CN107325274A - A kind of preparation method of low color polyoxyethylene sorbitan monoleate - Google Patents
A kind of preparation method of low color polyoxyethylene sorbitan monoleate Download PDFInfo
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- CN107325274A CN107325274A CN201710760065.XA CN201710760065A CN107325274A CN 107325274 A CN107325274 A CN 107325274A CN 201710760065 A CN201710760065 A CN 201710760065A CN 107325274 A CN107325274 A CN 107325274A
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- anhydrous sorbitol
- oleate
- polyoxyethylene sorbitan
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- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 229920001214 Polysorbate 60 Polymers 0.000 title claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims abstract description 41
- 239000000600 sorbitol Substances 0.000 claims abstract description 41
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 21
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 17
- 150000002148 esters Chemical group 0.000 claims abstract description 17
- 238000007046 ethoxylation reaction Methods 0.000 claims abstract description 15
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 14
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 14
- 229940049964 oleate Drugs 0.000 claims abstract description 13
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 9
- -1 sodium alkoxide Chemical class 0.000 claims abstract description 8
- 239000011734 sodium Substances 0.000 claims abstract description 7
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 3
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical group [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 claims description 6
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical group CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 claims description 6
- 229940073769 methyl oleate Drugs 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 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 4
- 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 claims description 4
- LVGKNOAMLMIIKO-UHFFFAOYSA-N Elaidinsaeure-aethylester Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC LVGKNOAMLMIIKO-UHFFFAOYSA-N 0.000 claims description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 4
- LVGKNOAMLMIIKO-QXMHVHEDSA-N ethyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC LVGKNOAMLMIIKO-QXMHVHEDSA-N 0.000 claims description 4
- 229940093471 ethyl oleate Drugs 0.000 claims description 4
- 239000003456 ion exchange resin Substances 0.000 claims description 4
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 4
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 4
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 4
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 claims description 3
- 229910001410 inorganic ion Inorganic materials 0.000 claims description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 12
- 230000032050 esterification Effects 0.000 abstract description 11
- 238000005886 esterification reaction Methods 0.000 abstract description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 10
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 abstract description 8
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 abstract description 8
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 abstract description 8
- 239000005642 Oleic acid Substances 0.000 abstract description 8
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 abstract description 8
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 abstract description 8
- 238000007796 conventional method Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000010792 warming Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 239000012043 crude product Substances 0.000 description 8
- 230000006837 decompression Effects 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000001593 sorbitan monooleate Substances 0.000 description 4
- 235000011069 sorbitan monooleate Nutrition 0.000 description 4
- 229940035049 sorbitan monooleate Drugs 0.000 description 4
- 238000010025 steaming Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 3
- 229920000053 polysorbate 80 Polymers 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000136 polysorbate Polymers 0.000 description 2
- 229950008882 polysorbate Drugs 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- SAJGCUXAHBJVRH-VFQQELCFSA-N (2r,3r,4r,5s)-hexane-1,2,3,4,5,6-hexol;hydrate Chemical compound O.OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO SAJGCUXAHBJVRH-VFQQELCFSA-N 0.000 description 1
- 241000220324 Pyrus Species 0.000 description 1
- NWGKJDSIEKMTRX-MDZDMXLPSA-N Sorbitan oleate Chemical compound CCCCCCCC\C=C\CCCCCCCC(=O)OCC(O)C1OCC(O)C1O NWGKJDSIEKMTRX-MDZDMXLPSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000006206 glycosylation reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 235000021017 pears Nutrition 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
- C08G2650/04—End-capping
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Furan Compounds (AREA)
Abstract
The present invention provides a kind of preparation method of low color polyoxyethylene sorbitan monoleate, including:In the presence of inorganic acid and antioxidant, sorbierite is carried out dehydration reaction, obtain anhydrous sorbitol;Add organic sodium alkoxide to adjust the pH value of anhydrous sorbitol to pH=10 12, oxirane is added afterwards and carries out ethoxylation with anhydrous sorbitol, anhydrous sorbitol APEO is obtained;And in a nitrogen atmosphere, add oleate and carry out ester exchange reaction with anhydrous sorbitol APEO, obtain low color polyoxyethylene sorbitan monoleate.The preparation method of the present invention avoids the process that the activated carbon used in conventional method, hydrogen peroxide carry out multistep decolouring, separating treatment is not needed in the middle of each course of reaction, ester exchange reaction is carried out using oleate simultaneously rather than direct esterification is carried out using oleic acid, good process repeatability, production efficiency is substantially improved, and product quality is stable.
Description
Technical field
The present invention relates to a kind of chemical industry synthesis method, and in particular to a kind of preparation method of low color polyoxyethylene sorbitan monoleate.
Background technology
Polyoxyethylene sorbitan monoleate, is commonly called as Tween 80, also referred to as polyoxyethylene (20) sorbitan monooleate, and it is a kind of hydrophilic
Type nonionic surfactant, there is significant resistance to electrolyte, and hydrophily is strong, is widely used in liquid, semisolid, solid
In preparation, as O/W types emulsifying agent, solubilizer, wetting agent, dispersant and stabilizer.Because there is preferable hydrotropy to act on for it,
When preparing the injection of insoluble drug, cosolvent, emulsifying agent and stabilizer are commonly used for.
Current polyoxyethylene sorbitan monoleate synthetic method generally has following two:(1) sorbierite is acted on oleic acid in base catalyst
It is lower that dehydration and esterification occur simultaneously, obtain sorbitan monooleate (being commonly called as sorbester p17), then again with 20 molar parts
Ring of numbers oxidative ethane condensation reaction, obtains Tween-80, refers to United States Patent (USP) US4297290.(2) sorbierite is in acidic catalyst
First it is dehydrated under agent effect, obtains anhydrous sorbitol, then occurring esterification with oleic acid again obtains sorbitan monooleate,
Finally reacted with 20 molfraction ethylene oxide condensations, obtain polyoxyethylene sorbitan monoleate.US8334397B2, which is disclosed, uses methyl oleate generation
The process that reaction prepares sorbitan monooleate, the hardship of its polyoxyethylene sorbitan monoleate prepared are carried out for oleic acid and anhydrous sorbitol
Taste can be significantly reduced.In addition, CN101701065B, CN102127217B etc. disclose a new preparation process:Sorbierite
First dehydration obtains anhydrous sorbitol under acidic catalyst effect, is then lost with the reaction of 20 molfraction ethylene oxide condensations
Water sorbitol polyoxyethylene ether, finally occurs esterification with oleic acid again and obtains polyoxyethylene sorbitan monoleate.
Three of the above method has the drawback that:In order to prepare the polyoxyethylene sorbitan monoleate of low color number, mistake is being prepared
It is required for being decolourized with activated carbon after water sorbierite or sorbitan monooleate, it is after 80s preparing polysorbate
It is also required to be decolourized with activated carbon or hydrogen peroxide, and then can just obtains the polyoxyethylene sorbitan monoleate of low color number.In preparation process not
Its application in downstream product all can be influenceed more than 500 using the color number of the polyoxyethylene sorbitan monoleate obtained by any decolorization process.
The content of the invention
In view of the deficienciess of the prior art, can conveniently prepare low color polysorbate it is an object of the invention to provide one kind
80 method, the problem of solving complicated decolorization process in the prior art, low production efficiency.
To achieve the above object, the present invention is adopted the following technical scheme that:
A kind of preparation method of low color polyoxyethylene sorbitan monoleate, including:
In the presence of inorganic acid and antioxidant, sorbierite is carried out dehydration reaction, obtain anhydrous sorbitol;
Add organic sodium alkoxide to adjust the pH value of anhydrous sorbitol to pH=10-12, oxirane and dehydration are added afterwards
Sorbierite carries out ethoxylation, obtains anhydrous sorbitol APEO;And
In a nitrogen atmosphere, add oleate and carry out ester exchange reaction with anhydrous sorbitol APEO, obtain low color
Number polyoxyethylene sorbitan monoleate.
In an embodiment of the preparation method of the present invention, the reaction temperature of the dehydration reaction is 100~180
DEG C, vacuum is 700~759mmHg, and the reaction time is 5-15h.
In another embodiment of the preparation method of the present invention, the inorganic acid is in sulfuric acid, phosphoric acid, phosphorous acid
One or more, the antioxidant is the one or more in sodium hypophosphite, sodium sulfite, sodium hydrogensulfite.
In another embodiment of the preparation method of the present invention, the consumption of the inorganic acid is sorbierite weight
0.5-1.5%, the consumption of the antioxidant is the 0.1-0.5% of sorbierite weight.
In another embodiment of the preparation method of the present invention, the organic sodium alkoxide is sodium methoxide or caustic alcohol.
In another embodiment of the preparation method of the present invention, the weight ratio of oxirane and anhydrous sorbitol is 1:
0.17~0.20.
In another embodiment of the preparation method of the present invention, the reaction temperature of the ethoxylation is 120
~160 DEG C, the reaction time is 4-10h.
In another embodiment of the preparation method of the present invention, the oleate is methyl oleate or ethyl oleate.
In another embodiment of the preparation method of the present invention, anhydrous sorbitol APEO and the oleate
Weight ratio be 1: 0.28~0.35.
In another embodiment of the preparation method of the present invention, the reaction temperature of the ester exchange reaction is 150-
210 DEG C, the reaction time is 6-14h.
The present invention preparation method another embodiment in, after ester exchange reaction, in addition to add go from
Sub- water, inorganic ions is removed by ion exchange resin post, is adjusted the electrical conductivity of product to less than 50, is then steamed moisture.
The preparation method of the present invention avoids the mistake that the activated carbon used in conventional method, hydrogen peroxide carry out multistep decolouring
Separating treatment is not needed in the middle of journey, each course of reaction, while carrying out ester exchange reaction using oleate rather than using oleic acid
Direct esterification is carried out, good process repeatability, production efficiency is substantially improved, product quality is stable.
Embodiment
Technical scheme is described further below according to specific embodiment.Protection scope of the present invention is not limited
In following examples, these examples are enumerated merely for exemplary purpose without limiting the present invention in any way.
The preparation method of the present invention is broadly divided into following several stages:Dehydration reaction prepares anhydrous sorbitol;Ethoxylation
Reaction prepares anhydrous sorbitol APEO;And ester exchange reaction prepares polyoxyethylene sorbitan monoleate.
It is in the presence of inorganic acid and antioxidant, sorbierite is carried out dehydration reaction, obtain dehydration in dehydration reaction
Sorbierite, reaction temperature is 100~180 DEG C, and vacuum is 700~759mmHg, and the reaction time is 5-15h.
Sorbierite used is usually sorbitol aqueous solution in dehydration reaction, and its mass concentration is 70% or so.
Inorganic acid used is the one or more in sulfuric acid, phosphoric acid, phosphorous acid in dehydration reaction, and consumption is sorbierite weight
The 0.5-1.5% of amount.
Antioxidant used is the one or more in sodium hypophosphite, sodium sulfite, sodium hydrogensulfite in dehydration reaction, is used
Measure as the 0.1-0.5% of sorbierite weight.Antioxidant is able to ensure that the oxygen dissolved in course of reaction cannot participate in reaction and produce
Coloring matter, so as to substantially reduce the color number of anhydrous sorbitol, and then reduces the color number of final product polyoxyethylene sorbitan monoleate.
Before ethoxylation, the pH of the anhydrous sorbitol obtained by previous step need to be adjusted to alkalescence, it is usually used to have
Machine sodium alkoxide such as sodium methoxide or caustic alcohol are adjusted, and the pH of anhydrous sorbitol is adjusted to pH=10-12.
Above-mentioned organic sodium alkoxide is added generally in the form of organic alcoholic solution, such as methanol solution of sodium methylate, in order to avoid
Low boiling Organic Alcohol also assists in ethoxylation generation accessory substance, in addition it is also necessary to carry out second again after carrying out vacuum removal low boiling Organic Alcohol
Oxygen glycosylation reaction.
It is that oxirane carries out the obtained dehydration mountain of reaction with the anhydrous sorbitol obtained by previous step in ethoxylation
Pears alcohol APEO, the addition total amount of its ethylene oxide and the weight ratio of anhydrous sorbitol are 1: 0.17~0.20, and it rubs
That ratio about 20:1, to ensure being smoothed out for reaction.
The reaction temperature of ethoxylation is 120~160 DEG C, and the reaction time is 4-10h.
After ethoxylation, it is passed through inert gas such as nitrogen to replace the air in reaction vessel, adjusts reaction gas
Atmosphere, adds oleate afterwards, it is carried out ester exchange reaction with the anhydrous sorbitol APEO obtained by previous step and is made
Polyoxyethylene sorbitan monoleate crude product.
Oleate used is methyl oleate or ethyl oleate in ester exchange reaction, and esterification is carried out using ester-interchange method
Rather than direct esterification is carried out using oleic acid, can so it reaction system is maintained close to neutrality, it is to avoid under the conditions of strong acid-base
Generate coloring matter.
In ester exchange reaction, the weight ratio of anhydrous sorbitol APEO and oleate is 1: 0.28~0.35, reaction
Temperature is 150-210 DEG C, and the reaction time is 6-14h.
Extra separating treatment need not be carried out in the middle of dehydration reaction, ethoxylation and ester exchange reaction, also
Avoid the process that the activated carbon used in conventional method, hydrogen peroxide carry out multistep decolouring.
After ester exchange reaction, can also deionization processing be carried out to polyoxyethylene sorbitan monoleate crude product, that is, add deionized water, led to
Cross ion exchange resin post and remove inorganic ions, adjust the electrical conductivity of product to less than 50, then steam moisture, finally give low color number
Polyoxyethylene sorbitan monoleate.
Ion exchange resin post used is the group that cationic resin column and resin anion (R.A.) post used in conventional deionization are formed
Close, evaporation efficiency can be improved using thin film evaporator by steaming moisture.
Unless otherwise defined, term used herein is the implication that those skilled in the art are generally understood that.
With reference to embodiment, the invention will be further described.
Embodiment
Determination of colority opens the SD-2 chromascopes of prestige electronics using Shanghai in each embodiment, and conductivity meter is DDS-307A types.
Embodiment 1
(1) at room temperature, 100g70% sorbitol aqueous solution is added into 250mL four-hole bottle, stirring is started and is warming up to
90 DEG C, vacuum 750mmHg is evacuated down to, water is steamed in decompression until water removal is complete.It is continuously heating to 125 DEG C of temperature in the kettle, Xiang Qi
It is middle to add the nitration mixture catalyst 0.7g (phosphoric acid configured:Sulfuric acid=17:1 weight ratio) and antioxidant sodium hypophosphite 0.14g.Subtract
Pressure is warming up to 135 DEG C, maintains vacuum 750mmHg, is incubated 5 hours, obtains anhydrous sorbitol 63g.
(2) 60 DEG C are cooled to, 20% methanol solution of sodium methylate is added thereto and is adjusted to pH=10.5, is stirred 30 minutes,
It is evacuated down to 350mmHg and removes low-boiling-point substance methanol therein.It is then transferred into 1L high pressure ethoxylation kettles, nitrogen displacement kettle
In air three times, be then warming up to 125 DEG C, oxirane added in batches and maintains pressure to be no more than 0.4MPa, until epoxy
The addition of ethane is 338g, continues to react 1h, and untill reaction pressure no longer declines, kettle is driven in decompression, obtains Sorbitan
Alcohol APEO 401g.
(3) above-mentioned anhydrous sorbitol APEO is transferred in 1L reaction kettle of the esterification, adds methyl oleate 115g, so
After be warming up to 180 DEG C, nitrogen bubble reaction 12h, cooling obtains polyoxyethylene sorbitan monoleate crude product 502g.
(4) added into polyoxyethylene sorbitan monoleate crude product after 500g deionized waters, 30min is stirred, then by resin cation
Post and resin anion (R.A.) post carry out ion exchange, control the electrical conductivity of product<50, further with thin film evaporator in 100 DEG C of steamings
The polyoxyethylene sorbitan monoleate product 485g that color number is 75 is obtained after water outlet.
Embodiment 2
(1) at room temperature, 100g70% sorbitol aqueous solution is added into 250mL four-hole bottle, stirring is started and is warming up to
90 DEG C, vacuum 720mmHg is evacuated down to, water is steamed in decompression until water removal is complete.It is continuously heating to 125 DEG C of temperature in the kettle, Xiang Qi
It is middle to add the phosphoric acid catalyst 0.7g and antioxidant Sodium Thiosulfate 0.14g configured.Decompression is warming up to 150 DEG C, maintains vacuum
720mmHg is spent, 10 hours is incubated, obtains anhydrous sorbitol 65g.
(2) 60 DEG C are cooled to, 20% methanol solution of sodium methylate is added thereto and is adjusted to pH=12, stirs 30 minutes, takes out
Vacuum removes low-boiling-point substance methanol therein to 350mmHg.It is then transferred into 1L high pressure ethoxylation kettles, nitrogen displacement kettle
Air three times, be then warming up to 155 DEG C, oxirane added in batches and maintains pressure to be no more than 0.4MPa, until epoxy second
The addition of alkane is 345g, continues to react 1h, and untill reaction pressure no longer declines, kettle is driven in decompression, obtains anhydrous sorbitol
APEO 407g.
(3) above-mentioned anhydrous sorbitol APEO is transferred in 1L reaction kettle of the esterification, adds methyl oleate 120g, so
After be warming up to 210 DEG C, nitrogen bubble reaction 6h, cooling obtains polyoxyethylene sorbitan monoleate crude product 506g.
(4) added into polyoxyethylene sorbitan monoleate crude product after 450g deionized waters, 30min is stirred, then by resin cation
Post and resin anion (R.A.) post carry out ion exchange, control the electrical conductivity of product<50, further with thin film evaporator in 100 DEG C of steamings
The polyoxyethylene sorbitan monoleate product 490g that color number is 85 is obtained after water outlet.
Embodiment 3
(1) at room temperature, 100g70% sorbitol aqueous solution is added into 250mL four-hole bottle, stirring is started and is warming up to
90 DEG C, vacuum 735mmHg is evacuated down to, water is steamed in decompression until water removal is complete.It is continuously heating to 125 DEG C of temperature in the kettle, Xiang Qi
It is middle to add the phosphorous acid catalyst 0.35g and antioxidant sodium hydrogensulfite 0.32g configured.Decompression is warming up to 175 DEG C, remains true
Reciprocal of duty cycle 735mmHg, is incubated 8 hours, obtains anhydrous sorbitol 60g.
(2) 60 DEG C are cooled to, 20% methanol solution of sodium methylate is added thereto and is adjusted to pH=11.5, is stirred 30 minutes,
It is evacuated down to 350mmHg and removes low-boiling-point substance methanol therein.It is then transferred into 1L high pressure ethoxylation kettles, nitrogen displacement kettle
In air three times, be then warming up to 135 DEG C, oxirane added in batches and maintains pressure to be no more than 0.4MPa, until epoxy
The addition of ethane is 335g, continues to react 1h, and untill reaction pressure no longer declines, kettle is driven in decompression, obtains Sorbitan
Alcohol APEO 395g.
(3) above-mentioned anhydrous sorbitol APEO is transferred in 1L reaction kettle of the esterification, adds ethyl oleate 135g, so
After be warming up to 170 DEG C, nitrogen bubble reaction 14h, cooling obtains polyoxyethylene sorbitan monoleate crude product 522g.
(4) added into polyoxyethylene sorbitan monoleate crude product after 530g deionized waters, 30min is stirred, then by resin cation
Post and resin anion (R.A.) post carry out ion exchange, control the electrical conductivity of product<50, further with thin film evaporator in 100 DEG C of steamings
The polyoxyethylene sorbitan monoleate product 510g that color number is 75 is obtained after water outlet.
In summary, preparation method of the invention reduces color number in the preparation of anhydrous sorbitol using antioxidant, it is to avoid
The activated carbon, the hydrogen peroxide that are used in conventional method be not required in the middle of the process of multistep decolouring, each course of reaction to be separated
Processing, while carrying out ester exchange reaction using oleate rather than carrying out direct esterification, good process repeatability, production using oleic acid
Efficiency is substantially improved, and product quality is stable.
Those skilled in the art should be noted that embodiment described in the invention is only exemplary, can be
Various other replacements, changes and improvements are made in the scope of the present invention.Thus, the invention is not restricted to above-mentioned embodiment, and only
It is defined by the claims.
Claims (11)
1. a kind of preparation method of low color polyoxyethylene sorbitan monoleate, including:
In the presence of inorganic acid and antioxidant, sorbierite is carried out dehydration reaction, obtain anhydrous sorbitol;
Add organic sodium alkoxide to adjust the pH value of anhydrous sorbitol to pH=10-12, oxirane and Sorbitan are added afterwards
Alcohol carries out ethoxylation, obtains anhydrous sorbitol APEO;And
In a nitrogen atmosphere, add oleate and carry out ester exchange reaction with anhydrous sorbitol APEO, obtain low color number and gather
Sorb ester 80.
2. preparation method according to claim 1, wherein the reaction temperature of dehydration reaction is 100~180 DEG C, vacuum
Spend for 700~759mmHg, the reaction time is 5-15h.
3. preparation method according to claim 1, wherein the inorganic acid be one kind in sulfuric acid, phosphoric acid, phosphorous acid or
A variety of, the antioxidant is the one or more in sodium hypophosphite, sodium sulfite, sodium hydrogensulfite.
4. preparation method according to claim 3, wherein the consumption of the inorganic acid is the 0.5- of sorbierite weight
1.5%, the consumption of the antioxidant is the 0.1-0.5% of sorbierite weight.
5. preparation method according to claim 1, wherein the organic sodium alkoxide is sodium methoxide or caustic alcohol.
6. the weight ratio of preparation method according to claim 1, its ethylene oxide and anhydrous sorbitol be 1: 0.17~
0.20。
7. preparation method according to claim 1, wherein the reaction temperature of the ethoxylation is 120~160 DEG C,
Reaction time is 4-10h.
8. preparation method according to claim 1, wherein the oleate is methyl oleate or ethyl oleate.
9. preparation method according to claim 8, wherein anhydrous sorbitol APEO and the weight of the oleate
Than for 1: 0.28~0.35.
10. preparation method according to claim 1, wherein the reaction temperature of the ester exchange reaction is 150-210 DEG C, instead
It is 6-14h between seasonable.
11. preparation method according to any one of claim 1 to 10, wherein after ester exchange reaction, in addition to add
Enter deionized water, inorganic ions is removed by ion exchange resin post, adjust the electrical conductivity of product to less than 50, then steam moisture.
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