CN1730585A - Method for directly synthesizing rosin acid sucrose ester by using rosin and sucrose - Google Patents
Method for directly synthesizing rosin acid sucrose ester by using rosin and sucrose Download PDFInfo
- Publication number
- CN1730585A CN1730585A CNA2005100189476A CN200510018947A CN1730585A CN 1730585 A CN1730585 A CN 1730585A CN A2005100189476 A CNA2005100189476 A CN A2005100189476A CN 200510018947 A CN200510018947 A CN 200510018947A CN 1730585 A CN1730585 A CN 1730585A
- Authority
- CN
- China
- Prior art keywords
- rosin
- sucrose
- product
- ester
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229930006000 Sucrose Natural products 0.000 title claims abstract description 75
- 239000005720 sucrose Substances 0.000 title claims abstract description 75
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 title claims abstract description 62
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 title claims abstract description 61
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 title claims abstract description 61
- -1 rosin acid sucrose ester Chemical class 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 37
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 title claims abstract description 31
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 239000000047 product Substances 0.000 claims description 55
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 claims description 36
- 238000010992 reflux Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 9
- 235000021355 Stearic acid Nutrition 0.000 claims description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 7
- 239000008117 stearic acid Substances 0.000 claims description 7
- 238000010189 synthetic method Methods 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 5
- 239000012454 non-polar solvent Substances 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 238000004821 distillation Methods 0.000 claims 1
- 230000001737 promoting effect Effects 0.000 claims 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 6
- 239000012043 crude product Substances 0.000 abstract description 3
- 239000003208 petroleum Substances 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract 3
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000000605 extraction Methods 0.000 description 9
- 238000004128 high performance liquid chromatography Methods 0.000 description 9
- 238000005886 esterification reaction Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 229960000583 acetic acid Drugs 0.000 description 7
- 230000032050 esterification Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 239000003995 emulsifying agent Substances 0.000 description 6
- 239000012362 glacial acetic acid Substances 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- AGUBCDYYAKENKG-UHFFFAOYSA-N Abietinsaeure-aethylester Natural products C1CC(C(C)C)=CC2=CCC3C(C(=O)OCC)(C)CCCC3(C)C21 AGUBCDYYAKENKG-UHFFFAOYSA-N 0.000 description 5
- AGUBCDYYAKENKG-YVNJGZBMSA-N Ethyl abietate Chemical compound C1CC(C(C)C)=CC2=CC[C@H]3[C@@](C(=O)OCC)(C)CCC[C@]3(C)[C@H]21 AGUBCDYYAKENKG-YVNJGZBMSA-N 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000001804 emulsifying effect Effects 0.000 description 4
- 125000004494 ethyl ester group Chemical group 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 238000000593 microemulsion method Methods 0.000 description 2
- 230000001473 noxious effect Effects 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical group CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- OVXRPXGVKBHGQO-UHFFFAOYSA-N abietic acid methyl ester Natural products C1CC(C(C)C)=CC2=CCC3C(C(=O)OC)(C)CCCC3(C)C21 OVXRPXGVKBHGQO-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 235000010985 glycerol esters of wood rosin Nutrition 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 239000003845 household chemical Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- OVXRPXGVKBHGQO-UYWIDEMCSA-N methyl (1r,4ar,4br,10ar)-1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylate Chemical compound C1CC(C(C)C)=CC2=CC[C@H]3[C@@](C(=O)OC)(C)CCC[C@]3(C)[C@H]21 OVXRPXGVKBHGQO-UYWIDEMCSA-N 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009923 sugaring Methods 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
Images
Landscapes
- Saccharide Compounds (AREA)
Abstract
The invention discloses a direct synthesis method of abietic acid sucrose ester using rosin and sucrose which comprises, at the presence of polyatomic alcohol dissolvent, using anhydrous sodium carbonate as catalyst, directly synthesizing from rosin and sucrose, extracting with acetone, washing and purifying the crude product yield with petroleum benzene. The process of the invention has the advantages of fast reaction rate, high yield, solvent reclamation and no environmental pollution.
Description
Technical field
The present invention relates to a kind of method that directly prepares the nontoxicity Sucrose Ester of Rosin Acid by rosin and sucrose.
Background technology
Sucrose ester is a class new non-ionic type tensio-active agent, harmless, not skin irritation and mucous membrane, nontoxic; Readily biodegradable becomes the absorbable material of human body; Effects such as good emulsifying, dispersion, decontamination, foaming, viscosity adjustment, antibiotic, anti-aging, anti-partial crystallization are arranged, and are solubility promoter, foodstuff additive and the preservation agents that Food and Argriculture OrganizationFAO and world health organisation recommendations are used.Can be used as the emulsifying agent of emulsifying agent, dispersion agent and viscosity modifier, washing composition, agricultural chemicals, medicine and the makeup of food.Be widely used in fields such as food, pharmacy, sugaring, household chemicals, market demand is very big.Traditional sucrose ester refers generally to stearic acid sucrose ester, its production technique mainly contains ester-interchange method (solvent method, micro emulsion method, scorification), direct esterification method (chloride method, direct evaporation) and microbial method three major types, these methods or use noxious solvent, or reaction conditions requires height, the time is long, cost is high, or the reaction system instability, quality product can not get guaranteeing.At present in the actual production based on ester-interchange method, wherein again with scorification and micro emulsion method from Financial cost and operate the controlled development prospect that has more.
Rosin and sucrose all are the abundant renewable resourcess in area, Guangxi.The rosin molecule contains a carboxyl, can esterification take place with alcohol.But because the space steric effect is big in the rosin molecule, the difficulty that esterification takes place is higher than lipid acid.In the document of having delivered, all be to adopt the transesterification reaction of methyl abietate (or ethyl ester) and sucrose to realize.Because these methods all will be carried out in two steps, at first rosin will be changed into rosin ester, make product by transesterification reaction again.Reaction process is very long, and uses poisonous raw material such as benzene, methyl alcohol etc. to carry out products production and purifying, is unfavorable for the application of industrial production and product.
With prior art like the present invention recently in, to be that synthetic method in " synthetic Sucrose Ester of Rosin Acid of mini-emulsion process and the application performance research thereof " of Feng Guangzhu etc. is the most representative with Zhengzhou Engineering College's chemical, this article is pointed out: rosin and ethanol under the basic catalyst effect prepared in reaction ethyl abietate, be raw material with ethyl abietate and sucrose again, under the micro-emulsifier condition, carry out transesterify and synthesized Sucrose Ester of Rosin Acid, investigated proportioning raw materials, temperature of reaction, reaction times, the kind of catalyzer and consumption, emulsifying agent and system pressure are to the influence of Sucrose Ester of Rosin Acid productive rate, the Sucrose Ester of Rosin Acid optimum synthesis condition that the quadratic regression orthogonal experiment is determined is an ethyl abietate: the sucrose mol ratio is 245: 1, emulsifying agent and sucrose mass ratio are 0.14: 1, catalyzer and reaction mass mass ratio are 0.045: 1,93 ℃ of temperature of reaction, pressure 4.86kPa, reaction times 3.45h, productive rate is 82.07%, monoester content 58.2%.Product has the surface of good activity, and its emulsifying capacity and foaming power and sodium lauryl sulphate are suitable, and froth stability is good.But this synthetic method still has following weak point:
1. the synthetic of Sucrose Ester of Rosin Acid will carry out in two steps: the first step prepares ethyl abietate, and second step, carried out building-up reactions with ethyl abietate and makes the Sucrose Ester of Rosin Acid product under the condition of the existence that emulsifying agent, catalyzer exist again with behind the sucrose hot melt.
2. higher to raw materials for production rosiny specification of quality.Requiring rosin is select quality, also will remove the purification process of insolubles and impurity.
3. the Sucrose Ester of Rosin Acid productive rate only is 82.07%, monoester content 58.2%.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of rosin and direct esterification reaction and the purifying products method of sucrose under the condition of catalyzer and solvent existence.
The present invention solves the problems of the technologies described above with following technical scheme.The production method of Sucrose Ester of Rosin Acid is as follows:
1. direct esterification: in container, add the sucrose of metering and rosin, with polyvalent alcohol, a certain amount of anhydrous sodium carbonate of weight such as rosin.Heating reflux reaction.
2. steam solvent: after above-mentioned esterification is finished, use reflux instead water distilling apparatus, heating, the moisture that solvent and reaction are generated steams.
3. separated product, treat that temperature reduces after, add acetone, the pH value with the Glacial acetic acid regulator solution is neutral simultaneously, refluxes more than 20 minutes to extract the product of generation.Filter, acetone in the filtrate is steamed, get brown thick product after the drying.
4. thick purifying products is removed unreacted rosin.Obtain Sucrose Ester of Rosin Acid, product purity is more than 95%, and product yield is more than 95%.
The production method of Sucrose Ester of Rosin Acid provided by the invention has the following advantages:
1. rosin and sucrose direct esterification, the reaction times is short.
2. in the inventive method rosin quality is not had special requirement, can use the low level rosin that goes out of use, and, greatly improved its added value of product without purification process.
3. with present method production Sucrose Ester of Rosin Acid, the product yield height more than 95%, reaches as high as 98%, and monoesters purity reaches more than 95%.
4. do not produce environmental pollutant in the reaction process, solvent for use is all recyclable, re-uses, and saves cost.
5. do not use Toxic in the synthetic reaction process, product does not contain Toxic matter, and the application of product is unrestricted.
6. adopt new separating technology, do not use noxious solvent, simple to operate, good separating effect.
Description of drawings
Fig. 1 is the product that obtains of the inventive method and the infrared spectrogram of related compound.Among the figure: I is a rosin, and II is the rosin ethyl ester, and III is a rosin ethylene glycol ester, and IV is an ester gum, and V is a Sucrose Ester of Rosin Acid.
Fig. 2 is the inventive method obtains 0.1% ethanolic soln of product with n-butanol extraction a HPLC analysis of spectra.
Fig. 3 is the HPLC analysis of spectra of the inventive method with 0.1% ethanolic soln of acetone extract-petroleum ether product.
Fig. 4 is 0.1% an ethanolic soln HPLC analysis of spectra of rosin raw material.
Fig. 5 is the HPLC analysis of spectra by literature method synthetic Sucrose Ester of Rosin Acid.
Embodiment
Sucrose Ester of Rosin Acid among the present invention is synthetic by following raw material:
Rosin: no rank requirement
Sucrose: technical grade
Anhydrous sodium carbonate: technical grade
Polyalcohols solvent (as ethylene glycol, propylene glycol, glycerol): technical grade.
Glacial acetic acid: technical grade
Sherwood oil (90 ℃ 120 ℃ of boiling ranges): technical grade
Acetone: technical grade
The production method of Sucrose Ester of Rosin Acid of the present invention is as follows:
1. direct esterification: in container, add metering without the sucrose of pulverization process and rosin (mol ratio 1～4: 1), with the propylene glycol of weight such as rosin and be equivalent to the anhydrous sodium carbonate of rosin amount 10-40% (w%), under 100-180 ℃ of temperature condition heating reflux reaction 1.5-3 hour.
2. steam solvent: make above-mentioned reaction unit into water distilling apparatus, 150-180 ℃ of heating is more than 0.5 hour, and the moisture that solvent and reaction are generated steams.
3. separated product: after treating that temperature reduces, add proper amount of acetone, add Glacial acetic acid regulator solution pH simultaneously for neutral, the product that extraction generates more than 20 minutes refluxes.After the filtration filter cake is extracted once by same way as with acetone again.Merging filtrate steams acetone, gets brown crude product after the drying.
4. remove unreacted rosin: with crude product with an amount of sherwood oil heated scrub for several times to remove remaining rosin.Be the product Sucrose Ester of Rosin Acid after the product drying.The analytical results of infrared spectra and liquid chromatography has all been verified this point, and productive rate mixes the different of mol ratio according to sucrose with rosin and changes, and reaches as high as more than 99%, and the purity of product is more than 95%.
This law institute synthetic Sucrose Ester of Rosin Acid outward appearance is a reddish-brown, and is soluble in water and pure, is slightly soluble in non-polar solvent.The results of FT-IR is seen Fig. 1.Can know from the comparison of rosin, rosin ethyl ester, rosin ethylene glycol ester, rosin glycerine ester and Sucrose Ester of Rosin Acid and to find out that the content of hydroxyl is much higher than all the other compounds in this product.Also can see the absorption peak of carbonyl and ester group in addition among the figure.In conjunction with the character of product, can determine that it is the rosin monoesters, because alcohol is excessive greatly under synthesis condition, the rosin polyester is a fat-soluble cpds in addition, can be eliminated in the product purification process.
Reaction conditions to productive rate to influence situation as follows:
1. solvent adding amount is to the influence of productive rate
11.0g sucrose, 5.0g rosin, 1.0g catalyzer anhydrous sodium carbonate prepares Sucrose Ester of Rosin Acid by adding various amounts of solvent by the previous reaction mode under 150 ℃ of conditions of temperature, and the productive rate changing conditions of product sees Table 1:
Table 1 solvent load is to the influence of productive rate
| Solvent adding amount (g) | 0 | 2.5 | 5 | 7.5 | 10 |
| Productive rate (%) | 0 | 86 | 98 | 98 | 95 |
2. different blended composition and division in a proportion and temperature of reaction are to the influence of productive rate
5.0g rosin, the 5.0g solvent, 1.0g catalyzer anhydrous sodium carbonate, the ratio of mixture 1: 1 of pressing rosin and sucrose, 1: 1.5,1: 2, after different ratios added sucrose in 1: 4, under 150 ℃ of conditions of temperature, prepare Sucrose Ester of Rosin Acid with aforementioned reactive mode, productive rate is as follows:
Table 2 different blended composition and division in a proportion is to the influence of productive rate
| Ratio of mixture (rosin/sucrose) | 1∶1 | 1∶1.5 | 1∶2 | 1∶4 |
| Productive rate (%) | 40 | 78 | 98 | 98 |
Therefore rosin/sucrose=1: 2 is proper.The too many productive rate of sucrose improves little.
Temperature of reaction also can exert an influence to productive rate.Subject to the foregoing, the selective reaction temperature is 100,150 and 180 ℃ respectively, and corresponding productive rate is respectively 74%, 98% and 98%.Therefore 150 ℃ proper.
3. catalyst levels is to the influence of productive rate
11.0g sucrose, 5g rosin, by adding the Preparation of Catalyst Sucrose Ester of Rosin Acid of different amounts, the productive rate changing conditions of product sees Table 3 by the previous reaction mode:
Table 3 catalyst levels is to the influence of productive rate
| Catalyst levels (g) | 0 | 0.5 | 1 | 2 |
| Productive rate (%) | 0 | 81 | 98 | 98 |
Major equipment of the present invention comprises equipment such as reaction vessel, filtration.
The essential property of Sucrose Ester of Rosin Acid: this law institute synthetic Sucrose Ester of Rosin Acid outward appearance is a dark-brown, and is soluble in water and pure, is slightly soluble in non-polar solvent.The The results of FT-IR See Figure.Can know from the comparison of rosin, rosin ethyl ester, rosin ethylene glycol ester, rosin glycerine ester and Sucrose Ester of Rosin Acid and to find out that the content of hydroxyl is much higher than all the other compounds in this product.Also can see the absorption peak of carbonyl and ester group in addition among the figure.In conjunction with the character of product, can determine that it is the rosin monoesters, because alcohol is excessive greatly under synthesis condition, the rosin polyester is a fat-soluble cpds in addition, can be eliminated in the product purification process.Measured the emulsifying power and the foam power of Sucrose Ester of Rosin Acid according to the method for document, the result is as follows:
The emulsifying power and the foam power of the Sucrose Ester of Rosin Acid product of table 4 the inventive method preparation
| Foam power/height mm | Breast | Change power/height mm | ||
| Initial | After 30 minutes | Oil | Water layer | |
| 20 | 12 | 38 | 58 | |
The basically identical as a result of this and document.The HPLC analytical results shows that unreacted rosin content is below 1% in the product, and the acid number of product is below 10mg KOH/g.
The product that the inventive method obtains and the infrared spectrogram of related compound as shown in Figure 1, spectrum analysis: the infrared spectrogram of synthetic product rosin sugarcane ester and rosin and other related compound relatively, 3430cm
-1The hydroxyl absorption peak at place obviously increases with the increase of hydroxy radical content in the ester, and the hydroxyl absorption peak of synthetic product is the strongest, illustrates that hydroxy radical content is higher than other compound in the product.At 1630cm
-1Place's carbonyl peak is at 1050cm
-1The C-O-C of place asymmetrical stretching vibration absorption peak shows that all product really is ester cpds.
0.1% ethanolic soln HPLC analysis of spectra of the inventive method usefulness n-butanol extraction products therefrom as shown in Figure 2.
0.1% ethanolic soln HPLC analysis of spectra of the inventive method usefulness acetone extract-petroleum ether product as shown in Figure 3.
0.1% ethanolic soln HPLC analysis of spectra of rosin raw material as shown in Figure 4.
The HPLC analysis of spectra of pressing literature method synthetic Sucrose Ester of Rosin Acid as shown in Figure 5.
In the liquid chromatography, product and press literature method synthetic Sucrose Ester of Rosin Acid under analysis condition at 1.9min appearance the last one chromatographic peak, and in the rosin various isomer retention time from 2.1～6min.These confirm that also product really is Sucrose Ester of Rosin Acid.In the product remaining rosin amount can from 3.8min rosin main peak and long-pending estimation.
Adopt above same synthetic method, replace rosin,, can obtain stearic acid sucrose ester equally with the sucrose building-up reactions with stearic acid.The present invention also is applicable to the synthetic of stearic acid sucrose ester.
Concrete experiment method of the present invention:
Embodiment 1: in the 500mL round-bottomed flask, add 55.0g sucrose (not making pulverization process) and 5.0g catalyzer anhydrous sodium carbonate, 25.0g rosin, do to mix the back slightly and add 25mL solvent propylene glycol, 150 ℃ of reactions 2 hours, change reflux into water distilling apparatus, continue reaction 1 hour, steam about 22mL liquid.Stop heating, product cools off the back slightly and drip 250mL acetone with dropping funnel under induction stirring, refluxes 20 minutes, adds glacial acetic acid again and regulates pH to neutral, fully stirs the back filtered while hot.With filter cake again with the extraction of 250mL acetone reflux once, merge extraction liquid twice, steam acetone, non-volatile brown oil is with sherwood oil heated scrub four times, promptly gets the product Sucrose Ester of Rosin Acid after removing sherwood oil.The thick productive rate of experimental calculation about 98%.
Embodiment 2: in flask at the bottom of the 100mL garden, add 11.0g sucrose (not making pulverization process) and 1.0g catalyzer anhydrous sodium carbonate, 5.0g rosin, do to mix the back slightly and add 5mL solvent propylene glycol, 150 ℃ of reactions 3 hours, stop heating, product cools off in the back impouring 200mL15%NaCl solution slightly, regulates the pH value to neutral with little acetic acid.Filter, filter cake with sherwood oil heated scrub four times, is promptly got the product Sucrose Ester of Rosin Acid after removing sherwood oil.The thick productive rate of experimental calculation about 71%.
Embodiment 3: in flask at the bottom of the 100mL garden, add 11.0g sucrose (not making pulverization process) and 2.0g catalyzer anhydrous sodium carbonate, 5.0g rosin, do to mix the back slightly and add 5mL solvent propylene glycol, 150 ℃ of reactions 2 hours, change reflux into water distilling apparatus, continue to react and distilled 1 hour.Stop heating, product cools off the back slightly and drip 250mL acetone with dropping funnel under induction stirring, refluxes 20 minutes, adds a small amount of glacial acetic acid again and regulates pH to neutral, fully stirs the back filtered while hot.With filter cake again with the extraction of 250mL acetone reflux once, merge extraction liquid twice, steam acetone, non-volatile tone tablet look oily matter is with sherwood oil heated scrub four times, promptly gets the product Sucrose Ester of Rosin Acid after removing sherwood oil.The thick productive rate of experimental calculation about 98%.
Embodiment 4: in the 500mL round-bottomed flask, add 55.0g sucrose (not making pulverization process) and 5.0g catalyzer anhydrous sodium carbonate, 22.9g stearic acid, do to mix the back slightly and add 25mL solvent propylene glycol, 150 ℃ of reactions 2 hours, change reflux into water distilling apparatus, continue reaction 1 hour, steam about 20mL liquid.Stop heating, product cools off the back slightly and drip 250mL acetone with dropping funnel under induction stirring, refluxes 20 minutes, adds glacial acetic acid again and regulates pH to neutral, fully stirs the back filtered while hot.With filter cake more once, merge extraction liquid twice, steam acetone and promptly get the product Sucrose Ester of Rosin Acid with the extraction of 250mL acetone reflux.The thick productive rate of experimental calculation about 96%.
Claims (5)
1, a kind of from the direct method of synthetic Sucrose Ester of Rosin Acid of rosin and sucrose, it is characterized in that promoting reaction directly to carry out by adding the polyalcohols solvent.
2, synthetic method according to claim 1 is characterized in that passing through earlier heating reflux reaction, uses distillation method again instead and removes the moisture that desolvates and generate, to obtain high yield.
3, synthetic method according to claim 1 is characterized in that utilizing acetone extract method purification reaction product.
4, synthetic method according to claim 1 is characterized in that product washs the rosin of removing the end reaction by sherwood oil or other non-polar solvent.
5, synthesize stearic acid sucrose ester according to the same quadrat method of claim 1 from stearic acid and sucrose.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100189476A CN100351334C (en) | 2005-06-16 | 2005-06-16 | Direct synthesis method of abietic acid sucrose ester using rosin and sucrose |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100189476A CN100351334C (en) | 2005-06-16 | 2005-06-16 | Direct synthesis method of abietic acid sucrose ester using rosin and sucrose |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1730585A true CN1730585A (en) | 2006-02-08 |
| CN100351334C CN100351334C (en) | 2007-11-28 |
Family
ID=35963008
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100189476A Expired - Fee Related CN100351334C (en) | 2005-06-16 | 2005-06-16 | Direct synthesis method of abietic acid sucrose ester using rosin and sucrose |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100351334C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103409744A (en) * | 2013-07-25 | 2013-11-27 | 鲁东大学 | Water-soluble modified rosin product, sealing agent and application of sealing agent |
| CN106398543A (en) * | 2016-08-31 | 2017-02-15 | 广西华林化工有限公司 | Preparation method of hydrogenated rosin sucrose ester through grinding method |
| CN106479366A (en) * | 2016-08-31 | 2017-03-08 | 广西华林化工有限公司 | A kind of preparation method of Hydrogenated Rosin Sucrose Esters |
| CN110143990A (en) * | 2019-05-31 | 2019-08-20 | 广西大学 | A method for preparing food-grade rosin xylose ester by catalytic esterification-separation coupling |
-
2005
- 2005-06-16 CN CNB2005100189476A patent/CN100351334C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103409744A (en) * | 2013-07-25 | 2013-11-27 | 鲁东大学 | Water-soluble modified rosin product, sealing agent and application of sealing agent |
| CN103409744B (en) * | 2013-07-25 | 2015-04-22 | 鲁东大学 | Water-soluble modified rosin product, sealing agent and application of sealing agent |
| CN106398543A (en) * | 2016-08-31 | 2017-02-15 | 广西华林化工有限公司 | Preparation method of hydrogenated rosin sucrose ester through grinding method |
| CN106479366A (en) * | 2016-08-31 | 2017-03-08 | 广西华林化工有限公司 | A kind of preparation method of Hydrogenated Rosin Sucrose Esters |
| CN106479366B (en) * | 2016-08-31 | 2019-05-21 | 广西华林化工有限公司 | A kind of preparation method of Hydrogenated Rosin Sucrose Esters |
| CN110143990A (en) * | 2019-05-31 | 2019-08-20 | 广西大学 | A method for preparing food-grade rosin xylose ester by catalytic esterification-separation coupling |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100351334C (en) | 2007-11-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6712867B1 (en) | Process for production of fatty acid methyl esters from fatty acid triglycerides | |
| DE60023710T2 (en) | A one-phase process for the preparation of fatty acid methyl esters from mixtures of triglycerides and fatty acids | |
| US9631161B2 (en) | Method of separating oil from a liquid stillage | |
| CN100351334C (en) | Direct synthesis method of abietic acid sucrose ester using rosin and sucrose | |
| CN1276926C (en) | Tannic acid purifying process | |
| EP3626700B1 (en) | Method for decolorizing and deodorizing polyhydric alcohol | |
| CN1634852A (en) | Separation and preparation method of eicosapentaenoic acid ethyl ester and docosahexaenoic acid ethyl ester | |
| CN101823928A (en) | Clean production process for derivatives of para aminobenzoic acid by reactor coupled simulated moving bed | |
| CN102060881A (en) | Method for preparing high-grade sucrose fatty acid ester from woody oil | |
| JP2015520749A (en) | Method for producing anhydrosugar alcohol with significantly reduced ion content and improved color characteristics | |
| CN102719319A (en) | Method for preparing biological aviation fuel by utilizing cornus wilsoniana oil | |
| CN102796619A (en) | Method for improving deodorizer distillate pretreatment process by supercritical methanol continuous reaction | |
| CN1580030A (en) | Method for synthesizing conjugated linoleic acid | |
| CN103025748A (en) | Method for crystallization of fucose | |
| CN102660594B (en) | Preparation method of lipase isomer Vc mixed fatty acid ester | |
| CN1297529C (en) | Acidifying, distilling and extracting method for natural propionic acid and acetic acid of propionic bacteria fermentation liquid | |
| CN1597702A (en) | Method of extrating bela dextran from highland barley | |
| Dwivedi et al. | A rapid chemical method for production of xylitol from D-xylose as a renewable feedstock from spent aromatic waste | |
| CN1167770A (en) | Preparation method of sucrose fatty acid ester | |
| CN101353554B (en) | Method for preparing allyl ester of rosin | |
| CN1293167C (en) | Method for preparing biologic diesel oil by using halophytic vegetation as raw material | |
| CN101896590B (en) | Production of fatty acid and fatty acid ester | |
| KR20070004049A (en) | How to Ethanol Extract Phytosterols from Corn Fibers | |
| CN113088363B (en) | Preparation method of coconut oil fatty acid composite ester | |
| CN1478776A (en) | Extraction and purification technology of natural vitamin E |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Hunan Kemao Forest Chemical Co., Ltd. Assignor: Guangxi National Univ. Contract record no.: 2010450000014 Denomination of invention: Direct synthesis method of abietic acid sucrose ester using rosin and sucrose Granted publication date: 20071128 License type: Exclusive License Open date: 20060208 Record date: 20100621 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20071128 Termination date: 20150616 |
|
| EXPY | Termination of patent right or utility model |