942 biocatalyst Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 1
- 229940073769 methyl oleate Drugs 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000000199 molecular distillation Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 229940116369 pancreatic lipase Drugs 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 108010079522 solysime Proteins 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ジグリセリン−１，２
−ジエステルを高収率及び高純度で得ることができるジ
グリセリン−１，２−ジエステルの製造方法に関する。FIELD OF THE INVENTION The present invention relates to diglycerin-1,2.
-A method for producing diglycerin-1,2-diester, which allows the diester to be obtained in high yield and high purity.
【０００２】[0002]
【従来の技術】一般式（３）2. Description of the Related Art General formula (3)
【０００３】[0003]
【化４】 [Chemical 4]
【０００４】（式中、Ｒは１〜２個の水酸基を有してい
てもよい炭素数３〜２１の飽和又は不飽和のアルキル基
を表わす）で表わされるジグリセリン−１，２−ジエス
テル（ジグリセリン隣位ジエステル）は、食品、化粧
品、医薬品等の広範囲の分野に於いて利用されている非
イオン界面活性剤である。(Wherein R represents a saturated or unsaturated alkyl group having 3 to 21 carbon atoms and optionally having 1 to 2 hydroxyl groups), and a diglycerin-1,2-diester ( Diglycerin vicinal diester) is a nonionic surfactant used in a wide range of fields such as foods, cosmetics and pharmaceuticals.
【０００５】ジグリセリンジエステルの製造方法として
は、ジグリセリンと脂肪酸とをアルカリ触媒の存在下で
高温エステル化反応させる方法、ジグリセリンと油脂と
をアルカリ触媒の存在下で高温でエステル交換反応させ
る方法、ジグリセリンと脂肪酸クロリドとを反応させる
方法等が知られている。例えば、エステル交換反応は、
２００〜２４０℃の高温で、０．１％前後の濃度の水酸
化カルシウムを触媒として使用して２〜６時間反応させ
ることによって行われる。これらの方法に於いてはモノ
エステル、トリエステル、テトラエステル等の副生物が
生成するので、反応混合物を分子蒸留等の方法により精
製してジエステルを単離取得している。As the method for producing diglycerin diester, diglycerin and fatty acid are subjected to a high temperature esterification reaction in the presence of an alkali catalyst, and diglycerin and fats and oils are subjected to a transesterification reaction at a high temperature in the presence of an alkali catalyst. , A method of reacting diglycerin with a fatty acid chloride is known. For example, the transesterification reaction is
The reaction is carried out at a high temperature of 200 to 240 ° C. for 2 to 6 hours using calcium hydroxide having a concentration of about 0.1% as a catalyst. In these methods, by-products such as monoesters, triesters, and tetraesters are produced, so the reaction mixture is purified by a method such as molecular distillation to obtain diesters.
【０００６】特開平２−１９３４２号公報には、脂肪酸
アルキルエステルとモノイソプロピリデンジグリセリン
とを、アルカリ性媒体中で、１４０〜２２０℃の温度お
よび９５０〜５ミリバールの真空で反応させ、反応生成
物のイソプロピリデン基を酸性加水分解により脱離し
て、ジグリセリン−１，２−ジエステルを製造する方法
が開示されている。In JP-A-2-19342, a fatty acid alkyl ester and monoisopropylidene diglycerin are reacted in an alkaline medium at a temperature of 140 to 220 ° C. and a vacuum of 950 to 5 mbar to give a reaction product. The method for producing diglycerin-1,2-diester by dissociating the isopropylidene group of 1 by acidic hydrolysis is disclosed.
【０００７】上記のような公知の方法に於ては、アルカ
リ性で高温で反応を行うので、生成物が着色したり着臭
したりすることが避けられず、高純度の生成物を得るた
めに精製が困難であるとか、脂肪酸クロリドを使用する
方法の場合は、共存させるアミン類を除去することが困
難であると言う問題点がある。更に、脂肪酸として熱に
対して不安定であるリノール酸のような不飽和脂肪酸を
使用する場合や、上記のような条件下で分子内縮合を起
こすリシノール酸を使用する場合には、収率が低下した
り不純物が多くなって、上記の方法は好ましくない。In the known method as described above, since the reaction is carried out at a high temperature in an alkaline manner, it is inevitable that the product is colored or has an odor, so that a highly pure product is obtained. There are problems that purification is difficult and that it is difficult to remove coexisting amines in the case of using a fatty acid chloride. Furthermore, when using an unsaturated fatty acid such as linoleic acid which is unstable to heat as a fatty acid, or when using ricinoleic acid which causes intramolecular condensation under the above-mentioned conditions, the yield is The above method is not preferable because it is reduced or the impurities are increased.
【０００８】[0008]
【発明が解決しようとする課題】本発明の目的は、温和
な反応条件下で、熱に対して不安定であったり分子内縮
合を起こし易い脂肪酸が含まれていてもよい脂肪酸又は
そのエステルを原料として使用して、純度が高く精製も
容易なジグリセリン−１，２−ジエステルを高収率で得
ることができるジグリセリン−１，２−ジエステルの製
造方法を提供することにある。DISCLOSURE OF THE INVENTION An object of the present invention is to provide a fatty acid or ester thereof which may contain a fatty acid which is unstable to heat or is likely to undergo intramolecular condensation under mild reaction conditions. It is an object of the present invention to provide a method for producing diglycerin-1,2-diester, which can be used as a raw material to obtain diglycerin-1,2-diester in high yield with high purity and easy purification.
【０００９】[0009]
【課題を解決するための手段】本発明は、１，２−イソ
プロピリデンジグリセリンと、１，２−イソプロピリデ
ンジグリセリン１モル当り１．５モル以上の、一般式
（１）：The present invention provides 1,2-isopropylidene diglycerin and 1.5 or more mol of 1,2-isopropylidene diglycerin represented by the general formula (1):
【００１０】[0010]
【化５】 [Chemical 5]
【００１１】（式中、Ｒは、１〜２個の水酸基を有して
いてもよい炭素数３〜２１の飽和又は不飽和のアルキル
基を表わし、Ｒ1 は水素原子又は炭素数１〜６のアルキ
ル基を表わす）で表わされる脂肪酸又はその低級アルキ
ルエステルとを、リパーゼの存在下で、生成する水又は
低級アルコールを反応系外に除去しながら反応させて、
一般式（２）：(In the formula, R represents a saturated or unsaturated alkyl group having 3 to 21 carbon atoms and optionally having 1 to 2 hydroxyl groups, and R 1 is a hydrogen atom or 1 to 6 carbon atoms. Represents an alkyl group of) or a lower alkyl ester thereof in the presence of lipase, while removing the produced water or lower alcohol out of the reaction system,
General formula (2):
【００１２】[0012]
【化６】 [Chemical 6]
【００１３】（式中、Ｒは上記の通りである）で表わさ
れるジエステル化合物を製造し、次いでこのジエステル
化合物を酸の存在下で加水分解して、一般式（３）：A diester compound represented by the formula (wherein R is as described above) is produced, and the diester compound is then hydrolyzed in the presence of an acid to give a compound represented by the general formula (3):
【００１４】[0014]
【化７】 [Chemical 7]
【００１５】（式中、Ｒは上記の通りである）で表わさ
れるジグリセリン−１，２−ジエステルを得ることを特
徴とするジグリセリン−１，２−ジエステルの製造方法
である。A method for producing diglycerin-1,2-diester is characterized in that diglycerin-1,2-diester represented by the formula (wherein R is as described above) is obtained.
【００１６】本発明の好適な態様は下記の通りである。 （１）上記リパーゼが、固定化リパーゼ又は菌体内リパ
ーゼである上記のジグリセリン−１，２−ジエステルの
製造方法。The preferred embodiments of the present invention are as follows. (1) The method for producing the diglycerin-1,2-diester, wherein the lipase is immobilized lipase or intracellular lipase.
【００１７】（２）上記の脂肪酸又はその低級アルキル
エステルと、１，２−イソプロピリデンジグリセリンと
の反応を、２０〜８０℃の範囲内の温度で行う上記のジ
グリセリン−１，２−ジエステルの製造方法。(2) The above-mentioned diglycerin-1,2-diester in which the reaction of the above-mentioned fatty acid or its lower alkyl ester with 1,2-isopropylidene diglycerin is carried out at a temperature within the range of 20 to 80 ° C. Manufacturing method.
【００１８】本発明のジグリセリン−１，２−ジエステ
ルの製造方法の第一工程に於いては、前記一般式（１）
で表わされる脂肪酸又はその低級エステルと１，２−イ
ソプロピリデンジグリセリンとを、リパーゼの存在下で
反応させて、前記一般式（２）で表わされるジエステル
化合物を製造する。In the first step of the method for producing diglycerin-1,2-diester of the present invention, the above-mentioned general formula (1) is used.
The fatty acid represented by or the lower ester thereof and 1,2-isopropylidene diglycerin are reacted in the presence of lipase to produce the diester compound represented by the general formula (2).
【００１９】前記一般式（１）で表わされる脂肪酸の具
体例としては、酪酸、吉草酸、カプロン酸、エナント
酸、カプリル酸、ペラルゴン酸、カプリン酸、ウンデカ
ン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ゾー
マリン酸、ステアリン酸、オレイン酸、エライジン酸、
リノール酸、リノレン酸、アラキドン酸、ガドレン酸、
アラキン酸、ベヘン酸、エルカ酸、リシノール酸等を挙
げることができる。また、前記一般式（１）で表わされ
る脂肪酸エステルの具体例としては、上記のような脂肪
酸のメチルエステル、エチルエステル、プロピルエステ
ル、イソプロピルエステル、ブチルエステル、ヘキシル
エステル等を挙げることができる。これらの脂肪酸又は
脂肪酸エステルは、単独で使用してもよく、二種以上の
混合物、例えば、二種以上の脂肪酸の混合物、脂肪酸単
位及び／又はアルコール単位が異なる二種以上の脂肪酸
エステルの混合物、脂肪酸と脂肪酸エステルとの混合物
等の形で使用してもよい。Specific examples of the fatty acid represented by the general formula (1) include butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid. , Zomarinic acid, stearic acid, oleic acid, elaidic acid,
Linoleic acid, linolenic acid, arachidonic acid, gadrenic acid,
Examples thereof include arachidic acid, behenic acid, erucic acid and ricinoleic acid. Specific examples of the fatty acid ester represented by the general formula (1) include methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, and hexyl ester of the above fatty acids. These fatty acids or fatty acid esters may be used alone, or a mixture of two or more kinds, for example, a mixture of two or more kinds of fatty acids, a mixture of two or more kinds of fatty acid esters having different fatty acid units and / or alcohol units, It may be used in the form of a mixture of fatty acid and fatty acid ester.
【００２０】また、１，２−イソプロピリデンジグリセ
リンは公知の化合物である。Further, 1,2-isopropylidene diglycerin is a known compound.
【００２１】１，２−イソプロピリデンジグリセリンと
脂肪酸又は脂肪酸エステルとの割合は、１，２−イソプ
ロピリデンジグリセリン１モル当り脂肪酸又は脂肪酸エ
ステルが１．５モル以上であり、好ましくは１．５〜
２．２モルである。The ratio of 1,2-isopropylidene diglycerin to fatty acid or fatty acid ester is 1.5 mol or more of fatty acid or fatty acid ester per 1 mol of 1,2-isopropylidene diglycerin, preferably 1.5. ~
It is 2.2 mol.
【００２２】本発明の第一工程の反応系に存在させるリ
パーゼは、微生物リパーゼ、膵臓リパーゼ等どのような
リパーゼであってもよい。本発明に使用するのに好まし
いリパーゼとしては、例えば、アスペルギルス(Aspergi
llus) 属、カンジダ(Candida) 属、フザリウム(Fuzariu
m)属、ゲオトリクム(Geotrichum)属、フミコーラ(Humic
ola)属、ムコール(Mucor) 属、ノカルディア(Nocardia)
属、ペニシリウム(Penicillium) 属、リゾプス(Rhizopu
s)属、アクロモバクター(Achromobactor) 属、クロモバ
クテリウム(Chormobacterium) 属、シュードモナス(Pse
udomonas) 属等の微生物を起源とするリパーゼを挙げる
ことができる。The lipase present in the reaction system of the first step of the present invention may be any lipase such as microbial lipase and pancreatic lipase. Preferred lipases for use in the present invention include, for example, Aspergis.
llus), Candida, Fusarium (Fuzariu)
m) genus, Geotrichum genus, Humicola
ola), Mucor, Nocardia
Genus Penicillium, Rhizopu
s), Achromobactor, Chromobacterium, Pseudomonas
Examples thereof include lipases originating from microorganisms such as the genus udomonas).
【００２３】上記リパーゼは、固定化リパーゼ（吸着性
能を有する担体にリパーゼを吸着させたもの）又は菌体
内リパーゼ（微生物菌体にリパーゼを吸着又は結合させ
たもの）の形で使用することが好ましい。固定化リパー
ゼはリパーゼをそれ自体公知の方法、例えば、「固定化
酵素」（千畑一郎編集、講談社刊）の９〜８５頁及び
「固定化生体触媒」（千畑一郎編集、講談社刊）の１２
〜１０１頁に記載の方法によって固定化して調製するこ
とができる。特に好ましい担体はイオン交換樹脂であ
る。固定化リパーゼ及び菌体内リパーゼの形態でのリパ
ーゼ製剤は市販されており、容易に入手することができ
る。The above-mentioned lipase is preferably used in the form of immobilized lipase (having a lipase adsorbed on a carrier having an adsorbing ability) or intracellular lipase (having a lipase adsorbed or bound to a microbial cell). . Immobilized lipase is a method known per se for lipase, for example, "immobilized enzyme" (edited by Ichiro Chibata, published by Kodansha) on pages 9 to 85 and 12 of "immobilized biocatalyst" (edited by Ichiro Chibata, published by Kodansha).
It can be prepared by immobilization by the method described on page 101. A particularly preferred carrier is an ion exchange resin. Lipase preparations in the form of immobilized lipase and intracellular lipase are commercially available and can be easily obtained.
【００２４】本発明の第一工程の反応系に存在させる上
記リパーゼの量は特に限定されないが、一般に脂肪酸又
は脂肪酸エステル１ｇ当り、１０〜３６０，０００単
位、特に５００〜１００，０００単位であることが好ま
しい。The amount of the above lipase to be present in the reaction system of the first step of the present invention is not particularly limited, but it is generally 10 to 360,000 units, particularly 500 to 100,000 units per 1 g of fatty acid or fatty acid ester. Is preferred.
【００２５】本発明の第一工程は、一般に２０〜８０
℃、特に４０〜７０℃の温度で行うことが好ましい。反
応中に、原料として脂肪酸を使用した場合は水が、脂肪
酸の低級エステルを使用した場合は低級アルコールが生
成するので、この水又はアルコールを反応系外に除去し
ながら反応を行う。水又はアルコールを反応系外に除去
する方法としては、減圧下で水又はアルコールを留去す
る方法、反応液中に乾燥した不活性ガスを通し、水又は
アルコールを不活性ガスに随伴させて除去する方法、モ
レキュラーシーブスのような吸収剤を反応液に添加して
水又はアルコールを吸収させる方法等が挙げられる。反
応液を汚染しない点で、減圧下で水又はアルコールを留
去する方法が特に好ましい。その詳細については、例え
ば、特開昭５７−８７８７号公報に記載されている。The first step of the present invention is generally 20-80.
It is preferable to carry out at a temperature of 40 ° C, particularly 40 to 70 ° C. During the reaction, water is produced when a fatty acid is used as a raw material and a lower alcohol is produced when a lower ester of a fatty acid is used. Therefore, the reaction is carried out while removing this water or alcohol out of the reaction system. As a method of removing water or alcohol out of the reaction system, a method of distilling off water or alcohol under reduced pressure, a dry inert gas is passed through the reaction solution, and water or alcohol is removed along with the inert gas. And a method of adding an absorbent such as molecular sieves to the reaction solution to absorb water or alcohol. The method of distilling off water or alcohol under reduced pressure is particularly preferable because it does not contaminate the reaction solution. Details thereof are described in, for example, Japanese Patent Application Laid-Open No. 57-8787.
【００２６】第一工程の反応は、リパーゼ製剤に含まれ
る水分を除いて、実質的に非水系で行う。第一工程の反
応に、ヘキサン、オクタン、石油エーテル等の溶媒を存
在させてもよいが、溶媒の除去や精製を考慮すると、こ
れらの溶媒を使用しない方が好ましい。The reaction of the first step is carried out in a substantially non-aqueous system except for the water content contained in the lipase preparation. A solvent such as hexane, octane, or petroleum ether may be present in the reaction of the first step, but it is preferable not to use these solvents in consideration of removal and purification of the solvent.
【００２７】本発明の第一工程が終了した後、反応生成
混合物からリパーゼを分離し、前記一般式（２）で表わ
されるジエステル化合物を含む反応生成物を得る。分離
したリパーゼは繰り返し使用することができる。After the first step of the present invention is completed, the lipase is separated from the reaction product mixture to obtain a reaction product containing the diester compound represented by the general formula (2). The separated lipase can be used repeatedly.
【００２８】上記第一工程で得られた反応生成物中に
は、一般式（２）で表わされるジエステル化合物が一般
に約８５重量％以上の高含有率で含まれており、更に未
反応の脂肪酸又は脂肪酸エステル、１，２−イソプロピ
リデンジグリセリン並びに１，２−イソプロピリデンジ
グリセリンの１−位又は２−位のモノエステルが含まれ
ている。第一工程で得られた反応生成物を第二工程に付
すに際し、上記の未反応原料及びモノエステルを除去し
てもよく、また含有させたままでもよい。The reaction product obtained in the first step generally contains a diester compound represented by the general formula (2) in a high content of about 85% by weight or more, and further unreacted fatty acid. Alternatively, a fatty acid ester, 1,2-isopropylidene diglycerin and a monoester at the 1-position or 2-position of 1,2-isopropylidene diglycerin are included. When the reaction product obtained in the first step is subjected to the second step, the above-mentioned unreacted raw material and monoester may be removed or may be left as it is.
【００２９】本発明のジグリセリン−１，２−ジエステ
ルの製造方法の第二工程に於いては、第一工程で得られ
たジエステル化合物を酸の存在下で加水分解して、前記
一般式（３）で表わされるジグリセリン−１，２−ジエ
ステルを製造する。In the second step of the method for producing diglycerin-1,2-diester of the present invention, the diester compound obtained in the first step is hydrolyzed in the presence of an acid to give the above-mentioned general formula ( The diglycerin-1,2-diester represented by 3) is produced.
【００３０】上記第二工程の加水分解は、それ自体公知
の方法により行うことができ、例えば、酸としては、塩
酸、硫酸、酢酸等を使用することができ、反応温度は一
般に０〜４０℃の範囲内である。また、この反応系にエ
ーテル、酢酸などの溶媒を添加することが好ましい。The hydrolysis in the second step can be carried out by a method known per se. For example, hydrochloric acid, sulfuric acid, acetic acid or the like can be used as the acid, and the reaction temperature is generally 0 to 40 ° C. Within the range of. It is also preferable to add a solvent such as ether or acetic acid to this reaction system.
【００３１】上記第二工程の加水分解が終了した後、使
用した酸を留去するか又は重炭酸ナトリウム等の塩基、
ＯＨ型イオン交換樹脂等を用いて中和し、必要に応じて
活性炭などを用いて脱色し、更に、加水分解で生成した
アセトンや使用した溶媒を留去して、ジグリセリン−
１，２−ジエステルを得る。After the hydrolysis of the second step is completed, the acid used is distilled off or a base such as sodium bicarbonate is added.
It is neutralized with an OH type ion exchange resin or the like, and if necessary, decolorized with activated carbon or the like, and further, acetone produced by hydrolysis and the solvent used are distilled off to give diglycerin-
The 1,2-diester is obtained.
【００３２】上記第二工程の反応生成物中のジグリセリ
ン−１，２−ジエステルの含有量は一般に約８５重量％
以上で非常に高い。上記反応生成物には、更に未反応の
脂肪酸又は脂肪酸エステル、ジグリセリン、ジグリセリ
ンの１−位又は２−位のモノエステル等が含まれている
ことがある。特に高純度のジグリセリン−１，２−ジエ
ステルを必要とする場合には、上記のような不純物は公
知の方法（分別蒸留、クロマトグラフィーなど）により
容易に分離することができる。一般に界面活性剤として
の用途にジグリセリン−１，２−ジエステルを使用する
場合は、上記のような不純物は含有量も非常に少なく、
混入していてもジグリセリン−１，２−ジエステルの性
能に悪影響を与えることはないので、特にこれらの不純
物を分離することなく、本発明の第二工程の反応生成物
をそのまま使用することができる。The content of diglycerin-1,2-diester in the reaction product of the second step is generally about 85% by weight.
It's very high above. The above reaction product may further contain unreacted fatty acid or fatty acid ester, diglycerin, monoester of 1-position or 2-position of diglycerin, and the like. Especially when high-purity diglycerin-1,2-diester is required, the above impurities can be easily separated by a known method (fractional distillation, chromatography, etc.). Generally, when diglycerin-1,2-diester is used for the purpose of use as a surfactant, the content of the impurities as described above is very small,
Even if it is mixed, it does not adversely affect the performance of diglycerin-1,2-diester, so that it is possible to use the reaction product of the second step of the present invention as it is without separating these impurities. it can.
【００３３】[0033]
【実施例】次に、実施例及び比較例により本発明を更に
詳細に説明する。EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples.
【００３４】［実施例１］攪拌機付きフラスコに、１，
２−イソプロピリデンジグリセリン２０６ｇ（１．０モ
ル）及びオレイン酸５６４ｇ（２．０モル）を入れて混
合し、得られた混合物に、カンジダ・シリンドラセ(Can
dida cylindracea) の変異菌起源のリパーゼを含む市販
リパーゼ製剤（名糖産業株式会社製、商品名「リパーゼ
ＯＦ」、３６万単位／ｇ）２１ｇを添加混合した。フラ
スコ内を１５０ｍｍＨｇの絶対圧に減圧し、４０℃に維
持して、反応の間に生成する水を連続的に系外に除去し
ながら、攪拌下に８時間反応させて、１，２−イソプロ
ピリデンジグリセリンのオレイン酸ジエステルを製造し
た。Example 1 In a flask equipped with a stirrer,
206 g (1.0 mol) of 2-isopropylidene diglycerin and 564 g (2.0 mol) of oleic acid were added and mixed, and the resulting mixture was mixed with Candida cylindrace (Can).
21 g of a commercially available lipase preparation containing a lipase originating from a mutant strain of dida cylindracea (manufactured by Meito Sangyo Co., Ltd., trade name "Lipase OF", 360,000 units / g) was added and mixed. The inside of the flask was depressurized to an absolute pressure of 150 mmHg and maintained at 40 ° C., while continuously removing water generated during the reaction to the outside of the system, the mixture was reacted for 8 hours with stirring to give 1,2-isopropylamine. An oleic acid diester of lidene diglycerin was prepared.
【００３５】上記の反応生成混合物を５℃に冷却して、
これにエーテル２００ｍｌを添加した後リパーゼ製剤を
濾別し、濾液に濃塩酸２００ｍｌを１５〜０℃で添加混
合し、室温で３０分間攪拌下に加水分解反応を行った。
反応生成物を静置し、酸水溶液相を分離した後、飽和重
炭酸ナトリウム水溶液を添加して中和した。次いで中和
物を静置して水相を分離し、油相からエーテルを蒸発除
去して、ペースト状の生成物６２５ｇを得た。この生成
物はガスクロマトグラフィーによりジグリセリン−１，
２−オレイン酸ジエステルである（１，２−イソプロピ
リデンジグリセリンからの収率：９０％）ことが確認さ
れた。Cooling the above reaction product mixture to 5 ° C.,
After adding 200 ml of ether to this, the lipase preparation was filtered off, and 200 ml of concentrated hydrochloric acid was added to and mixed with the filtrate at 15 to 0 ° C., and a hydrolysis reaction was carried out at room temperature for 30 minutes with stirring.
The reaction product was allowed to stand and the aqueous acid phase was separated and then neutralized by adding saturated aqueous sodium bicarbonate solution. The neutralized product was then allowed to stand and the aqueous phase separated and the ether removed from the oil phase by evaporation to give 625 g of a pasty product. This product was analyzed by gas chromatography to give diglycerin-1,
It was confirmed to be 2-oleic acid diester (yield from 1,2-isopropylidene diglycerin: 90%).
【００３６】［実施例２］攪拌機付きフラスコに、１，
２−イソプロピリデンジグリセリン２０６ｇ（１．０モ
ル）及びオレイン酸メチル５９２ｇ（２．０モル）を入
れて混合し、得られた混合物に、実施例１で使用したリ
パーゼ製剤２１ｇを添加混合した。フラスコ内を２００
ｍｍＨｇの絶対圧に減圧し、４０℃に維持して、反応の
間に生成するメタノールを連続的に系外に除去しなが
ら、攪拌下に１０時間反応させて、１，２−イソプロピ
リデンジグリセリンのオレイン酸ジエステルを製造し
た。Example 2 In a flask equipped with a stirrer,
206 g (1.0 mol) of 2-isopropylidene diglycerin and 592 g (2.0 mol) of methyl oleate were added and mixed, and to the resulting mixture, 21 g of the lipase preparation used in Example 1 was added and mixed. 200 in the flask
The pressure was reduced to an absolute pressure of mmHg and maintained at 40 ° C., and while continuously removing methanol generated during the reaction, the reaction was carried out for 10 hours with stirring to obtain 1,2-isopropylidenediglycerin. An oleic acid diester of was prepared.
【００３７】上記の反応生成混合物を、実施例１に於け
ると同様に加水分解処理して、ペースト状の生成物６２
５ｇを得た。この生成物はガスクロマトグラフィーによ
りジグリセリン−１，２−オレイン酸ジエステルである
（１，２−イソプロピリデンジグリセリンからの収率：
９０％）ことが確認された。The above reaction product mixture was hydrolyzed in the same manner as in Example 1 to give a pasty product 62.
5 g was obtained. This product is diglycerin-1,2-oleic acid diester by gas chromatography (yield from 1,2-isopropylidene diglycerin:
90%) was confirmed.
【００３８】［実施例３］攪拌機付きフラスコに、１，
２−イソプロピリデンジグリセリン２０６ｇ（１．０モ
ル）及びリシノール酸５９６ｇ（２．０モル）を入れて
混合し、得られた混合物に、実施例１で使用したリパー
ゼ製剤２１ｇを添加混合した。フラスコ内を２００ｍｍ
Ｈｇの絶対圧に減圧し、４０℃に維持して、反応の間に
生成する水を連続的に系外に除去しながら、攪拌下に１
２時間反応させて、１，２−イソプロピリデンジグリセ
リンのリシノール酸ジエステルを製造した。Example 3 In a flask equipped with a stirrer,
206 g (1.0 mol) of 2-isopropylidene diglycerin and 596 g (2.0 mol) of ricinoleic acid were added and mixed, and 21 g of the lipase preparation used in Example 1 was added and mixed to the resulting mixture. 200 mm inside the flask
The pressure was reduced to an absolute pressure of Hg and maintained at 40 ° C., and water generated during the reaction was continuously removed from the system while stirring 1
By reacting for 2 hours, ricinoleic acid diester of 1,2-isopropylidene diglycerin was produced.
【００３９】上記の反応生成混合物を、実施例１に於け
ると同様に加水分解処理して、ペースト状の生成物６５
０ｇを得た。この生成物はガスクロマトグラフィーによ
りジグリセリン−１，２−リシノール酸ジエステルであ
る（１，２−イソプロピリデンジグリセリンからの収
率：８９．５％）ことが確認された。The above reaction product mixture was hydrolyzed in the same manner as in Example 1 to give a pasty product 65.
0 g was obtained. It was confirmed by gas chromatography that the product was diglycerin-1,2-ricinoleic acid diester (yield from 1,2-isopropylidene diglycerin: 89.5%).
【００４０】[0040]
【発明の効果】本発明のジグリセリン−１，２−ジエス
テルの製造方法は、熱に対して不安定であったり分子内
縮合を起こし易い脂肪酸が含まれていてもよい脂肪酸又
はそのエステルと１，２−イソプロピリデンジグリセリ
ンとから、温和な反応条件下で、純度が高く着色や異臭
もなく、精製の容易なジグリセリン−１，２−ジエステ
ルを高収率で得ることができるという顕著に優れた効果
を奏するものである。INDUSTRIAL APPLICABILITY The method for producing diglycerin-1,2-diester of the present invention comprises a fatty acid or an ester thereof which may contain a fatty acid which is unstable to heat or which easily causes intramolecular condensation. Remarkably, diglycerin-1,2-diester with high purity and without coloring or off-flavor, which is easy to purify, can be obtained in a high yield from 2,2-isopropylidene diglycerin under mild reaction conditions. It has an excellent effect.
Claims (1)
と、１，２−イソプロピリデンジグリセリン１モル当り
１．５モル以上の、一般式（１）： 【化１】 （式中、Ｒは、１〜２個の水酸基を有していてもよい炭
素数３〜２１の飽和又は不飽和のアルキル基を表わし、
Ｒ1 は水素原子又は炭素数１〜６のアルキル基を表わ
す）で表わされる脂肪酸又はその低級アルキルエステル
とを、リパーゼの存在下で、生成する水又は低級アルコ
ールを反応系外に除去しながら反応させて、一般式
（２）： 【化２】 （式中、Ｒは上記の通りである）で表わされるジエステ
ル化合物を製造し、次いでこのジエステル化合物を酸の
存在下で加水分解して、一般式（３）： 【化３】 （式中、Ｒは上記の通りである）で表わされるジグリセ
リン−１，２−ジエステルを得ることを特徴とするジグ
リセリン−１，２−ジエステルの製造方法。1. 1,2-isopropylidene diglycerin and 1.5 mol or more of 1,2-isopropylidene diglycerin per 1 mol of general formula (1): (In the formula, R represents a saturated or unsaturated alkyl group having 3 to 21 carbon atoms, which may have 1 to 2 hydroxyl groups,
R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) and a fatty acid or a lower alkyl ester thereof represented by the reaction in the presence of lipase while removing generated water or a lower alcohol out of the reaction system. Then, the general formula (2): A diester compound represented by the formula (wherein R is as described above) is produced, and the diester compound is hydrolyzed in the presence of an acid to give a compound represented by the general formula (3): A diglycerin-1,2-diester represented by the formula (wherein R is as described above) is obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5342344A JPH07163381A (en) | 1993-12-13 | 1993-12-13 | Production of diglycerin-1,2-diester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5342344A JPH07163381A (en) | 1993-12-13 | 1993-12-13 | Production of diglycerin-1,2-diester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07163381A true JPH07163381A (en) | 1995-06-27 |
Family
ID=18353004
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5342344A Pending JPH07163381A (en) | 1993-12-13 | 1993-12-13 | Production of diglycerin-1,2-diester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07163381A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0750848A4 (en) * | 1994-12-22 | 1999-06-02 | Kao Corp | Modifier and modifier composition for protein-containing substance |
| EP1483973A1 (en) * | 2003-06-04 | 2004-12-08 | Kao Corporation | Fat or oil composition |
| JP2009278930A (en) * | 2008-05-23 | 2009-12-03 | Mitsubishi Gas Chem Co Inc | Method for producing optically active organic carboxylic acid from organic carboxylic acid ester |
| JP2013100492A (en) * | 2011-10-17 | 2013-05-23 | Nof Corp | Branched polyethylene glycol linked with diacylglycerol, method for producing the same, and polyethylene glycol-modified liposome |
| JP2015110570A (en) * | 2013-12-05 | 2015-06-18 | エヴォニク インダストリーズ アーゲー | Polyglycerol partial esters, their preparation and use |
-
1993
- 1993-12-13 JP JP5342344A patent/JPH07163381A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0750848A4 (en) * | 1994-12-22 | 1999-06-02 | Kao Corp | Modifier and modifier composition for protein-containing substance |
| EP1483973A1 (en) * | 2003-06-04 | 2004-12-08 | Kao Corporation | Fat or oil composition |
| US7494680B2 (en) | 2003-06-04 | 2009-02-24 | Kao Corporation | Fat or oil composition |
| JP2009278930A (en) * | 2008-05-23 | 2009-12-03 | Mitsubishi Gas Chem Co Inc | Method for producing optically active organic carboxylic acid from organic carboxylic acid ester |
| JP2013100492A (en) * | 2011-10-17 | 2013-05-23 | Nof Corp | Branched polyethylene glycol linked with diacylglycerol, method for producing the same, and polyethylene glycol-modified liposome |
| JP2015110570A (en) * | 2013-12-05 | 2015-06-18 | エヴォニク インダストリーズ アーゲー | Polyglycerol partial esters, their preparation and use |
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