CN102285946A - Diacetyl epoxy glyceryl oleates and synthesis method thereof - Google Patents
Diacetyl epoxy glyceryl oleates and synthesis method thereof Download PDFInfo
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- CN102285946A CN102285946A CN201110176425A CN201110176425A CN102285946A CN 102285946 A CN102285946 A CN 102285946A CN 201110176425 A CN201110176425 A CN 201110176425A CN 201110176425 A CN201110176425 A CN 201110176425A CN 102285946 A CN102285946 A CN 102285946A
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- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000004593 Epoxy Substances 0.000 title abstract description 35
- 125000003976 glyceryl group Chemical group [H]C([*])([H])C(O[H])([H])C(O[H])([H])[H] 0.000 title abstract 8
- 238000001308 synthesis method Methods 0.000 title 1
- 235000012424 soybean oil Nutrition 0.000 claims abstract description 36
- 239000003549 soybean oil Substances 0.000 claims abstract description 36
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 28
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 28
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 24
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 19
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 18
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000005642 Oleic acid Substances 0.000 claims abstract description 18
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 16
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000019253 formic acid Nutrition 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims description 47
- 239000003921 oil Substances 0.000 claims description 44
- 235000019198 oils Nutrition 0.000 claims description 44
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 125000005456 glyceride group Chemical group 0.000 claims description 32
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 23
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 19
- 239000008158 vegetable oil Substances 0.000 claims description 19
- 235000013311 vegetables Nutrition 0.000 claims description 18
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 claims description 15
- 229960004232 linoleic acid Drugs 0.000 claims description 13
- IPCSVZSSVZVIGE-UHFFFAOYSA-N palmitic acid group Chemical group C(CCCCCCCCCCCCCCC)(=O)O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 13
- 235000011187 glycerol Nutrition 0.000 claims description 12
- 238000010189 synthetic method Methods 0.000 claims description 12
- 229960000583 acetic acid Drugs 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 10
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 10
- 239000012362 glacial acetic acid Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- 235000007164 Oryza sativa Nutrition 0.000 claims description 8
- 241000269319 Squalius cephalus Species 0.000 claims description 8
- 235000021355 Stearic acid Nutrition 0.000 claims description 8
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 claims description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 8
- 235000009566 rice Nutrition 0.000 claims description 8
- 239000008117 stearic acid Chemical group 0.000 claims description 8
- OXEDXHIBHVMDST-UHFFFAOYSA-N 12Z-octadecenoic acid Natural products CCCCCC=CCCCCCCCCCCC(O)=O OXEDXHIBHVMDST-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 6
- 238000005809 transesterification reaction Methods 0.000 claims description 6
- 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 claims description 5
- 235000020661 alpha-linolenic acid Nutrition 0.000 claims description 5
- 125000005908 glyceryl ester group Chemical group 0.000 claims description 5
- 229960004488 linolenic acid Drugs 0.000 claims description 5
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 claims description 5
- 150000002632 lipids Chemical class 0.000 claims description 5
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 claims description 4
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 claims description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 235000021314 Palmitic acid Nutrition 0.000 claims description 3
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical group CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims description 3
- 239000012346 acetyl chloride Substances 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 239000003456 ion exchange resin Substances 0.000 claims description 3
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 3
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 3
- 230000021736 acetylation Effects 0.000 claims description 2
- 238000006640 acetylation reaction Methods 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 8
- 231100000252 nontoxic Toxicity 0.000 abstract description 4
- 230000003000 nontoxic effect Effects 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 125000004185 ester group Chemical group 0.000 abstract 1
- 230000009969 flowable effect Effects 0.000 abstract 1
- 239000008031 plastic plasticizer Substances 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 55
- 239000004215 Carbon black (E152) Substances 0.000 description 30
- 229930195733 hydrocarbon Natural products 0.000 description 30
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 30
- 239000004902 Softening Agent Substances 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 238000005452 bending Methods 0.000 description 16
- 150000002148 esters Chemical class 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 238000002329 infrared spectrum Methods 0.000 description 15
- 238000010992 reflux Methods 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- 244000068988 Glycine max Species 0.000 description 13
- 235000010469 Glycine max Nutrition 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- RZRNAYUHWVFMIP-HXUWFJFHSA-N glycerol monolinoleate Natural products CCCCCCCCC=CCCCCCCCC(=O)OC[C@H](O)CO RZRNAYUHWVFMIP-HXUWFJFHSA-N 0.000 description 10
- 229940074096 monoolein Drugs 0.000 description 10
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 10
- 239000004033 plastic Substances 0.000 description 8
- 229920003023 plastic Polymers 0.000 description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 7
- 229910052740 iodine Inorganic materials 0.000 description 7
- 239000011630 iodine Substances 0.000 description 7
- 229920000915 polyvinyl chloride Polymers 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 241000209094 Oryza Species 0.000 description 6
- HLLSOEKIMZEGFV-UHFFFAOYSA-N 4-(dibutylsulfamoyl)benzoic acid Chemical compound CCCCN(CCCC)S(=O)(=O)C1=CC=C(C(O)=O)C=C1 HLLSOEKIMZEGFV-UHFFFAOYSA-N 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 150000004292 cyclic ethers Chemical class 0.000 description 5
- 230000006837 decompression Effects 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000004519 grease Substances 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 4
- SLPFAJNQMSNEKK-VHXPQNKSSA-N CCCCCCCC/C(=C(\CCCCCCCC(=O)OCC(CO)O)/C(=O)C)/C(=O)C Chemical compound CCCCCCCC/C(=C(\CCCCCCCC(=O)OCC(CO)O)/C(=O)C)/C(=O)C SLPFAJNQMSNEKK-VHXPQNKSSA-N 0.000 description 3
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 3
- -1 diacetyl epoxy oleic acid Chemical compound 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 description 3
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 1
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000004500 asepsis Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 239000000834 fixative Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 1
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-M hexadecanoate Chemical compound CCCCCCCCCCCCCCCC([O-])=O IPCSVZSSVZVIGE-UHFFFAOYSA-M 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229940049918 linoleate Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- NJTGANWAUPEOAX-UHFFFAOYSA-N molport-023-220-454 Chemical compound OCC(O)CO.OCC(O)CO NJTGANWAUPEOAX-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002924 oxiranes Chemical group 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000000176 photostabilization Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
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- 239000011347 resin Substances 0.000 description 1
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- 238000007493 shaping process Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 230000003019 stabilising effect Effects 0.000 description 1
- 235000020238 sunflower seed Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
Images
Abstract
The invention discloses diacetyl epoxy glyceryl oleates. The general formula of the diacetyl epoxy glyceryl oleates may be (I) or (II). The diacetyl epoxy glyceryl oleates are more stable and flowable than epoxidized soybean oil, the molecular weight of the diacetyl epoxy glyceryl oleates is low, and the diacetyl epoxy glyceryl oleates have high compatibility with polyvinyl chloride (PVC) and are high-performance nontoxic plastic plasticizer. The invention also discloses a method for synthesizing diacetyl epoxy glyceryl oleates by starting from oleic acid, which comprises: performing ester exchange of oleic acid and glycerol in the presence of a catalyst to obtain monooleins; compounding monooleins with acetyl to obtain diacetyl monooleins; and performing an epoxidation reaction in an environment with formic acid and hydrogen peroxide, and thus synthesizing diacetyl epoxy glyceryl oleates.
Description
Technical field
The present invention relates to a kind of softening agent, also relate to the synthetic method of this softening agent simultaneously, especially synthesize the method for this softening agent from vegetables oil.
Background technology
In recent years, China has become Asia area plasticizer production and the maximum country of consumption, and along with the enhancing of people's environmental protection consciousness, plastics such as medicine and food product pack, daily necessities, toy have proposed higher hygienic requirements to softening agent.Softening agent mainly is based on adjacent benzene-type products for a long time, but it is found that such softening agent is poisonous, has carcinogenic potentially dangerous.The EFSA of food safety mechanism of European Union limits the concentration of DOP, DOA, so the softening agent of asepsis environment-protecting becomes the emphasis of global softening agent research.PVC fusing point height, but processing temperature narrow range, the words that do not add stabilising system are difficult to machine-shaping, improving its plasticity-must add softening agent and reduce its flow temperature (Tf), and can reduce Van der Waals force between polymer molecule behind the adding softening agent, increase the movability of macromolecular chain, improve the plasticity-of polymkeric substance, enlarge its processing temperature scope, thereby can produce the flexible article that has than high-tensile and elongation at break, hardness, modulus, softening temperature and embrittlement temperature are descended, and elongation, flexibility and snappiness improve.
Epoxy Rice pollard oil, epoxy oleum lini, epoxy soybean wet goods epoxy compounds, because it is it has the hold concurrently premium properties of thermo-stabilizer of softening agent, of many uses in plastics industry.Epoxy soybean oil is owing to have good thermotolerance, photostabilization, oozing property, low temperature flexibility mutually, and volatility is low, it is the softening agent of reasonable nontoxic, the environmental protection of present plasticization effect, renewable resources preparation, it is unique softening agent that can be used for the instrumentation package material of united States food and drug administration (FDA) approval, use very extensive, especially for the aspects such as auxiliary agent of food, medicine Plastic Packaging Materials, toy for children and home decoration material.According to Chinese patent CN101691524A introduction, use the PVC plastics of epoxy soybean oil as softening agent, not only its raw materials cost can decrease, and its every physicals also has raising in various degree, as anti-processibility, heat-resistant aging, folding resistance etc.In the hard sheet bending and unbending test of PVC, fracture after not adding tortuous about 200 times of the PVC of epoxy soybean oil, add 4% epoxy soybean oil after, this numerical value reaches 3600 times.Its another distinguishing feature is that the low temperature plasticity is very good, the polyvinyl chloride resin behind the interpolation epoxy soybean oil, and under low temperature condition, its plasticization effect is better than other softening agent commonly used.Epoxy soybean oil is a kind of Chemicals that soybean oil makes through peroxide oxidation.Along with the development of plastics industry, the Epoxy oil with multiple function is used more and more.Epoxy aliphatic acid methyl ester is crude vegetal and alcohols esterification after epoxidation is made, wherein Chinese patent CN1966497, CN101235021A, CN101885710A and CN101891713A have reported its synthetic method respectively, and point out that they are a kind of use nontoxic polyvinyl chloride softening agent widely, volatility is low, in the PVC goods course of processing, epoxy soybean oil and DOP have been replaced fully, the consistency of product is better than DOP, add man-hour heat-resisting volatility and be better than DBP, in the processing of goods, can obviously improve physical properties of articles and prolong goods duration of service.With metal(lic)stabilizer and time spent, good synergisticing stable effect is arranged.
Glycerine triacetate has purposes widely, mainly as the softening agent of cigarette filter, also can be used as foodstuff additive, and its toxicity is low, can make the gentle sterilant of vegetables, fruit, gelatin and synthetical glue, also can make fixative of some spices or the like.
Stearinsaeure di-acetyl glyceryl ester (Fully acetylated glycerol monostearate) and single 12-hydroxyl ethyl ester stearic acid di-acetyl glyceryl ester (Fully acetylated glycerol monoester on 12-hydroxystearic acid) have less molecular weight (about about 500), have higher boiling point (greater than 300 ℃) and higher flash-point (245 ℃), have good mobility and lower viscosity, can be used as the softening agent of igelite.Epoxy soybean oil is mainly the mixture of epoxy linoleate, Epoxy oil acid esters, epoxy cetylate, and normal temperature is down light yellow viscous liquid, yield point-1 ℃, 150 ℃ of boiling points, 310 ℃ at point of ignition, viscosity 325mPa.S (25 ℃), refractive index 1.4713 (25 ℃).
The epoxy soybean oil molecular weight is big, viscosity is big, mobile poor, but owing to comprise epoxide group in its structure, have thermostability preferably and and the intermiscibility of plastics; The glycerine triacetate molecule is less, and its viscosity is little than epoxy soybean oil, and we are in conjunction with the feature and the character of their mutual structures, and hope can find a kind of plasticization effect similar to epoxy soybean oil, but molecular weight is low, the epoxy acetate esters softening agent of good fluidity.
Summary of the invention
Diacetyl epoxidized vegetable oil acid glyceride, it is than epoxy soybean oil good stability, and good fluidity is good with the intermiscibility of plastic pvc, is a kind of novel good non-toxic plastic softening agent of character.
Its composition principle is: at first carry out transesterify with vegetables oil and glycerine under catalyst action; obtain the vegetable oil acid direactive glyceride; and then acetylize synthesis of diacetyl vegetable oil acid glyceryl ester; the last epoxidation reaction of in the environment of formic acid and hydrogen peroxide, carrying out, the synthetic diacetyl epoxidized vegetable oil acid glyceride that obtains.Its reaction principle can be represented with following chemical equation:
1. vegetables oil and glycerine carry out transesterify
2. acetylize synthesis of diacetyl vegetable oil acid glyceryl ester
3. diacetyl vegetable oil acid glyceryl ester epoxidation reaction
Wherein, R
1, R
2, R
3Be 20 lipid acid below the carbon atom in the vegetables oil.
Preferably: described: R is selected from palmitic acid, stearic acid, cis-9-octadecenic acid, cis 9, cis-I2 octadecenic acid, cis-9, cis-I2, the cis-I5 octadecenic acid in the soybean oil; Or be selected from oleic acid, linolic acid, palmitinic acid in the Rice pollard oil; Or be selected from stearic acid, oleic acid, linolic acid in the plam oil; Or be selected from eicosanoic acid, oleic acid, linolic acid, erucic acid, linolenic acid in the rapeseed oil.
Preferably: the glycerine consumption of described step a is the 18-25% (w/w) of vegetables oil consumption.
Preferably: the transesterification reaction of described step a also can add catalyzer, and described catalyzer is selected from least a in Qing Yangization Na, potassium hydroxide, calcium oxide, calcium hydroxide, sodium methylate, the sodium ethylate.
Preferably: the consumption of described transesterification catalyst is the 0.01-0.04% (w/w) of vegetables oil consumption.
Preferably: the acetylization reaction among the described step b can also add catalyzer, and described catalyzer is selected from least a in sulfuric acid, tosic acid, the acidic ion exchange resin, and consumption is the 0.3%-0.6% (w/w) of vegetable oil acid list glyceride consumption.
Preferably: the acetylation reagent among the described step b is selected from Acetyl Chloride 98Min., Glacial acetic acid, diacetyl oxide, and consumption is 40%-50 (w/w) % of vegetable oil acid list glyceride consumption.
Preferably: can also use among the described step b and hang aqua, the described aqua that hangs is selected from benzene, hexanaphthene, hexane, and its consumption is the 35-40% (w/w) of vegetable oil acid list glyceride consumption.
Preferably: among the step c, also add formic acid or acetate, wherein, diacetyl soybean oil acid glyceride: hydrogen peroxide: formic acid or acetate: catalyzer=1: 0.4-0.7: 0.04-0.08: 0.001-0.003 (mol ratio).
Preferably: can also add sulfuric acid or phosphoric acid in the epoxidation reaction among the described step c.
Description of drawings
Accompanying drawing 1 is the infrared spectrogram of soybean monoolein.
Accompanying drawing 2 is the infrared spectrogram of diacetyl soybean oil acid glyceride.
Accompanying drawing 3 is the infrared spectrogram of diacetyl epoxy soybean olein.
Accompanying drawing 4 is the infrared spectrogram of oleic acid direactive glyceride.
Accompanying drawing 5 is the infrared spectrogram of diacetyl oleic acid glyceryl ester.
Accompanying drawing 6 is the infrared spectrogram of diacetyl epoxy oleic acid glyceryl ester.
Embodiment
The used vegetables oil of transesterify has soybean oil, Rice pollard oil, oleum lini, rapeseed oil, plam oil, Viscotrol C, sunflower seed oil, and the catalyzer of transesterify has Qing Yangization Na, potassium hydroxide, calcium oxide, calcium hydroxide, sodium methylate, sodium ethylate; The vegetables oil raw material is example with the soybean oil, and used soybean oil iodine number is at 120-140I
2/ 100g, acid number 0.5-2mgKOH/g.The consumption of glycerine is the 18-25% (w/w) of soybean oil consumption, and the transesterification catalyst consumption is the 0.01-0.04% of soybean oil consumption, and transesterification reaction temperature is at 150-220 ℃, and the reaction times was controlled at 1.5-4.5 hour.
The acetyl catalyzer can be used sulfuric acid, tosic acid, acidic ion exchange resin.
Hang aqua and can use benzene, hexanaphthene, hexane.The effect of hanging aqua is: after vegetables oil and glycerine (glycerol) carry out transesterify; get the vegetable oil acid direactive glyceride; it is an esterification reaction process that it and acetic acid further carry out acetylizad reaction process; the generation of water is arranged; this is a balanced reaction, and the lasting generation of water can make the acetyl reaction can not carry out fully, needs to add the aqua that hangs that can form azeotrope with water; water is constantly removed from resultant of reaction, impelled reaction to move right.
The used acetylizing agent of acetylize can be used Acetyl Chloride 98Min., Glacial acetic acid, diacetyl oxide; acetylizing agent is example with the Glacial acetic acid; the Glacial acetic acid consumption is the 40-50% of soybean monoolein consumption; hang the 35-40% that the aqua consumption is a soybean monoolein consumption, the consumption of acetyl catalyst sulfuric acid (98%) is the 0.3-0.6% of soybean monoolein amount.
Epoxidation reaction adopts hydrogen peroxide, makes intermediate carrier with formic acid or acetate, and epoxidation catalyst can adopt sulfuric acid, phosphoric acid.Epoxidation reaction adopts 80-85% formic acid, the 30-50% hydrogen peroxide, and 98% sulfuric acid is made catalyzer.Epoxidation reaction charging capacity ratio control exists, diacetyl soybean oil acid glyceride: hydrogen peroxide: formic acid: catalyzer=1: 0.4-0.7: 0.04-0.08: 0.001-0.003.
Reacted material meets the general feature of softening agent through the detection of infared spectrum.
With the soybean oil is basic raw material.As can be seen from Table 1: soybean oil belongs to triglyceride, and main composition is 18 carbon fatty acids, and other is C
14-C
20Some lipid acid in the scope.
Raw soybeans fatty acid oil composed as follows:
Transesterify: with 838g soybean oil, 162g glycerine, join in three mouthfuls of round-bottomed bottles that have whipping appts, thermometer, reflux condensing tube successively, feed nitrogen and stir and heat up, when temperature reaches 120 ℃, add calcium oxide catalyst 0.2g, 200 ℃ of insulation reaction 2 hours.Batch take-off when the ethanol of 1 part sample and 10 parts dissolves each other, finishes reaction.Obtain light yellow oil soybean monoolein.Survey infrared spectra, as shown in Figure 1, IR (KBr): 3383cm-
1Broad peak is-the OH peak 3009cm-
1C-H stretching vibration absorption for unsaturated hydrocarbons; 2926cm-
1C-H asymmetrical stretching vibration absorption for stable hydrocarbon CH2; 2855cm-
1C-H symmetrical stretching vibration absorption for stable hydrocarbon CH2; 1741cm-
1C=O stretching vibration absorption for ester; 1463cm-
1C-H asymmetric bending vibration for methyl; 1380cm-
1C-H symmetric curvature vibration for methyl; 1176cm-
1Be the asymmetric stretching vibration of C-O-C; 1117cm-
1Be the C-O-C symmetrical stretching vibration;
Acetylize: whipping appts, thermometer are being housed, are hanging in three mouthfuls of round-bottomed bottles of water device and reflux condensing tube; add above-mentioned sample soybean monoolein 296g, Glacial acetic acid 136g, benzene 110g and catalyst sulfuric acid 1.5g successively; the water back flow reaction is hung in intensification; stopped reaction when aquifer yield reaches theoretical amount, decompression is extracted unreacted acetate out and is hung aqua benzene.Get grey black oily matter diacetyl soybean oil acid glyceride.Survey infrared spectra, as shown in Figure 2, IR (KBr): 3009cm-
1C-H stretching vibration absorption for unsaturated hydrocarbons; 2927cm-
1C-H asymmetrical stretching vibration absorption for stable hydrocarbon CH2; 2855cm-
1C-H symmetrical stretching vibration absorption for stable hydrocarbon CH2; 1744cm-
1C=O stretching vibration absorption for ester; 1462cm-
1C-H asymmetric bending vibration for methyl; 1372cm-
1C-H symmetric curvature vibration for methyl; 1170cm-
1Be the asymmetric stretching vibration of C-O-C; 1100cm-
1Be the C-O-C symmetrical stretching vibration;
Epoxidation: with above-mentioned quantitative diacetyl soybean oil acid glyceride 300g; formic acid 20g; catalyzer 0.7g adds and has whipping appts; thermometer; dropping funnel; in the four-hole bottle of reflux condensing tube; be warming up to 60-65 ℃ under stirring; stir and slowly splash into 50% hydrogen peroxide 200g down; add the back 75-80 ℃ of reaction 4 hours; tell lower floor's sour water; the upper strata grease is successively used buck; be washed to neutrality; but acid number underpressure distillation below 0.6 dewater and filter light yellow oil diacetyl epoxy soybean olein; its oxirane value is 2.3; acid number is 12, and iodine number is 2.7.Survey infrared spectra, as shown in Figure 3, IR (KBr): 2927cm-
1C-H asymmetrical stretching vibration absorption for stable hydrocarbon CH2; 2855cm-
1C-H symmetrical stretching vibration absorption for stable hydrocarbon CH2; 1745cm-
1C=O stretching vibration absorption for ester; 1466cm-
1C-H asymmetric bending vibration for methyl; 1373cm-
1C-H symmetric curvature vibration for methyl; 1170cm-
1Be the asymmetric stretching vibration of C-O-C; 1103cm-
1Be the C-O-C symmetrical stretching vibration; 826cm-
1Be the asymmetric stretching vibration of ternary cyclic ethers C-O-C; 722cm-
1Rocking vibration for methylene radical.
With the soybean oil is basic raw material.
Transesterify: with 100g soybean oil, 20.2g glycerine, join in three mouthfuls of round-bottomed bottles that have whipping appts, thermometer, reflux condensing tube successively, feed nitrogen and stir and heat up, when temperature reaches 120 ℃, add sodium hydroxide catalyst 0.02g, 200 ℃ of insulation reaction 4 hours.Batch take-off when the ethanol of 1 minute sample and 10 parts dissolves each other, finishes reaction.Get a light yellow oil soybean monoolein.Survey infrared spectra, IR (KBr): 3385cm-
1Broad peak is-the OH peak 3009cm-
1C-H stretching vibration absorption for unsaturated hydrocarbons; 2926cm-
1C-H asymmetrical stretching vibration absorption for stable hydrocarbon CH2; 2854cm-
1C-H symmetrical stretching vibration absorption for stable hydrocarbon CH2; 1741cm-
1C=O stretching vibration absorption for ester; 1464cm-
1C-H asymmetric bending vibration for methyl; 1378cm-
1C-H symmetric curvature vibration for methyl; 1177cm-
1Be the asymmetric stretching vibration of C-O-C; 1119cm-
1Be the C-O-C symmetrical stretching vibration;
Acetylize: whipping appts, thermometer are being housed, are hanging in three mouthfuls of round-bottomed bottles of water device and reflux condensing tube; add above-mentioned sample soybean monoolein 300g, Glacial acetic acid 136g, benzene 110g and catalyst sulfuric acid (98%) 1.5g successively; the water back flow reaction is hung in intensification; stopped reaction when aquifer yield reaches theoretical amount, decompression is extracted unreacted acetate out and is hung aqua benzene.Get grey black oily matter diacetyl soybean oil acid glyceride.Survey infrared spectra: IR (KBr): 3009cm-
1C-H stretching vibration absorption for unsaturated hydrocarbons; 2927cm-
1C-H asymmetrical stretching vibration absorption for stable hydrocarbon CH2; 2855cm-
1C-H symmetrical stretching vibration absorption for stable hydrocarbon CH2; 1748cm-
1C=O stretching vibration absorption for ester; 1462cm-
1C-H asymmetric bending vibration for methyl; 1371cm-
1C-H symmetric curvature vibration for methyl; 1169cm-
1Be the asymmetric stretching vibration of C-O-C; 1100cm-
1Be the C-O-C symmetrical stretching vibration;
Epoxidation: above-mentioned quantitative diacetyl soybean oil acid glyceride 500g, formic acid 22g, adding are had in the four-hole bottle of whipping appts, thermometer, dropping funnel, reflux condensing tube, be warming up to 55 ℃ under stirring, stir and slowly splash into 50% hydrogen peroxide 200g (98%H down
2SO
4Catalyzer 0.7g); add the back 75-80 ℃ of reaction 4 hours; tell lower floor's sour water; the upper strata grease successively with buck, be washed to neutrality; but acid number underpressure distillation below 0.6 dewater and filter light yellow oil diacetyl epoxy soybean olein; its oxirane value is 2.45, acid number 1.77 iodine numbers 2.44.Survey infrared spectra: IR (KBr): 2927cm-
1C-H asymmetrical stretching vibration absorption for stable hydrocarbon CH2; 2855cm-
1C-H symmetrical stretching vibration absorption for stable hydrocarbon CH2; 1745cm-
1C=O stretching vibration absorption for ester; 1463cm-
1C-H asymmetric bending vibration for methyl; 1376cm-
1C-H symmetric curvature vibration for methyl; 1167cm-
1Be the asymmetric stretching vibration of C-O-C; 1102cm-
1Be the C-O-C symmetrical stretching vibration; 825cm-
1Be the asymmetric stretching vibration of ternary cyclic ethers C-O-C; 725cm-
1Rocking vibration for methylene radical.
With the Rice pollard oil is basic raw material, and Rice pollard oil is the same with soybean oil, and its main component is the tri-fatty glyceride.Its fatty acid component is oleic acid 40-50%, linolic acid 29-42%, palmitinic acid 12-18%.The lipid acid molecular-weight average is 278-285, iodine number 98-110.
Transesterify: with 100g Rice pollard oil, 20.2g glycerine, join in three mouthfuls of round-bottomed bottles that have whipping appts, thermometer, reflux condensing tube successively, feed nitrogen and stir and heat up, when temperature reaches 120 ℃, add sodium hydroxide catalyst 0.02g, 200 ℃ of insulation reaction 4 hours.Batch take-off when the ethanol of 1 minute sample and 10 parts dissolves each other, finishes reaction.Get a light yellow oil oleic acid direactive glyceride.Survey infrared spectra, as shown in Figure 4, IR (KBr): 3415cm-
1Broad peak is-the OH peak 3008cm-
1C-H stretching vibration absorption for unsaturated hydrocarbons; 2926cm-
1C-H asymmetrical stretching vibration absorption for stable hydrocarbon CH2; 2855cm-
1C-H symmetrical stretching vibration absorption for stable hydrocarbon CH2; 1742cm-
1C=O stretching vibration absorption for ester; 1463cm-
1C-H asymmetric bending vibration for methyl; 1380cm-
1C-H symmetric curvature vibration for methyl; 1173cm-
1Be the asymmetric stretching vibration of C-O-C; 1118cm-
1Be the C-O-C symmetrical stretching vibration;
Acetylize: whipping appts, thermometer are being housed, are hanging in three mouthfuls of round-bottomed bottles of water device and reflux condensing tube; add above-mentioned sample oleic acid direactive glyceride 300g, Glacial acetic acid 136g, benzene 110g and catalyst sulfuric acid (98%) 1.5g successively; the water back flow reaction is hung in intensification; stopped reaction when aquifer yield reaches theoretical amount, decompression is extracted unreacted acetate out and is hung aqua benzene.Get grey black oily matter diacetyl oleic acid glyceryl ester.Survey infrared spectra, as shown in Figure 5, IR (KBr): 3007cm-
1C-H stretching vibration absorption for unsaturated hydrocarbons; 2926cm-
1C-H asymmetrical stretching vibration absorption for stable hydrocarbon CH2; 2855cm-
1C-H symmetrical stretching vibration absorption for stable hydrocarbon CH2; 1743cm-
1C=O stretching vibration absorption for ester; 1462cm-
1C-H asymmetric bending vibration for methyl; 1376cm-
1C-H symmetric curvature vibration for methyl; 1172cm-
1Be the asymmetric stretching vibration of C-O-C; 1118cm-
1Be the C-O-C symmetrical stretching vibration;
Epoxidation: above-mentioned quantitative diacetyl oleic acid glyceryl ester 500g, formic acid 22g, adding are had in the four-hole bottle of whipping appts, thermometer, dropping funnel, reflux condensing tube, be warming up to 55 ℃ under stirring, stir and slowly splash into 50% hydrogen peroxide 200g (98%H down
2SO
4Catalyzer 0.7g); add the back 75-80 ℃ of reaction 4 hours; tell lower floor's sour water; the upper strata grease successively with buck, be washed to neutrality; but acid number underpressure distillation below 0.6 dewater and filter light yellow oil diacetyl epoxy oleic acid glyceryl ester; its oxirane value is 1.5, and acid number is 2.1, and iodine number is 2.5.Survey infrared spectra, as shown in Figure 6, IR (KBr): 2927cm-
1C-H asymmetrical stretching vibration absorption for stable hydrocarbon CH2; 2855cm-
1C-H symmetrical stretching vibration absorption for stable hydrocarbon CH2; 1742cm-
1C=O stretching vibration absorption for ester; 1463cm-
1C-H asymmetric bending vibration for methyl; 1377cm-
1C-H symmetric curvature vibration for methyl; 1174cm-
1Be the asymmetric stretching vibration of C-O-C; 1113cm-
1Be the C-O-C symmetrical stretching vibration; 823cm-
1Be the asymmetric stretching vibration of ternary cyclic ethers C-O-C; 725cm-
1Rocking vibration for methylene radical.
Embodiment 4
With the plam oil is basic raw material, and palmitinic acid in the plam oil composition (C16:0) accounts for 67.056%, and stearic acid (C18:0) accounts for 4.905%, and oleic acid (C18:1) accounts for 17.116%, and linolic acid (C18:2) accounts for 3.942%.
Transesterify: with 100g plam oil, 20.2g glycerine, join in three mouthfuls of round-bottomed bottles that have whipping appts, thermometer, reflux condensing tube successively, feed nitrogen and stir and heat up, when temperature reaches 120 ℃, add sodium hydroxide catalyst 0.02g, 200 ℃ of insulation reaction 4 hours.Batch take-off when the ethanol of 1 minute sample and 10 parts dissolves each other, finishes reaction.Get a light yellow oil Zoomeric acid direactive glyceride.Survey infrared spectra, IR (KBr): 3385cm-
1Broad peak is-the OH peak 3009cm-
1C-H stretching vibration absorption for unsaturated hydrocarbons; 2926cm-
1C-H asymmetrical stretching vibration absorption for stable hydrocarbon CH2; 2854cm-
1C-H symmetrical stretching vibration absorption for stable hydrocarbon CH2; 1741cm-
1C=O stretching vibration absorption for ester; 1464cm-
1C-H asymmetric bending vibration for methyl; 1378cm-
1C-H symmetric curvature vibration for methyl; 1177cm-
1Be the asymmetric stretching vibration of C-O-C; 1119cm-
1Be the C-O-C symmetrical stretching vibration;
Acetylize: whipping appts, thermometer are being housed, are hanging in three mouthfuls of round-bottomed bottles of water device and reflux condensing tube; add above-mentioned sample Zoomeric acid direactive glyceride 300g, Glacial acetic acid 136g, benzene 110g and catalyst sulfuric acid (98%) 1.5g successively; the water back flow reaction is hung in intensification; stopped reaction when aquifer yield reaches theoretical amount, decompression is extracted unreacted acetate out and is hung aqua benzene.Get grey black oily matter diacetyl Zoomeric acid glyceryl ester.Survey infrared spectra: IR (KBr): 3009cm-
1C-H stretching vibration absorption for unsaturated hydrocarbons; 2927cm-
1C-H asymmetrical stretching vibration absorption for stable hydrocarbon CH2; 2855cm-
1C-H symmetrical stretching vibration absorption for stable hydrocarbon CH2; 1748cm-
1C=O stretching vibration absorption for ester; 1462cm-
1C-H asymmetric bending vibration for methyl; 1371cm-
1C-H symmetric curvature vibration for methyl; 1169cm-
1Be the asymmetric stretching vibration of C-O-C; 1100cm-
1Be the C-O-C symmetrical stretching vibration;
Epoxidation: above-mentioned quantitative diacetyl Zoomeric acid glyceryl ester 500g, formic acid 22g, adding are had in the four-hole bottle of whipping appts, thermometer, dropping funnel, reflux condensing tube, be warming up to 55 ℃ under stirring, stir and slowly splash into 50% hydrogen peroxide 180g (98%H down
2SO
4Catalyzer 0.7g); add the back 75-80 ℃ of reaction 4 hours; tell lower floor's sour water; the upper strata grease successively with buck, be washed to neutrality; but acid number underpressure distillation below 0.6 dewater and filter light yellow oil diacetyl epoxy palm oil acid glyceride; its oxirane value 1.5, acid number are 2.1, and iodine number is 22.Survey infrared spectra: IR (KBr): 2927cm-
1C-H asymmetrical stretching vibration absorption for stable hydrocarbon CH2; 2855cm-
1C-H symmetrical stretching vibration absorption for stable hydrocarbon CH2; 1745cm-
1C=O stretching vibration absorption for ester; 1463cm-
1C-H asymmetric bending vibration for methyl; 1376cm-
1C-H symmetric curvature vibration for methyl; 1165cm-
1Be the asymmetric stretching vibration of C-O-C; 1102cm-
1Be the C-O-C symmetrical stretching vibration; 822cm-
1Be the asymmetric stretching vibration of ternary cyclic ethers C-O-C; 723cm-
1Rocking vibration for methylene radical.
Embodiment 5
With the rapeseed oil is basic raw material, contains eicosanoic acid 0.4-1.0% in the rapeseed oil, oleic acid 14-19%, linolic acid 12-24%, erucic acid 31-55%, linolenic acid 1-10%.
Transesterify: with 100g rapeseed oil, 20.2g glycerine, join in three mouthfuls of round-bottomed bottles that have whipping appts, thermometer, reflux condensing tube successively, feed nitrogen and stir and heat up, when temperature reaches 120 ℃, add sodium hydroxide catalyst 0.02g, 200 ℃ of insulation reaction 4 hours.Batch take-off when the ethanol of 1 minute sample and 10 parts dissolves each other, finishes reaction.Get a light yellow oil vegetable seed monoolein.Survey infrared spectra, IR (KBr): 3385cm-
1Broad peak is-the OH peak 3009cm-
1C-H stretching vibration absorption for unsaturated hydrocarbons; 2926cm-
1C-H asymmetrical stretching vibration absorption for stable hydrocarbon CH2; 2854cm-
1C-H symmetrical stretching vibration absorption for stable hydrocarbon CH2; 1741cm-
1C=O stretching vibration absorption for ester; 1464cm-
1C-H asymmetric bending vibration for methyl; 1378cm-
1C-H symmetric curvature vibration for methyl; 1177cm-
1Be the asymmetric stretching vibration of C-O-C; 1119cm-
1Be the C-O-C symmetrical stretching vibration;
Acetylize: whipping appts, thermometer are being housed, are hanging in three mouthfuls of round-bottomed bottles of water device and reflux condensing tube; add above-mentioned sample vegetable seed monoolein 300g, Glacial acetic acid 136g, benzene 110g and catalyst sulfuric acid (98%) 1.5g successively; the water back flow reaction is hung in intensification; stopped reaction when aquifer yield reaches theoretical amount, decompression is extracted unreacted acetate out and is hung aqua benzene.Get grey black oily matter diacetyl rapeseed oil acid glyceride.Survey infrared spectra: IR (KBr): 3009cm-
1C-H stretching vibration absorption for unsaturated hydrocarbons; 2927cm-
1C-H asymmetrical stretching vibration absorption for stable hydrocarbon CH2; 2855cm-
1C-H symmetrical stretching vibration absorption for stable hydrocarbon CH2; 1748cm-
1C=O stretching vibration absorption for ester; 1462cm-
1C-H asymmetric bending vibration for methyl; 1371cm-
1C-H symmetric curvature vibration for methyl; 1169cm-
1Be the asymmetric stretching vibration of C-O-C; 1100cm-
1Be the C-O-C symmetrical stretching vibration;
Epoxidation: above-mentioned quantitative diacetyl rapeseed oil acid glyceride 500g, formic acid 22g, adding are had in the four-hole bottle of whipping appts, thermometer, dropping funnel, reflux condensing tube, be warming up to 55 ℃ under stirring, stir and slowly splash into 50% hydrogen peroxide 200g (98%H down
2SO
4Catalyzer 0.7g); add the back 75-80 ℃ of reaction 4 hours; tell lower floor's sour water; the upper strata grease successively with buck, be washed to neutrality; but acid number underpressure distillation below 0.6 dewater and filter light yellow oil diacetyl epoxy rapeseed oil acid glyceride; its oxirane value is 2.09, and acid number is 2.1, and iodine number is 32.Survey infrared spectra: IR (KBr): 2927cm-
1C-H asymmetrical stretching vibration absorption for stable hydrocarbon CH2; 2855cm-
1C-H symmetrical stretching vibration absorption for stable hydrocarbon CH2; 1745cm-
1C=O stretching vibration absorption for ester; 1463cm-
1C-H asymmetric bending vibration for methyl; 1376cm-
1C-H symmetric curvature vibration for methyl; 1166cm-
1Be the asymmetric stretching vibration of C-O-C; 1102cm-
1Be the C-O-C symmetrical stretching vibration; 821cm-
1Be the asymmetric stretching vibration of ternary cyclic ethers C-O-C; 726cm-
1Rocking vibration for methylene radical.
Claims (12)
1. diacetyl epoxidized vegetable oil acid glyceride, general formula is (I) or compound (II),
Wherein, R is 20 lipid acid that carbon atom is following in the vegetables oil.
2. diacetyl epoxidized vegetable oil acid glyceride as claimed in claim 1 is characterized in that: R is palmitic acid, stearic acid, cis-9-octadecenic acid, cis 9, cis-I2 octadecenic acid, cis-9, cis-I2, the cis-I5 octadecenic acid that is selected from the soybean oil; Or be selected from oleic acid, linolic acid, palmitinic acid in the Rice pollard oil; Or be selected from stearic acid, oleic acid, linolic acid in the plam oil; Or be selected from eicosanoic acid, oleic acid, linolic acid, erucic acid, linolenic acid in the rapeseed oil.
3. method from the synthetic diacetyl epoxidized vegetable oil acid glyceride as claimed in claim 1 of vegetables oil may further comprise the steps:
A. vegetables oil and glycerine carry out transesterify;
B. acetylize synthesis of diacetyl vegetable oil acid glyceryl ester;
C. diacetyl vegetable oil acid glyceryl ester epoxidation reaction;
Wherein, R
1, R
2, R
3Be 20 lipid acid below the carbon atom in the vegetables oil.
4. synthetic method as claimed in claim 3 is characterized in that: R
1, R
2, R
3For being selected from palmitic acid, stearic acid, cis-9-octadecenic acid (oleic acid), cis 9, cis-I2 octadecenic acid (linolic acid), cis-9, cis-I2, the cis-I5 octadecenic acid (linolenic acid) in the soybean oil; Or be selected from oleic acid, linolic acid, palmitinic acid in the Rice pollard oil; Or be selected from stearic acid, oleic acid, linolic acid in the plam oil; Or be selected from eicosanoic acid, oleic acid, linolic acid, erucic acid, linolenic acid in the rapeseed oil.
5. synthetic method as claimed in claim 3 is characterized in that: the glycerine consumption of described step a is the 18-25% (w/w) of vegetables oil consumption.
6. synthetic method as claimed in claim 3 is characterized in that: the transesterification reaction of described step a also can add catalyzer, and described catalyzer is selected from least a in Qing Yangization Na, potassium hydroxide, calcium oxide, calcium hydroxide, sodium methylate, the sodium ethylate.
7. synthetic method as claimed in claim 6 is characterized in that: the consumption of described transesterification catalyst is the 0.01-0.04% (w/w) of vegetables oil consumption.
8. synthetic method as claimed in claim 3; it is characterized in that: the acetylization reaction among the described step b can also add catalyzer; described catalyzer is selected from least a in sulfuric acid, tosic acid, the acidic ion exchange resin, and consumption is the 0.3%-0.6% of vegetable oil acid list glyceride consumption.
9. synthetic method as claimed in claim 3 is characterized in that: the acetylation reagent among the described step b is selected from Acetyl Chloride 98Min., Glacial acetic acid, diacetyl oxide, and consumption is the 40%-50% of vegetable oil acid list glyceride consumption.
10. synthetic method as claimed in claim 3 is characterized in that: can also use among the described step b and hang aqua, the described aqua that hangs is selected from benzene, hexanaphthene, hexane, and its consumption is the 35-40% of vegetable oil acid list glyceride consumption.
11. synthetic method as claimed in claim 3, it is characterized in that: among the step c, also add formic acid or acetate, wherein, diacetyl soybean oil acid glyceride: hydrogen peroxide: formic acid or acetate: catalyzer=1: 0.4-0.7: 0.04-0.08: 0.001-0.003 (mol ratio).
12. synthetic method as claimed in claim 11 is characterized in that: can also add sulfuric acid or phosphoric acid in the epoxidation reaction among the described step c.
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