JPH11222521A - Production of polyglycerol monofatty acid ester - Google Patents
Production of polyglycerol monofatty acid esterInfo
- Publication number
- JPH11222521A JPH11222521A JP3977098A JP3977098A JPH11222521A JP H11222521 A JPH11222521 A JP H11222521A JP 3977098 A JP3977098 A JP 3977098A JP 3977098 A JP3977098 A JP 3977098A JP H11222521 A JPH11222521 A JP H11222521A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- acid ester
- glycidol
- fatty acid
- polyglycerin
- 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.)
- Granted
Links
- 150000002148 esters Chemical class 0.000 title claims abstract description 58
- 239000002253 acid Substances 0.000 title claims abstract description 56
- 229920000223 polyglycerol Polymers 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 239000000194 fatty acid Substances 0.000 claims abstract description 56
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 54
- 229930195729 fatty acid Natural products 0.000 claims abstract description 54
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims abstract description 50
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 45
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 17
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- 239000005639 Lauric acid Substances 0.000 claims abstract description 8
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 235000021355 Stearic acid Nutrition 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 5
- 239000008117 stearic acid Substances 0.000 claims description 5
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 26
- -1 lauric acid Chemical class 0.000 abstract description 22
- 239000000203 mixture Substances 0.000 abstract description 3
- 241001550224 Apha Species 0.000 abstract description 2
- WOKDXPHSIQRTJF-UHFFFAOYSA-N 3-[3-[3-[3-[3-[3-[3-[3-[3-(2,3-dihydroxypropoxy)-2-hydroxypropoxy]-2-hydroxypropoxy]-2-hydroxypropoxy]-2-hydroxypropoxy]-2-hydroxypropoxy]-2-hydroxypropoxy]-2-hydroxypropoxy]-2-hydroxypropoxy]propane-1,2-diol Chemical compound OCC(O)COCC(O)COCC(O)COCC(O)COCC(O)COCC(O)COCC(O)COCC(O)COCC(O)COCC(O)CO WOKDXPHSIQRTJF-UHFFFAOYSA-N 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 34
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 19
- 235000011007 phosphoric acid Nutrition 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000012644 addition polymerization Methods 0.000 description 9
- 235000011187 glycerol Nutrition 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 7
- 239000000839 emulsion Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000000499 gel Substances 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- 235000013305 food Nutrition 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 235000013373 food additive Nutrition 0.000 description 3
- 239000002778 food additive Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003995 emulsifying agent Substances 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
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- SIOLDWZBFABPJU-UHFFFAOYSA-N isotridecanoic acid Chemical compound CC(C)CCCCCCCCCC(O)=O SIOLDWZBFABPJU-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- 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
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 1
- KIHBGTRZFAVZRV-UHFFFAOYSA-N 2-Hydroxyoctadecanoic acid Natural products CCCCCCCCCCCCCCCCC(O)C(O)=O KIHBGTRZFAVZRV-UHFFFAOYSA-N 0.000 description 1
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-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
- OWNRRUFOJXFKCU-UHFFFAOYSA-N Bromadiolone Chemical compound C=1C=C(C=2C=CC(Br)=CC=2)C=CC=1C(O)CC(C=1C(OC2=CC=CC=C2C=1O)=O)C1=CC=CC=C1 OWNRRUFOJXFKCU-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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 235000021319 Palmitoleic acid Nutrition 0.000 description 1
- YDHWWBZFRZWVHO-UHFFFAOYSA-N [hydroxy(phosphonooxy)phosphoryl] phosphono hydrogen phosphate Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(=O)OP(O)(O)=O YDHWWBZFRZWVHO-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical group OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- FJTUUPVRIANHEX-UHFFFAOYSA-N butan-1-ol;phosphoric acid Chemical compound CCCCO.OP(O)(O)=O FJTUUPVRIANHEX-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- SECPZKHBENQXJG-UHFFFAOYSA-N cis-palmitoleic acid Natural products CCCCCCC=CCCCCCCCC(O)=O SECPZKHBENQXJG-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- QPPQHRDVPBTVEV-UHFFFAOYSA-N isopropyl dihydrogen phosphate Chemical compound CC(C)OP(O)(O)=O QPPQHRDVPBTVEV-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- CABDEMAGSHRORS-UHFFFAOYSA-N oxirane;hydrate Chemical compound O.C1CO1 CABDEMAGSHRORS-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 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
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 229940048102 triphosphoric acid Drugs 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyethers (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ポリグリセリンモ
ノ脂肪酸エステルの製造方法に関する。更に詳しくは、
ポリグリセリンモノ脂肪酸エステルの含有率が高く、ポ
リグリセリンの重合度が高く、色相に優れ、ゲル状物を
副生しないポリグリセリンモノ脂肪酸エステルの製造方
法に関する。本発明により得られたポリグリセリンモノ
脂肪酸エステルは食品、化粧品、医薬などの分野におけ
る乳化剤や基剤として有用である。The present invention relates to a method for producing a polyglycerol monofatty acid ester. More specifically,
The present invention relates to a method for producing a polyglycerin monofatty acid ester having a high content of polyglycerin monofatty acid ester, a high degree of polymerization of polyglycerin, an excellent hue, and which does not produce a gel. The polyglycerol monofatty acid ester obtained according to the present invention is useful as an emulsifier or base in the fields of food, cosmetics, medicine and the like.
【０００２】[0002]
【従来の技術】近年、ポリグリセリン脂肪酸エステルは
食品添加物として認可され、使用量も次第に増加してい
る。一般に、このエステルは、原料として重合度の異な
るポリグリセリンと鎖長の異なる脂肪酸とを組合わせる
ことにより広い範囲のＨＬＢ値のエステルが得られ、ま
た酸性領域で高い安定性を示すことから、特に食品分野
において、乳化剤や粘度調整剤として広く用いられてい
る。ポリグリセリン脂肪酸エステルの製造法としては、
（１）ポリグリセリンと脂肪酸のエステル化反応、
（２）ポリグリセリンと脂肪酸エステルとのエステル交
換反応、（３）ポリグリセリンと油脂とのエステル交換
反応、（４）グリシドールと脂肪酸モノグリセライドと
の付加重合反応、（５）グリシドールと脂肪酸との付加
重合反応などがある。このうち、（２）〜（３）の方法
については反応性、生成したポリグリセリン脂肪酸エス
テルの品質、純度、などから制約の多い方法である。2. Description of the Related Art In recent years, polyglycerin fatty acid esters have been approved as food additives, and their use has been gradually increasing. In general, this ester is obtained by combining esters of polyglycerin having different degrees of polymerization with fatty acids having different chain lengths as raw materials to obtain an ester having a wide range of HLB values, and showing high stability in an acidic region. In the food field, it is widely used as an emulsifier and a viscosity modifier. As a method for producing polyglycerin fatty acid ester,
(1) polyglycerin and fatty acid esterification reaction,
(2) transesterification reaction between polyglycerin and fatty acid ester, (3) transesterification reaction between polyglycerin and fat, (4) addition polymerization reaction between glycidol and fatty acid monoglyceride, (5) addition polymerization between glycidol and fatty acid There are reactions. Among them, the methods (2) and (3) have many restrictions in terms of reactivity, quality and purity of the produced polyglycerol fatty acid ester, and the like.
【０００３】（１）の方法はＪＡＯＣＳ（Journal of A
merican 0il Chemists’ Society）第５８巻、第８７８
頁（１９８ｌ年）に記載され、ポリグリセリンと脂肪酸
とをアルカリ触媒の存在下にエステル化反応を行ってポ
リグリセリン脂肪酸エステルを得る方法が開示されてい
る。また特開平６−４１００７号公報にも同様の方法が
開示されている。この方法では、一般に、原料のポリグ
リセリンとしては、反応活性水酸基が平均で４〜１０の
ものが使用され、モノ置換の脂肪酸エステル体を製造し
ようとしても、使用する脂肪酸の当量に対し、反応活性
水酸基の割合が多く、生成したポリグリセリンモノ脂肪
酸エステル中には、目的とするモノ脂肪酸エステル体の
みならず、未反応のポリグリセリン、ジエステル、トリ
エステル、テトラエステル等の多置換エステル化物が残
存していることが指摘されている（N.Garti,et al,ＪＡ
ＯＣＳ（Journal of American 0il Chemists’ Societ
y）第５９巻、第３１７〜３１９頁（１９８２年））。
（４）の方法については、ＵＳＰ４，５１５，７７５に
記載されている。この方法では、原料の脂肪酸モノグリ
セライドの精製の度合により、反応生成物の純度が大き
く作用される。特に、グリセリンと脂肪酸との反応によ
り得られる、脂肪酸モノグリセライドを原料に使用した
場合には、（１）と同様に、原料中にグリセリン成分の
残存が認められ、グリシドールの付加重合反応で得られ
たポリグリセリンモノ脂肪酸エステル中のモノ脂肪酸エ
ステル体含有率は約４０％であり、残りの６０％程度は
未反応のグリセリンおよび２置換以上のエステルとなる
ことが認められている（津田滋、モノグリセリド、P67
(1985)、槙書店）。（５）の方法については、特開昭５
１−６５７０５号公報にグリセリンのモノ脂肪酸エステ
ルに関して記載されているが、この開示された技術によ
れば、不活性な溶剤の存在下で高度百分比率のカルボン
酸−１−モノグリセライド（後記化学式［１］において
ｎの値が平均で１である。）を製造する方法で、グリセ
リンの重合度が平均で１のものであり、ポリグリセリン
のモノ脂肪酸エステルに関しては、全く言及されておら
ず、実際の検討がなされていない。The method (1) is based on JAOCS (Journal of A).
American 0il Chemists' Society) Vol. 58, No. 878
(1981) discloses a method for obtaining a polyglycerin fatty acid ester by subjecting polyglycerin and a fatty acid to an esterification reaction in the presence of an alkali catalyst. A similar method is disclosed in Japanese Patent Application Laid-Open No. 6-41007. In this method, generally, a raw material polyglycerol having an average of 4 to 10 reactive hydroxyl groups is used. Even if an attempt is made to produce a mono-substituted fatty acid ester, the reactive activity is based on the equivalent of the fatty acid used. In the polyglycerol monofatty acid ester having a large ratio of hydroxyl groups, not only the intended monofatty acid ester but also unreacted polyglycerol, diester, triester, tetraester, and other polysubstituted esterified compounds remain. (N. Garti, et al, JA
OCS (Journal of American 0il Chemists' Societ
y) Vol. 59, pp. 317-319 (1982)).
The method (4) is described in US Pat. No. 4,515,775. In this method, the purity of the reaction product is greatly affected by the degree of purification of the raw material fatty acid monoglyceride. In particular, when fatty acid monoglyceride obtained by the reaction between glycerin and a fatty acid was used as a raw material, a glycerin component remained in the raw material, as in (1), and the glycerol was obtained by an addition polymerization reaction of glycidol. The monofatty acid ester content in the polyglycerin monofatty acid ester is about 40%, and it is recognized that the remaining about 60% is unreacted glycerin and di- or higher-substituted esters (Shigeru Tsuda, Monoglyceride, P67
(1985), Maki Shoten). The method (5) is described in
No. 1-65705 describes a monofatty acid ester of glycerin. According to the disclosed technology, a high percentage of carboxylic acid-1-monoglyceride (described later in the chemical formula [1] Wherein the value of n is 1 on average.), The degree of polymerization of glycerin is 1 on average, and no mention is made of polyglycerol monofatty acid esters at all. Not considered.
【０００４】なお、グリシドールの付加重合反応を使用
した技術としては、（１）〜（３）の方法で使用するポ
リグリセリンを製造する際のグリセリンとグリシドール
の付加重合反応（特公平１−５５２５４号公報、特公平
４−１１５３２号公報、特公平５−１２９１号公報）ま
たは脂肪酸とグリシドールの付加重合反応後、加水分解
反応を経たポリグリセリンの製造（特公平４−６９６２
１号公報）、ポリグリセリンモノアルキルエーテル、ポ
リグリセリンモノアルキルチオエーテルの製造（ＵＳＰ
３，８２１，３７２、ＵＳＰ３，９６６，３９８、ＵＳ
Ｐ４，０８７，４６６等）等が開示されている。[0004] As a technique using the addition polymerization reaction of glycidol, there is known an addition polymerization reaction of glycerin and glycidol in producing polyglycerin used in the methods (1) to (3) (Japanese Patent Publication No. 1-55254). JP-B-4-11532, JP-B5-11291) or production of polyglycerin which is subjected to an addition polymerization reaction of a fatty acid and glycidol followed by a hydrolysis reaction (Japanese Patent Publication 4-6962).
No. 1), production of polyglycerin monoalkyl ether and polyglycerin monoalkylthioether (USP
3,821,372, USP 3,966,398, US
P4, 087, 466).
【０００５】しかしながら、特公平４−６９６２１号公
報の脂肪酸とグリシドールの付加重合反応後、加水分解
反応を経由したポリグリセリンの製造では、用いる脂肪
酸が低級（炭素数２〜６）脂肪酸であり、かつ、目的は
ポリグリセリンの製造であり、ポリグリセリン脂肪酸エ
ステルについては全く言及されていない。このように、
従来使用されているポリグリセリンモノ脂肪酸エステル
には、未置換のポリグリセリンおよび２置換以上のエス
テル化物が多く残存し、それらを界面活性剤、食品分野
の乳化安定剤に応用した場合に、表面張力の低下、分散
力の低下、起泡力の低下、乳化安定性の低下が危惧され
ている。However, in the production of polyglycerin via a hydrolysis reaction after the addition polymerization reaction of a fatty acid and glycidol disclosed in Japanese Patent Publication No. 4-69621, the fatty acid used is a lower (2 to 6 carbon atoms) fatty acid, and The purpose is to produce polyglycerin, and there is no mention of polyglycerin fatty acid esters. in this way,
Conventionally used polyglycerol monofatty acid esters contain a large amount of unsubstituted polyglycerin and esterified products having two or more substitutions, and when these are applied to surfactants and emulsion stabilizers in the food field, the surface tension is reduced. It is feared that the water content, the dispersing power, the foaming power, and the emulsification stability are lowered.
【０００６】一方、未置換のポリグリセリンの除去方法
としては、水溶性有機溶剤及び水の中から選ばれた少な
くとも１種と、非水溶性有機溶剤の中から選ばれた少な
くとも１種とを併用した混合溶剤で未反応ポリグリセリ
ンを分液除去する方法（特開昭６３−２３８３７号公
報）、エステル化反応生成物の溶液をアルキルシリル化
シリカゲルと接触、吸着させ未反応ポリグリセリンを除
去する方法（特開平３−８１２５２号公報）、水溶性有
機溶剤及び水または塩析剤を含む水溶液を併用して未反
応ポリグリセリンを抽出除去する方法（特開平６−４１
００７号公報）が提案されている。On the other hand, as a method for removing unsubstituted polyglycerin, at least one selected from water-soluble organic solvents and water and at least one selected from non-water-soluble organic solvents are used in combination. (Japanese Unexamined Patent Publication (Kokai) No. 63-23837), a method of contacting and adsorbing a solution of an esterification reaction product with an alkylsilylated silica gel to remove unreacted polyglycerin. (JP-A-3-81252), a method of extracting and removing unreacted polyglycerin using a water-soluble organic solvent and an aqueous solution containing water or a salting-out agent (JP-A-6-41)
007 publication) has been proposed.
【０００７】しかしながら、特開昭６３−２３８３７号
公報記載の方法では、非水溶性有機溶剤として述べられ
ているベンゼン、トルエン等の芳香族系炭化水素は、そ
の安全性に疑問が持たれ、食品用途に関しては問題があ
る。また、この方法に於ては、ポリグリセリンに対する
脂肪酸の反応モル比が１以下に限定されており、１を越
えるモル比の場合の有効性については記載されていな
い。また、反応モル比が１以下の場合でも、トルエン／
メタノール系などでは、含水メタノール相にかなりの量
の高ＨＬＢのポリグリセリン脂肪酸エステルが移行する
ことが認められ、さらに、トルエン／メタノール系など
では、未反応ポリグリセリンの分離が極めて不十分であ
るなど工業的に実施するにはいくつもの問題点があり、
特開平３−８１２５２号公報記載のアルキルシリル化シ
リカゲルによって分割する方法は、運転コストが高く、
また操作も煩雑であるという欠点がある。さらに、これ
らの先行技術は特開平６−４１００７号公報記載方法も
含め未反応ポリグリセリンは除去できるが、２置換以上
のエステル化物の除去は不可能であるという欠点を有し
ている。However, in the method described in Japanese Patent Application Laid-Open No. 63-23837, aromatic hydrocarbons such as benzene and toluene described as water-insoluble organic solvents are questioned about their safety, There are problems with use. Further, in this method, the reaction molar ratio of the fatty acid to polyglycerin is limited to 1 or less, and the effectiveness in the case of a molar ratio exceeding 1 is not described. Even when the reaction molar ratio is 1 or less, toluene /
In the case of a methanol system, a considerable amount of high HLB polyglycerin fatty acid ester is observed to be transferred to the aqueous methanol phase, and in the case of the toluene / methanol system, separation of unreacted polyglycerin is extremely insufficient. There are a number of issues with industrial implementation,
The method of separating with an alkylsilylated silica gel described in JP-A-3-81252 has a high operating cost,
There is also a disadvantage that the operation is complicated. Further, these prior arts have the disadvantage that unreacted polyglycerin can be removed, including the method described in JP-A-6-41007, but it is impossible to remove di- or more-substituted esterified products.
【０００８】そこで、界面活性剤、食品分野の乳化安定
剤に応用した場合に、表面張力の向上、分散力の向上、
起泡力の向上、乳化安定性の向上が期待される、モノ脂
肪酸エステル体含有率の高いポリグリセリンモノ脂肪酸
エステルおよびその製造方法が求められていた。Therefore, when applied to surfactants and emulsion stabilizers in the field of foods, the surface tension and the dispersing power can be improved.
There has been a demand for a polyglycerol monofatty acid ester having a high monofatty acid ester content, which is expected to improve foaming power and emulsion stability, and a method for producing the same.
【０００９】しかし、従来の技術では、反応が無触媒で
行われる場合には、生成物の色相が悪くなったり、未反
応グリシドールが多かったり、触媒の存在下で行われる
としても触媒を脂肪酸と共に予め存在させておき、そこ
にグリシドールを添加する方法であるので、生成物中に
ゲル状物が発生するという問題があった。However, in the prior art, when the reaction is carried out in the absence of a catalyst, the color of the product deteriorates, the amount of unreacted glycidol is large, or even if the reaction is carried out in the presence of a catalyst, the catalyst is combined with the fatty acid. Since glycidol is added to glycidol in advance, there is a problem that a gel is generated in the product.
【００１０】[0010]
【発明が解決しようとする課題】本発明の目的は、ポリ
グリセリンモノ脂肪酸エステルの含有率が高く、ポリグ
リセリンの重合度が高く、色相に優れ、ゲル状物を副生
せず、未反応グリシドールの少ないポリグリセリンモノ
脂肪酸エステルの製造方法を提供することである。SUMMARY OF THE INVENTION It is an object of the present invention to provide a polyglycerol monofatty acid ester having a high content, a high degree of polymerization of polyglycerin, an excellent hue, no gel-like substance, and an unreacted glycidol. It is an object of the present invention to provide a method for producing a polyglycerol monofatty acid ester having a low content.
【００１１】[0011]
【課題を解決するための手段】本発明者は、脂肪酸とグ
リシドールを反応させてポリグリセリンモノ脂肪酸エス
テルを製造する際に、リン酸触媒を反応の途中で添加す
ることにより、上記問題を解決できることを見いだし本
発明を完成させるに至った。すなわち本発明の第１によ
れば、脂肪酸にグリシドールの一部を加えて反応させた
後、触媒を加え、グリシドールの残りを加えて反応させ
ることを特徴とする、モノ脂肪酸エステル体を主成分と
するポリグリセリンモノ脂肪酸エステルの製造方法が提
供される。本発明の第２によれば、脂肪酸のアルキル基
が炭素数６〜２１である本発明の第１に記載のポリグリ
セリンモノ脂肪酸エステルの製造方法が提供される。本
発明の第３によれば、脂肪酸がラウリン酸またはステア
リン酸のいずれかであることを特徴とする本発明の第１
〜２のいずれかに記載のポリグリセリンモノ脂肪酸エス
テルの製造方法が提供される。本発明の第４によれば、
触媒が、リン酸または酸性リン酸エステルである本発明
の第１〜３のいずれかに記載のポリグリセリンモノ脂肪
酸エステルの製造方法が提供される。本発明の第５によ
れば、グリシドールの一部の量が、脂肪酸と等モル以上
の量であることを特徴とする本発明の第１〜４のいずれ
かに記載のポリグリセリンモノ脂肪酸エステルの製造方
法が提供される。本発明の第６によれば、ポリグリセリ
ンの重合度が２以上である本発明の第１〜５のいずれか
に記載のポリグリセリンモノ脂肪酸エステルの製造方法
が提供される。Means for Solving the Problems The present inventor can solve the above problem by adding a phosphoric acid catalyst in the course of the reaction when a fatty acid and glycidol are reacted to produce a polyglycerol monofatty acid ester. And completed the present invention. That is, according to the first aspect of the present invention, a fatty acid ester is reacted with a part of glycidol added to a fatty acid, a catalyst is added, and the remaining glycidol is added and reacted. A method for producing a polyglycerin monofatty acid ester is provided. According to a second aspect of the present invention, there is provided the method for producing a polyglycerol monofatty acid ester according to the first aspect, wherein the alkyl group of the fatty acid has 6 to 21 carbon atoms. According to a third aspect of the present invention, the fatty acid is either lauric acid or stearic acid.
3. A method for producing a polyglycerin monofatty acid ester according to any one of (1) to (2). According to a fourth aspect of the invention,
The method for producing a polyglycerol monofatty acid ester according to any one of the first to third aspects of the present invention, wherein the catalyst is phosphoric acid or an acidic phosphoric acid ester. According to a fifth aspect of the present invention, the polyglycerol monofatty acid ester according to any one of the first to fourth aspects of the present invention, wherein a part of the amount of glycidol is at least equimolar to the amount of the fatty acid. A manufacturing method is provided. According to a sixth aspect of the present invention, there is provided the method for producing a polyglycerin monofatty acid ester according to any one of the first to fifth aspects of the present invention, wherein the degree of polymerization of the polyglycerin is 2 or more.
【００１２】[0012]
【発明の実施の形態】グリシドールとの付加重合反応で
用いられる酸としては、特に制限はなく、ギ酸、酢酸の
ような低分子量のカルボン酸でも芳香族カルボン酸のよ
うな酸でも、二価のカルボン酸でも、フェノール性水酸
基を持つ酸でもよいが、好ましくはアルキル基の炭素数
が６〜２１の脂肪酸であり、特に好ましくは炭素数が７
〜２１の脂肪酸である。脂肪酸は飽和脂肪酸でも不飽和
脂肪酸でもよく、また直鎖状脂肪酸でも側鎖をもつ脂肪
酸でも、更には炭素鎖がヒドロキシル基で置換された置
換脂肪酸でもよい。これらの脂肪酸としては、例えばカ
プロン酸、カプリル酸、２−エチルヘキサン酸、カプリ
ン酸、ラウリン酸、イソトリデカン酸、ミリスチン酸、
パルミチン酸、パルミトレイン酸、ステアリン酸、イソ
ステアリン酸、オレイン酸、リノール酸、ベヘン酸、エ
ルカ酸、リシノール酸、ヒドロキシステアリン酸などが
ある。これらの中でも特にラウリン酸またはステアリン
酸であることが好ましい。これら脂肪酸は単独で使用で
きるほか、２種以上を任意に混合して反応に用いてもよ
い。BEST MODE FOR CARRYING OUT THE INVENTION The acid used in the addition polymerization reaction with glycidol is not particularly limited, and a low-molecular-weight carboxylic acid such as formic acid or acetic acid or an acid such as an aromatic carboxylic acid may be used. Although it may be a carboxylic acid or an acid having a phenolic hydroxyl group, it is preferably a fatty acid having 6 to 21 carbon atoms in the alkyl group, particularly preferably 7 to 21 carbon atoms.
~ 21 fatty acids. The fatty acid may be a saturated fatty acid or an unsaturated fatty acid, a linear fatty acid, a fatty acid having a side chain, or a substituted fatty acid having a carbon chain substituted by a hydroxyl group. Examples of these fatty acids include caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid,
Examples include palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, behenic acid, erucic acid, ricinoleic acid, and hydroxystearic acid. Of these, lauric acid or stearic acid is particularly preferred. These fatty acids can be used alone, or two or more kinds may be arbitrarily mixed and used in the reaction.
【００１３】前記脂肪酸とグリシドールとの反応は、反
応初期においては無触媒で行われる。具体的には、反応
容器中に脂肪酸をとり、これにグリシドールを少量ずつ
添加しながら反応を行う。反応温度は５０〜１８０℃、
好ましくは７０〜１６０℃であり、より好ましくは１２
０〜１４０℃である。５０℃未満では反応速度が小さ
く、また１８０℃を越えると着色が激しくなり、２３０
℃以上ではグリシドールが分解して副反応を起こし好ま
しくない。この場合、反応温度の上昇を防止するため
に、グリシドールと反応しない低沸点化合物または不活
性な溶媒を添加してもよい。また反応は窒素ガス雰囲気
下で行うことが望ましく、必要に応じて加圧してもよ
い。The reaction between the fatty acid and glycidol is carried out without a catalyst at the beginning of the reaction. Specifically, a fatty acid is placed in a reaction vessel, and the reaction is performed while glycidol is added little by little to the fatty acid. The reaction temperature is 50-180 ° C,
Preferably it is 70-160 degreeC, More preferably, it is 12 degreeC.
0-140 ° C. If the temperature is lower than 50 ° C., the reaction rate is low.
If the temperature is higher than ℃, glycidol is decomposed to cause a side reaction, which is not preferable. In this case, a low-boiling compound that does not react with glycidol or an inert solvent may be added to prevent the reaction temperature from rising. The reaction is desirably performed in a nitrogen gas atmosphere, and may be pressurized if necessary.
【００１４】触媒の反応系への添加は、グリシドールの
一部が添加された後に、好ましくは脂肪酸と等モル以上
のグリシドールが添加された後に、さらに好ましくは脂
肪酸に対して２〜３倍モルのグリシドールが添加された
後に行われる。触媒をグリシドールの添加前に存在させ
ると、ゲル状物が生成し製品中に混入するか、それを除
くために分離操作が必要になる。なお、ここでゲル状物
はポリグリセリンの多置換エステル体（エステル基が２
個以上付加したもの）等と考えられる。しかし、触媒の
反応系への添加は、グリシドールの全量が添加される前
であり、好ましくは、グリシドールの６０％が未添加の
時点である。触媒の反応系への添加が、グリシドールの
全量が添加された後であると反応生成物の色相が悪くな
り、またグリシドールの残存量も多くなりがちである。
触媒の反応系への添加は、一括して行われても分割して
行われてもよい。The catalyst is added to the reaction system after a part of glycidol is added, preferably after glycidol is added in an amount equal to or more than an equimolar amount to the fatty acid, and more preferably in an amount of 2 to 3 times the molar amount of the fatty acid. This is done after the glycidol has been added. If the catalyst is present prior to the addition of glycidol, a gel will be formed and incorporated into the product, or a separation operation will be required to remove it. Here, the gel is a polyglycerol polysubstituted ester (ester group having 2
Or more). However, the catalyst is added to the reaction system before the entire amount of glycidol is added, preferably at a point where 60% of the glycidol has not been added. When the catalyst is added to the reaction system after the entire amount of glycidol has been added, the color of the reaction product becomes poor and the residual amount of glycidol tends to increase.
The addition of the catalyst to the reaction system may be performed all at once or separately.
【００１５】前記で使用する触媒は、好ましくは、リン
酸系酸性触媒である。ここで言うリン酸系酸性触媒とし
ては、リン酸類またはリン酸のエステル類であり、具体
的には、リン酸、無水リン酸、ポリリン酸、オルトリン
酸、メタリン酸、ピロリン酸、三リン酸、四リン酸など
のリン酸類または、メチルアシッドホスフェート、エチ
ルアシッドホスフェート、イソプロピルアシッドホスフ
ェート、ブチルアシッドホスフェート、２−エチルヘキ
シルアシッドホスフェート等の酸性リン酸エステル類な
どを用いることができる。なお、これらの酸性リン酸エ
ステルはモノエステル体、ジエステル体、及びそれらの
混合物のいずれも使用することができる。以上の中で
は、リン酸および酸性リン酸エステルを用いることが好
ましい。[0015] The catalyst used above is preferably a phosphoric acid acidic catalyst. The phosphoric acid-based acidic catalyst referred to herein is a phosphoric acid or an ester of phosphoric acid, and specifically, phosphoric acid, phosphoric anhydride, polyphosphoric acid, orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, Phosphoric acids such as tetraphosphoric acid, or acidic phosphates such as methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, 2-ethylhexyl acid phosphate, and the like can be used. In addition, as these acidic phosphates, any of a monoester body, a diester body, and a mixture thereof can be used. Among the above, it is preferable to use phosphoric acid and acidic phosphoric acid esters.
【００１６】なお、上記触媒は１種を単独で使用しても
よく、また２種以上を混合して使用してもよい。触媒の
添加量は脂肪酸に対して０．０１〜１０重量％、好まし
くは０．１〜５重量％である。０．０１量％未満では反
応速度が小さく、また反応生成物の色相（ＡＰＨＡ値）
が高く、１０重量％を越えると添加効果の向上は期待で
きず、使用する触媒によっては、触媒が開始剤となるグ
リシドールの付加重合体が多く生成し、好ましくない。The above catalysts may be used alone or in a combination of two or more. The amount of the catalyst is 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the fatty acid. If the amount is less than 0.01% by weight, the reaction rate is low and the hue (APHA value) of the reaction product is low.
If the content exceeds 10% by weight, the effect of addition cannot be expected to be improved, and depending on the catalyst used, a large amount of a glycidol addition polymer, which is used as an initiator, is generated, which is not preferable.
【００１７】以上の反応により脂肪酸にグリシドールが
付加重合して、下記式［１］ ＲＣＯ−［ＯＣＨ2ＣＨ（ＯＨ）ＣＨ2］n−ＯＨ ［１］ （但し、Ｒは好ましくは、炭素数６〜２１のアルキル
基、アルケニル基またはヒドロキシル基で置換されたア
ルキル基を表し、ｎは平均量体数で１を超える数値であ
る。便宜上、式［１］はグリセリンの１級アルコールの
みで結合した表現になっているが、エステル及び／又は
エーテル結合が２級アルコールで結合したものを含んで
もよい。）で示される高重合度のポリグリセリンモノ脂
肪酸エステルが生成する。モノ脂肪酸エステル体のｎは
グリセリンの平均量体数であり、反応させる脂肪酸とグ
リシドールのモル比と略同じであり、容易に変えること
ができる。ｎは１を超え、好ましくは２以上に、更に好
ましくは４〜１０にすることが可能であり、上限として
は特にないが、１，０００程度のものまでは可能であろ
う。反応操作は、回分でも半回分でも、連続でも行うこ
とができる。Glycidol is addition-polymerized to the fatty acid by the above reaction, and the following formula [1] RCO- [OCH 2 CH (OH) CH 2 ] n-OH [1] (where R is preferably 6 carbon atoms) Represents an alkyl group substituted with an alkyl group, an alkenyl group or a hydroxyl group of from 21 to 21, and n is a numerical value exceeding 1 in terms of the average number of monomers.For convenience, the formula [1] is bonded only with the primary alcohol of glycerin. As described above, a polyglycerol monofatty acid ester having a high polymerization degree represented by the formula (1) may be used, in which an ester and / or an ether bond may be bonded by a secondary alcohol. N of the monofatty acid ester is an average number of glycerin, which is almost the same as the molar ratio of the fatty acid to be reacted and glycidol, and can be easily changed. n exceeds 1, preferably 2 or more, and more preferably 4 to 10. There is no particular upper limit, but it may be up to about 1,000. The reaction operation can be performed batchwise, semi-batchwise, or continuously.
【００１８】生成物は、モノ脂肪酸エステル体を主成分
とする、ポリグリセリンモノ脂肪酸エステルである。モ
ノ脂肪酸エステル体を主成分とするとは、生成物中にポ
リグリセリンモノ脂肪酸エステルを７０％以上、好まし
くは８０％以上含むものである。前記方法で得られるポ
リグリセリンモノ脂肪酸エステルは、カラムクロマト分
析法で溶離し、紫外線吸収検出器を用いて検出される前
記一般式［１］で示されるモノ脂肪酸エステル体のピー
ク面積比で表した含有率が７０％以上である。ここでカ
ラムクロマト分析法とは、官能基としてオクタデシルシ
リル基、オクチルシリル基、ブチルシリル基、トリメチ
ルシリル基、フェニルシリル基を結合したシリカゲルを
担体として用いる逆相分配カラム分析法、官能基として
シアノプロピル基、アミノプロピル基を有するシリカゲ
ルを担体として用いる順相分配カラム分析法、官能基と
して４級アンモニウム基、フェニルスルホン酸基を有す
るイオン交換カラム分析法、多孔性シリカゲルの吸着カ
ラム分析法が挙げられる。これらの分析法において、好
ましくはオクタデシルシリル（ＯＤＳ）基が結合したシ
リカゲルを担体として用いる逆相分配カラム分析法が使
用される。また分離性能を向上させるため、カラムサイ
ズは４．６ｍｍφ×２５０ｍｍ以上が好ましく、カラム
を直列に繋ぐと分離能を向上させることができるので、
より好ましい。前記モノ脂肪酸エステル体のピーク面積
比が７０％以上とは、具体的には下記ＨＰＬＣ（高速液
体クロマトグラフィー）の分析条件において、モノ脂肪
酸エステルに帰属されるピーク面積比が全ピーク面積に
対し７０％以上であることを意味する。The product is a polyglycerol monofatty acid ester containing a monofatty acid ester as a main component. The term "mainly composed of a monofatty acid ester" means that the product contains 70% or more, preferably 80% or more of polyglycerin monofatty acid ester. The polyglycerol monofatty acid ester obtained by the above method was eluted by column chromatography, and represented by the peak area ratio of the monofatty acid ester represented by the general formula [1], which was detected using an ultraviolet absorption detector. The content is 70% or more. Here, column chromatography analysis refers to a reversed-phase distribution column analysis using silica gel to which an octadecylsilyl group, an octylsilyl group, a butylsilyl group, a trimethylsilyl group, and a phenylsilyl group are bonded as a functional group, and a cyanopropyl group as a functional group. And column chromatography using silica gel having an aminopropyl group as a carrier, ion exchange column analysis having a quaternary ammonium group and phenylsulfonic acid group as functional groups, and adsorption column analysis using porous silica gel. In these analytical methods, a reversed-phase distribution column analytical method using silica gel to which an octadecylsilyl (ODS) group is bonded as a carrier is preferably used. In order to improve the separation performance, the column size is preferably 4.6 mmφ × 250 mm or more.
More preferred. Specifically, the peak area ratio of the monofatty acid ester is 70% or more when the peak area ratio attributed to the monofatty acid ester is 70% of the total peak area under the following HPLC (high performance liquid chromatography) analysis conditions. % Or more.
【００１９】また、前記で得られるポリグリセリンモノ
脂肪酸エステルは、必要に応じて種々の精製工程を経て
更に精製したのち、例えば食品添加剤に使用することも
可能であり、また好ましい。具体的な精製方法として
は、（イ）減圧下に飽和加熱水蒸気を吹き込んで水蒸気
脱臭を行う脱臭方法、（ロ）次亜燐酸ソーダまたは過酸
化水素による漂白等の脱色方法等がある。The polyglycerol monofatty acid ester obtained as described above may be further purified, if necessary, through various purification steps, and then used, for example, as a food additive. Specific purification methods include (a) a deodorizing method in which saturated heated steam is blown under reduced pressure to deodorize steam, and (b) a decolorizing method such as bleaching with sodium hypophosphite or hydrogen peroxide.
【００２０】以上の通り、本発明においては、純度の高
いポリグリセリンモノ脂肪酸エステル、特にはグリシド
ールと脂肪酸との付加重合反応により、モノ脂肪酸エス
テル体の前記ピーク面積比で表した含有率が７０％以上
であるポリグリセリンモノ脂肪酸エステルが得られる。
このようなポリグリセリンモノ脂肪酸エステルは、界面
活性剤や乳化安定剤等の食品添加剤として使用するの
で、表面張力の向上、分散力の向上、起泡力の向上、乳
化安定性の向上などの効果がある。As described above, in the present invention, a polyglycerol monofatty acid ester having a high purity, in particular, a content of the monofatty acid ester represented by the peak area ratio of 70% by the addition polymerization reaction of glycidol and the fatty acid is 70%. The above polyglycerin monofatty acid ester is obtained.
Since such a polyglycerin monofatty acid ester is used as a food additive such as a surfactant or an emulsion stabilizer, it can improve surface tension, dispersing power, foaming power, and emulsion stability. effective.
【００２１】従って、本発明で得られるポリグリセリン
モノ脂肪酸エステルは、従来からポリグリセリンモノ脂
肪酸エステル等が使用されている種々の用途に用いら
れ、その目的とする機能を十分に発揮することができ
る。Accordingly, the polyglycerin monofatty acid ester obtained in the present invention is used for various applications in which polyglycerin monofatty acid ester and the like are conventionally used, and can sufficiently exhibit its intended function. .
【００２２】[0022]
【実施例】以下、実施例により本発明を具体的に説明す
るが、本発明はこれらに限定されるものではない。な
お、実施例および比較例を通じて、ＨＰＬＣの分析条件
は下記の通りである。EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. Throughout the examples and comparative examples, HPLC analysis conditions are as follows.
【００２３】（ＨＰＬＣの分析条件） カラム：Ｗａｋｏｓｉｌ ５Ｃ１８×２（和光純薬工業
（株）製；逆相分配カラムであるオクタデシルシリル基
を官能基として持つカラム）、展開溶媒：メタノール、
流速：０．７５ｍｌ／ｍｉｎ．、カラムオーブン温度：
４０℃、検出方法：紫外線吸収法（λ＝２１０ｎｍ）、
試料濃度：１０％（溶媒：ＭｅＯＨ）、注入量：５μ
ｌ。 各成分のリテンションタイムは、例えばポリグリセリン
モノラウリン酸エステルの場合、ポリグリセリン：８分
以前、モノラウリン酸エステル体：８分〜１２分、ジラ
ウリン酸エステル体以上：１２分以降である。(HPLC analysis conditions) Column: Wakosil 5C18 × 2 (manufactured by Wako Pure Chemical Industries, Ltd .; column having an octadecylsilyl group as a functional group which is a reversed-phase distribution column), developing solvent: methanol,
Flow rate: 0.75 ml / min. , Column oven temperature:
40 ° C., detection method: ultraviolet absorption method (λ = 210 nm),
Sample concentration: 10% (solvent: MeOH), injection amount: 5μ
l. For example, in the case of polyglycerin monolaurate, the retention time of each component is 8 minutes or less for polyglycerin, 8 to 12 minutes for monolaurate, and 12 minutes or more for dilaurate or more.
【００２４】（実施例１）窒素導入管、攪拌機、冷却
管、温度調節器、滴下シリンダーを備えた１リットルの
４ツ口フラスコにラウリン酸０．９ｍｏｌ（１８０．３
ｇ）を加え、１４０℃に加熱した。次いで、反応温度を
１３０℃に保ちながらグリシドールを滴下し、グリシド
ールの１．８ｍｏｌ（全量の２０％）を添加した時点
で、リン酸（４２．５％水溶液）０．６８ｇを加えた
後、残りのグリシドールを滴下し、全体でグリシドール
９．０ｍｏｌ（６６６．７ｇ）を５時間かけて滴下し終
えた。滴下後、同温度で、熟成反応を続けて系中のオキ
シラン酸素濃度が熟成２４時間後には０．１２％、２６
時間後には０．０７２％になった。オキシラン酸素濃度
が０．１％以下になったので、冷却し、反応物を取り出
してデカグリセリンモノラウリン酸エステルを約８４５
ｇ得た。得られたデカグリセリンモノラウリン酸エステ
ルの色相はＡＰＨＡ３０であり、ゲル状物の生成は見ら
れなかった。結果を表−１に示した。(Example 1) 0.9 mol (180.3) of lauric acid was placed in a 1-liter four-necked flask equipped with a nitrogen inlet tube, a stirrer, a cooling tube, a temperature controller, and a dropping cylinder.
g) was added and heated to 140 ° C. Then, while maintaining the reaction temperature at 130 ° C., glycidol was added dropwise, and when 1.8 mol (20% of the total amount) of glycidol was added, 0.68 g of phosphoric acid (42.5% aqueous solution) was added. Of glycidol was added dropwise, and 9.0 mol (666.7 g) of glycidol in total was added dropwise over 5 hours. After dropping, the ripening reaction was continued at the same temperature until the oxirane oxygen concentration in the system became 0.12%, 26
After hours, it was 0.072%. Since the oxygen concentration of oxirane became 0.1% or less, the mixture was cooled, the reaction product was taken out, and decaglycerin monolaurate was added to about 845.
g was obtained. The color of the obtained decaglycerin monolaurate was APHA30, and no gel was formed. The results are shown in Table 1.
【００２５】（実施例２）グリシドールを３．６ｍｏｌ
（全量の４０％）滴下した時点で、リン酸を添加した以
外は実施例１と同様に行った。添加したリン酸は系中に
均一に分散、溶解し、反応に作用した。結果を表−１に
示した。Example 2 3.6 mol of glycidol
(40% of the total amount) The same operation as in Example 1 was performed except that phosphoric acid was added at the time of dropping. The phosphoric acid added was uniformly dispersed and dissolved in the system, and acted on the reaction. The results are shown in Table 1.
【００２６】（実施例３）グリシドールを７．２ｍｏｌ
（全体の８０％）滴下した時点で、リン酸を添加した以
外は実施例１と同様に行った。結果を表−１に示した。Example 3 7.2 mol of glycidol
(80% of the whole) The same operation as in Example 1 was performed except that phosphoric acid was added at the time of dropping. The results are shown in Table 1.
【００２７】（実施例４）脂肪酸にステアリン酸を使用
し、グリシドールを脂肪酸と等モル滴下した時点で、リ
ン酸を添加した以外は実施例１と同様に行った。結果を
表−１に示した。Example 4 The procedure of Example 1 was repeated except that stearic acid was used as the fatty acid, and glycidol was added in an equimolar amount to the fatty acid, and phosphoric acid was added. The results are shown in Table 1.
【００２８】（比較例１：触媒を予め添加した場合）リ
ン酸を予めラウリン酸０．９ｍｏｌ（２００．３ｇ）に
加えて、１３０℃に加熱してリン酸をラウリン酸に分散
させながらグリシドールを滴下した以外は実施例１と同
様に行った。結果を表−１に示した。(Comparative Example 1: When a catalyst was previously added) Phosphoric acid was previously added to 0.9 mol (200.3 g) of lauric acid, and heated to 130 ° C. to disperse glycidol in lauric acid. The procedure was performed in the same manner as in Example 1 except that the solution was dropped. The results are shown in Table 1.
【００２９】（比較例２：触媒をグリシドール滴下終了
後添加した場合）グリシドールを９．０ｍｏｌ滴下し終
わった時点で、リン酸を添加した以外は実施例１と同様
に行った。結果を表−１に示した。表−１において、触
媒添加時期は、グリシドールの全滴下量（１００％）に
対する触媒添加時迄に滴下したグリシドールの滴下量を
％で表示した。(Comparative Example 2: When the catalyst was added after the completion of dropping of glycidol) The procedure was the same as in Example 1 except that phosphoric acid was added when 9.0 mol of glycidol had been dropped. The results are shown in Table 1. In Table 1, the catalyst addition time is indicated by% of the amount of glycidol added dropwise until the catalyst addition relative to the total amount of glycidol added (100%).
【００３０】[0030]
【表１】 [Table 1]
【００３１】[0031]
【発明の効果】本発明によれば、ポリグリセリンモノ脂
肪酸エステルの含有率が高く、ポリグリセリンの重合度
が高く、色相に優れ、ゲル状物を副生せず、未反応グリ
シドールの少ないポリグリセリンモノ脂肪酸エステルが
得られ、得られたポリグリセリンモノ脂肪酸エステルは
界面活性剤、食品分野の乳化安定剤に応用した場合に、
表面張力の向上、分散力の向上、起泡力の向上、乳化安
定性が良い。According to the present invention, polyglycerol having a high content of polyglycerol monofatty acid ester, a high degree of polymerization of polyglycerin, excellent color, no by-product gel, and low unreacted glycidol is obtained. A mono-fatty acid ester is obtained, and the obtained polyglycerin mono-fatty acid ester is applied to a surfactant and an emulsion stabilizer in the food field,
Good surface tension, good dispersion power, good foaming power, good emulsion stability.
Claims (6)
応させた後、触媒を加え、グリシドールの残りを加えて
反応させることを特徴とする、モノ脂肪酸エステル体を
主成分とするポリグリセリンモノ脂肪酸エステルの製造
方法。1. A polyglycerol monofatty acid containing a monofatty acid ester as a main component, wherein a fatty acid is reacted by adding a part of glycidol to the fatty acid and then reacting by adding a catalyst. Method for producing ester.
ある請求項１記載のポリグリセリンモノ脂肪酸エステル
の製造方法。2. The method for producing a polyglycerol monofatty acid ester according to claim 1, wherein the alkyl group of the fatty acid has 6 to 21 carbon atoms.
のいずれかであることを特徴とする請求項１〜２のいず
れかに記載のポリグリセリンモノ脂肪酸エステルの製造
方法。3. The method for producing a polyglycerol monofatty acid ester according to claim 1, wherein the fatty acid is either lauric acid or stearic acid.
ルである請求項１〜３のいずれかに記載のポリグリセリ
ンモノ脂肪酸エステルの製造方法。4. The method for producing a polyglycerol monofatty acid ester according to claim 1, wherein the catalyst is phosphoric acid or an acidic phosphoric acid ester.
モル以上の量であることを特徴とする請求項１〜４のい
ずれかに記載のポリグリセリンモノ脂肪酸エステルの製
造方法。5. The method for producing a polyglycerol monofatty acid ester according to claim 1, wherein a part of glycidol is at least equimolar to the fatty acid.
請求項１〜５のいずれかに記載のポリグリセリンモノ脂
肪酸エステルの製造方法。6. The method for producing a polyglycerol monofatty acid ester according to claim 1, wherein the degree of polymerization of the polyglycerin is 2 or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03977098A JP3828657B2 (en) | 1998-02-06 | 1998-02-06 | Process for producing polyglycerol mono-fatty acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03977098A JP3828657B2 (en) | 1998-02-06 | 1998-02-06 | Process for producing polyglycerol mono-fatty acid ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11222521A true JPH11222521A (en) | 1999-08-17 |
| JP3828657B2 JP3828657B2 (en) | 2006-10-04 |
Family
ID=12562179
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03977098A Expired - Lifetime JP3828657B2 (en) | 1998-02-06 | 1998-02-06 | Process for producing polyglycerol mono-fatty acid ester |
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| Country | Link |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6344167B1 (en) | 1994-02-18 | 2002-02-05 | Basf Corporation | Process for the production of superconductor containing filaments |
| WO2013111441A1 (en) * | 2012-01-23 | 2013-08-01 | 株式会社ダイセル | Transparent gel cosmetic preparation |
| WO2024247897A1 (en) * | 2023-05-26 | 2024-12-05 | 株式会社ダイセル | Polyglycerin mono-fatty acid ester product and method for producing same |
-
1998
- 1998-02-06 JP JP03977098A patent/JP3828657B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6344167B1 (en) | 1994-02-18 | 2002-02-05 | Basf Corporation | Process for the production of superconductor containing filaments |
| WO2013111441A1 (en) * | 2012-01-23 | 2013-08-01 | 株式会社ダイセル | Transparent gel cosmetic preparation |
| JPWO2013111441A1 (en) * | 2012-01-23 | 2015-05-11 | 株式会社ダイセル | Transparent gel cosmetic |
| WO2024247897A1 (en) * | 2023-05-26 | 2024-12-05 | 株式会社ダイセル | Polyglycerin mono-fatty acid ester product and method for producing same |
| JP7603890B1 (en) * | 2023-05-26 | 2024-12-20 | 株式会社ダイセル | Polyglycerol mono fatty acid ester product and its manufacturing method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3828657B2 (en) | 2006-10-04 |
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