CN104447432B - A kind of preparation method of new sulfonation dehydrogenation rosin acid bismuth - Google Patents
A kind of preparation method of new sulfonation dehydrogenation rosin acid bismuth Download PDFInfo
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- CN104447432B CN104447432B CN201410668697.XA CN201410668697A CN104447432B CN 104447432 B CN104447432 B CN 104447432B CN 201410668697 A CN201410668697 A CN 201410668697A CN 104447432 B CN104447432 B CN 104447432B
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- sulfonation
- rosin acid
- water
- filter cake
- dehydrogenation rosin
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- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 64
- 238000006277 sulfonation reaction Methods 0.000 title claims abstract description 60
- 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 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910052797 bismuth Inorganic materials 0.000 title abstract description 22
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- 239000012065 filter cake Substances 0.000 claims description 37
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 17
- 235000011187 glycerol Nutrition 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 9
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical class [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 claims description 9
- 238000005360 mashing Methods 0.000 claims description 9
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 8
- 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 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 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 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 150000007513 acids Chemical class 0.000 claims description 6
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 238000007605 air drying Methods 0.000 claims description 5
- 239000010813 municipal solid waste Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- -1 rosin acid bismuth salt Chemical class 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 235000019439 ethyl acetate Nutrition 0.000 description 20
- 239000003814 drug Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 6
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- 230000009858 acid secretion Effects 0.000 description 5
- 229940079593 drug Drugs 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 208000007882 Gastritis Diseases 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 102000057297 Pepsin A Human genes 0.000 description 3
- 108090000284 Pepsin A Proteins 0.000 description 3
- 208000025865 Ulcer Diseases 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 235000021050 feed intake Nutrition 0.000 description 3
- 229940111202 pepsin Drugs 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- 230000001458 anti-acid effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 229960001380 cimetidine Drugs 0.000 description 2
- CCGSUNCLSOWKJO-UHFFFAOYSA-N cimetidine Chemical compound N#CNC(=N/C)\NCCSCC1=NC=N[C]1C CCGSUNCLSOWKJO-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- 210000001156 gastric mucosa Anatomy 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 229960004503 metoclopramide Drugs 0.000 description 2
- TTWJBBZEZQICBI-UHFFFAOYSA-N metoclopramide Chemical compound CCN(CC)CCNC(=O)C1=CC(Cl)=C(N)C=C1OC TTWJBBZEZQICBI-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 231100000397 ulcer Toxicity 0.000 description 2
- YPELFRMCRYSPKZ-UHFFFAOYSA-N 4-amino-5-chloro-2-ethoxy-N-({4-[(4-fluorophenyl)methyl]morpholin-2-yl}methyl)benzamide Chemical compound CCOC1=CC(N)=C(Cl)C=C1C(=O)NCC1OCCN(CC=2C=CC(F)=CC=2)C1 YPELFRMCRYSPKZ-UHFFFAOYSA-N 0.000 description 1
- 206010067484 Adverse reaction Diseases 0.000 description 1
- 206010003671 Atrioventricular Block Diseases 0.000 description 1
- HWSISDHAHRVNMT-UHFFFAOYSA-N Bismuth subnitrate Chemical compound O[NH+]([O-])O[Bi](O[N+]([O-])=O)O[N+]([O-])=O HWSISDHAHRVNMT-UHFFFAOYSA-N 0.000 description 1
- BQENDLAVTKRQMS-SBBGFIFASA-L Carbenoxolone sodium Chemical compound [Na+].[Na+].C([C@H]1C2=CC(=O)[C@H]34)[C@@](C)(C([O-])=O)CC[C@]1(C)CC[C@@]2(C)[C@]4(C)CC[C@@H]1[C@]3(C)CC[C@H](OC(=O)CCC([O-])=O)C1(C)C BQENDLAVTKRQMS-SBBGFIFASA-L 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 206010017865 Gastritis erosive Diseases 0.000 description 1
- 208000010271 Heart Block Diseases 0.000 description 1
- 241000590002 Helicobacter pylori Species 0.000 description 1
- 206010030113 Oedema Diseases 0.000 description 1
- 208000008469 Peptic Ulcer Diseases 0.000 description 1
- 102100037505 Secretin Human genes 0.000 description 1
- 108010086019 Secretin Proteins 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 208000007107 Stomach Ulcer Diseases 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 230000006838 adverse reaction Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229960001482 bismuth subnitrate Drugs 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- JTZPPHUZZDKEOC-RBQAPOGLSA-A chembl2367706 Chemical compound O[Al](O)O.O[Al](O)O.O[Al](O)O.O[Al](O)O.O[Al](O)O.O[Al](O)O.O[Al](O)O.O[Al](O)O.O[Al](O)OS(=O)(=O)O[C@@H]1[C@@H](OS(=O)(=O)O[Al](O)O)[C@H](OS(=O)(=O)O[Al](O)O)[C@@H](COS(=O)(=O)O[Al](O)O)O[C@H]1O[C@@]1(COS(=O)(=O)O[Al](O)O)[C@@H](OS(=O)(=O)O[Al](O)O)[C@H](OS(=O)(=O)O[Al](O)O)[C@@H](OS(=O)(=O)O[Al](O)O)O1 JTZPPHUZZDKEOC-RBQAPOGLSA-A 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 208000023652 chronic gastritis Diseases 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000019621 digestibility Nutrition 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 229960001253 domperidone Drugs 0.000 description 1
- FGXWKSZFVQUSTL-UHFFFAOYSA-N domperidone Chemical compound C12=CC=CC=C2NC(=O)N1CCCN(CC1)CCC1N1C2=CC=C(Cl)C=C2NC1=O FGXWKSZFVQUSTL-UHFFFAOYSA-N 0.000 description 1
- 210000001198 duodenum Anatomy 0.000 description 1
- 201000006549 dyspepsia Diseases 0.000 description 1
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- 150000002576 ketones Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
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- 229960004085 mosapride Drugs 0.000 description 1
- 230000001175 peptic effect Effects 0.000 description 1
- 208000011906 peptic ulcer disease Diseases 0.000 description 1
- VMXUWOKSQNHOCA-LCYFTJDESA-N ranitidine Chemical compound [O-][N+](=O)/C=C(/NC)NCCSCC1=CC=C(CN(C)C)O1 VMXUWOKSQNHOCA-LCYFTJDESA-N 0.000 description 1
- 229960000620 ranitidine Drugs 0.000 description 1
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- 229960002101 secretin Drugs 0.000 description 1
- OWMZNFCDEHGFEP-NFBCVYDUSA-N secretin human Chemical compound C([C@@H](C(=O)N[C@H](C(=O)N[C@@H](CO)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CO)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](CCC(O)=O)C(=O)NCC(=O)N[C@@H](C)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CCC(N)=O)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CCC(N)=O)C(=O)NCC(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](C(C)C)C(N)=O)[C@@H](C)O)NC(=O)[C@@H](NC(=O)CNC(=O)[C@H](CC(O)=O)NC(=O)[C@H](CO)NC(=O)[C@@H](N)CC=1NC=NC=1)[C@@H](C)O)C1=CC=CC=C1 OWMZNFCDEHGFEP-NFBCVYDUSA-N 0.000 description 1
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Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of preparation method of sulfonation dehydrogenation rosin acid bismuth, the feature of this method includes the ethanol dissolving sulfonation dehydrogenation rosin acid with certain concentration, make sulfonation dehydrogenation rosin acid and bismuth react after the mol ratio of products therefrom be 1: 1.This method is simple to operate, gained sulfonation dehydrogenation rosin acid bismuth complies fully with the requirement of quality standard, is applicable to industrialized production.
Description
Technical field
The invention belongs to pharmaceutical technology field, and in particular to one kind can be used for treatment digestive tract ulcer, acute or chronic gastritis and
The preparation method of erosive gastritis medicine.
Background technology
Peptic gastric ulcer be due to the digestion of hydrochloric acid in gastric juice, pepsin caused by ulcer disease, be mainly in stomach and
Duodenum, the easy recurrent exerbation of such disease, easily causes canceration.Conventional medicine has antiacid sodium acid carbonate, phosphoric acid
Aluminium, anti-gastric acid secretion drug secretin, Cimetidine, ranitidine, gastric mucosa protectant ulcerlmin, Bismuth Subnitrate Compoun, for general
Auspicious ketone, dynamics-promoting medicine Metoclopramide, domperidone, Mosapride etc..Antiacid easily causes hypochlorhydria using excessively,
So as to substantially reduce the digestion activity of pepsin, cause indigestion；Gastric mucosa protectant such as sanodin can cause oedema, blood
The symptoms such as pressure rise, and some dynamics-promoting medicines such as Metoclopramide causes the adverse reaction of maincenter larger.Treatment digestibility at present
The choice drug of ulcer is exactly anti-gastric acid secretion drug, and heart block can be caused by commonly using anti-gastric acid secretion drug Cimetidine
Deng side effect.Therefore, it is badly in need of researching and developing new anti-gastric acid secretion medicine.
The sulfonation dehydrogenation rosinate being related in the present invention early in the eighties Tanade Seiyaku Co., Ltd of Japan just it is entered
Research is gone, it is found that these compounds have significant gastric mucosal protection, the suppression of pepsin activity and anti-gastric acid secretion, nothing
Drug resistance kills effect of helicobacter pylori etc., can be used as peptic ulcer and the medicine of various gastritis.
United States Patent (USP) US7015343, Chinese patent 01120289.0 disclose the synthetic route of sulfonation dehydrogenation rosin acid bismuth.
The existing synthetic route of sulfonation dehydrogenation rosin acid bismuth is as follows：
Chinese patent：201410004745.5 further disclose sulfonation dehydrogenation rosin acid bismuth with 201410004774.1
Preparation method, but find when being prepared according to the technique of above-mentioned patent, existing technique is not very stable, is produced sometimes
Sulfonation dehydrogenation rosin acid bismuth do not meet quality standard, the content of sulfonation dehydrogenation rosin acid or bismuth is not in the range of quality standard.
The content of the invention
The present invention is intended to provide a kind of preparation technology of the sulfonation dehydrogenation rosin bismuth of favorable reproducibility, process stabilizing, so as to rich
Rich prior art.
Technical scheme is as follows：
(1) sulfonation of dehydrogenation rosin acid
Gained dehydrogenation rosin is added in the concentrated sulfuric acid pre-cooled and reacted, then reaction solution is added drop-wise in trash ice, treated
The complete molten rear suction filtration of ice, with water leaching cake, is added to the water mashing by filter cake, filters, the filter cake after mashing is added to the water, heating boiling
Rise, complete molten rear cooling crystallization, filtering, filter cake forced air drying, obtain sulfonation dehydrogenation rosin acid crude.
Process for purification：Sulfonation dehydrogenation rosin acid crude is added in the ethyl acetate of 6~9 times of amounts (w/v),
It is heated to flowing back, Quan Ronghou, cooling, adds water, is cooled down after the precipitation of a large amount of solids, filter, obtain wet cake.Wet cake is added
Into the ethyl acetate of 2~4 times of amounts, flow back complete molten, addition activated carbon, diatomite decolouring, filtering are heated to, filtrate cools down, analysis
Go out a large amount of solids, filter, a small amount of cold ethyl acetate elutes filter cake, and gained filter cake is dried in vacuo, and obtains the sulfonation dehydrogenation pine of off-white color
Fragrant acid.
Further preferably：Take the concentrated sulfuric acid to add in reactor, sulfuric acid be cooled to -10 DEG C, is slowly added into dehydrogenation rosin acid,
- 10 DEG C~-5 DEG C are maintained to react 0.5~3 hour.Then reaction solution is added drop-wise in trash ice, drop finishes, and ice all after dissolving, is taken out
Filter, filter cake is eluted with cold water.
Filter cake is added to the water mashing, then filtered.
Filter cake after mashing is added to the water, is heated to seething with excitement, solid it is complete it is molten after, cooling, filtered after separating out a large amount of solids,
Filter cake forced air drying, obtain sulfonation dehydrogenation rosin acid crude.
Process for purification：Sulfonation dehydrogenation rosin acid crude is added in 7~8 times of amount ethyl acetate, is heated to flowing back, Quan Rong
Afterwards, cool down, add water, be cooled to 0 DEG C~-10 DEG C after the precipitation of a large amount of solids, filter, obtain wet cake.By wet cake plus (wet filter
Contain 40%~60% ethyl acetate in cake) enter into 3~4 times of amount ethyl acetate, it is heated to complete molten, the addition activity that flows back
Charcoal, diatomite decolourize, and filtering, filtrate cools down 0 DEG C~-10 DEG C, separates out a large amount of solids, filter, a small amount of cold ethyl acetate elution filter
Cake, gained filter cake are dried in vacuo, and obtain the sulfonation dehydrogenation rosin acid of off-white color.
(2) preparation of sulfonation dehydrogenation rosin acid bismuth
Five water bismuth nitrates are dissolved in the glycerine of 8~12 times of amounts (w/v): water=1: 3 in the mixed solvent, Quan Rong
Afterwards, filter, then sulfonation dehydrogenation rosin acid is dissolved into the ethanol of 8~12 times of amount (w/vs) 55%~75%, Quan Rong
Afterwards, the glycerine water solution of bismuth nitrate is instilled and wherein reacted, filtered, then be beaten with pure water, filter cake vacuum drying, sulfonation dehydrogenation pine
Fragrant sour bismuth.
Further preferably：Five water bismuth nitrates are dissolved in the glycerine of 10 times of amounts (w/v): water=1: 3 mixed solvent
In, Quan Ronghou, filtering, then sulfonation dehydrogenation rosin acid is dissolved into the ethanol of 10 times of amount (w/vs) 60%, Quan Ronghou,
The glycerine water solution of bismuth nitrate is instilled wherein, reacts 30min, filtering, then be beaten for 3.4L*3 time with pure water, 60 DEG C of vacuum of filter cake
Dry 24 hours, obtain sulfonation dehydrogenation rosin acid bismuth.
Heat filtering after thermosol in the sulfonation process of dehydrogenation rosin acid in the prior art, the inventors discovered that heat filtering after thermosol
Method can only partly remove grease and impurity, and the quality of product can not reach quality standards sometimes, and the heat filtering of the concentrated sulfuric acid
Requirement to instrument is high, easy consumption instrument.Not heat filtering after thermosol in the sulfonation process of dehydrogenation rosin acid of the present invention, adopt after thermosol
With decrease temperature crystalline, and by the recrystallization of multiple ethyl acetate, crystalline product is set to be practically free of grease, quality can guarantee that
It is qualified, add the stability of technique.
In the prior art, the solvent that sulfonation dehydrogenation rosin acid is dissolved in the preparation process of sulfonation dehydrogenation rosin acid bismuth uses
It is 75% ethanol, measures 1.97 times of volumes for sulfonation dehydrogenation rosin acid, the amount for dissolving the solvent glycerin water of five water bismuth nitrates is
12.12 times of volumes of five water bismuth nitrates.The solvent of present invention dissolving sulfonation dehydrogenation rosin acid uses 60% ethanol, measures and is
10 times of volumes of sulfonation dehydrogenation rosin acid, the amount of solvent glycerin water is five water bismuth nitrates, 10 times of volumes, and advantage is：Amount of alcohol is big,
Sulfonation dehydrogenation rosin acid is relatively low, loses small in material transfer process, can ensure accurately to feed intake so that the quality index of product compared with
To be stable, and reaction system size is just, and mixing effect is good, and system mass-and heat-transfer is uniform.
The following examples will be more specifically explained the present invention, but the present invention is not limited only to these implementations
Example, these same embodiments are not also limit the invention in any way.
Embodiment 1：The screening of ethyl acetate dosage in-sulfonation dehydrogenation rosin acid subtractive process
By 100g crude product sulfonation dehydrogenation rosin acids be added separately to 500ml, 600ml, 700ml, 800ml, 900ml,
In 1000ml ethyl acetate, it is heated to flowing back, Quan Ronghou, cooling, adds 5ml water, there are a large amount of solids to separate out quickly, be cooled to 0 DEG C
~-10 DEG C, filter, obtain wet cake.Wet cake is added in the ethyl acetate of 3 times of amounts, is heated to complete molten, the addition 2g work that flows back
Property charcoal, 2g diatomite decolourize, filtering, filtrate is cooled to 0 DEG C~10 DEG C, separates out a large amount of solids, filters, a small amount of cold ethyl acetate elution
Filter cake, 40 DEG C of gained filter cake are dried in vacuo 12 hours, obtain off-white powder.
Table 1- dissolves the garbled data of sulfonation dehydrogenation rosin acid crude ethyl acetate dosage
| The inventory (g) of sulfonation dehydrogenation rosin acid | The dosage (ml) of ethyl acetate | Yield |
| 100 | 500 | Reaction system poor fluidity, feed intake highly difficult |
| 100 | 600 | Reaction system poor fluidity, feed intake difficulty |
| 100 | 700 | 30% |
| 100 | 800 | 28% |
| 100 | 900 | 25% |
| 100 | 1000 | 19% |
As shown in Table 1, in the subtractive process of sulfonation dehydrogenation rosin acid ethyl acetate amount for sulfonation dehydrogenation rosin acid 7~
At 8 times, reaction system mobility is preferable, and yield is of a relatively high.
Embodiment 2：The screening of concentration of alcohol in the preparation process of-sulfonation dehydrogenation rosin acid bismuth
The water bismuth nitrates of 31.19g five are dissolved in 282ml glycerine: water=1: 3 in the mixed solvent, Quan Ronghou, filtered, then will
28.2g sulfonation dehydrogenation rosin acids are dissolved into the ethanol of 282ml30%, 40%, 50%, 60%, 70%, 80% respectively, Quan Rong
Afterwards, the glycerine water solution of bismuth nitrate is instilled wherein, reacts 30min, filtering, then be beaten for 3.4L*3 time with pure water, 60 DEG C of filter cake
Vacuum drying 24 hours, obtains off-white powder 185g.
Table 2- dissolves the garbled data of sulfonation dehydrogenation rosin acid concentration of alcohol
Note：Required in the quality standard of sulfonation dehydrogenation rosin acid bismuth the content of sulfonation dehydrogenation rosin acid bismuth for 60.5~
67.5%, the content of bismuth is 32.5~36%, and mol ratio is 1: 1 or so.
As shown in Table 2：When 30%~50% ethanol is as solvent, the content of bismuth is less than the content range of quality standard.It is molten
When agent is 80% ethanol, crystallization is slow, and solid is too thin, filtration difficulty.When the concentration of ethanol is 60%~70%, sulfonation dehydrogenation
The mol ratio of sulfonation dehydrogenation rosin acid and bismuth is in rosin acid bismuth compound：1: 1 or so, the content of sulfonation dehydrogenation rosin acid and bismuth
All in the range of quality standard, and the speed for separating out gel-like product is moderate, feeds intake relatively easy.Plus the consideration to cost,
Therefore it is preferred that 60% ethanol removes the solvent of light rosin acid as dissolving sulfonation.
Embodiment 3：
(1) take the 500ml concentrated sulfuric acids to add in 1L there-necked flasks, sulfuric acid is cooled to -10 DEG C, is slowly added into dehydrogenation rosin acid
100g, maintain -10 DEG C~-5 DEG C 1 hour.Then reaction solution is added drop-wise in 1.2Kg trash ices, drop finishes, and ice all after dissolving, is taken out
Filter, filter cake is eluted with 120ml cold water.
Filter cake is added in 800ml water and is beaten 2 hours, is then filtered.
Filter cake after mashing is added in 800ml water, is heated to seething with excitement, solid it is complete it is molten after, cooling, water temperature is down to 0 DEG C~5
DEG C, a large amount of solids are separated out, filters, the forced air drying 20 hours of 40 DEG C of filter cake, obtains sulfonation dehydrogenation rosin acid crude 94.4g.
Process for purification：The thick sulfonation dehydrogenation rosin acids of 94.4g are added in 660ml ethyl acetate, are heated to flowing back, Quan Rong
Afterwards, cool down, add 5ml water, there are a large amount of solids to separate out quickly, be cooled to 0 DEG C~-10 DEG C, filter, obtain 90g wet cakes.By wet cake
It is added in 265ml ethyl acetate, is heated to flow back complete molten, addition 2g activated carbons, the decolouring of 2g diatomite, filtering, filtrate is cooled to 0
DEG C~-10 DEG C, a large amount of solids are separated out, are filtered, a small amount of cold ethyl acetate elutes filter cake, and the 40 DEG C of vacuum drying 12 of gained filter cake are small
When, obtain off-white powder 28.2g.
(2) the water bismuth nitrates of 31.19g five are dissolved in 282ml glycerine: water=1: 3 in the mixed solvent, Quan Ronghou, filtered, then
28.2g sulfonation dehydrogenation rosin acids are dissolved into 282ml60% ethanol, Quan Ronghou, the glycerine water solution of bismuth nitrate is instilled
Wherein, 30min, filtering are reacted, then is dried in vacuo 24 hours with 3.4L*3 mashing of pure water, 60 DEG C of filter cake, obtains off-white powder
185g。
Comparative example 1：
(1) take the 15L concentrated sulfuric acids to add in 20L reactors, sulfuric acid is cooled to -10 DEG C, is slowly added into dehydrogenation rosin acid
3Kg, maintain -10 DEG C~-5 DEG C 1.5 hours.Then reaction solution being added drop-wise in 36Kg trash ices, drop finishes, after ice all dissolves, from
The heart, filter cake is eluted with 6L cold water.
Filter cake is added in 45L boiling water, Quan Ronghou, add 300g activated carbons and 500g diatomite, flowed back 10 minutes, mistake
Filter, diatomite and activated carbon are removed, collect filtrate cooling, water temperature is down to 0 DEG C~5 DEG C, separates out a large amount of solids, filters, filter cake 40
DEG C forced air drying 48 hours, obtains sulfonation dehydrogenation rosin acid crude 1.9Kg.
Process for purification：1.9Kg crude product sulfonation dehydrogenations rosin acid is added in 19L ethyl acetate, is heated to flowing back, Quan Rong
Afterwards, heat filtering, filtrate are cooled to 0 DEG C~5 DEG C crystallizations, centrifugation, 1L cold ethyl acetates elution filter cake, the 40 DEG C of vacuum drying of gained filter cake
12 hours, obtain off-white powder 1.44Kg.
(2) the water bismuth nitrates of 1.654kg five are dissolved in 20L glycerine: water=1: 3 in the mixed solvent, Quan Ronghou, filtered, then
1.44kg sulfonation dehydrogenation rosin acids are dissolved into 2.8L75% ethanol, Quan Ronghou, instilled in the glycerine water solution of bismuth nitrate,
30min, centrifugation are reacted, then is dried in vacuo 24 hours with 25L*3 mashing of pure water, 60 DEG C of filter cake, obtains off-white powder 1.6kg.
The comparison of table 3- comparative examples 1 and embodiment 3
Claims (1)
1. a kind of preparation method of sulfonation dehydrogenation rosin acid bismuth salt, it is characterised in that its preparation method is as follows：
1) sulfonation of dehydrogenation rosin acid：
Take the 500ml concentrated sulfuric acids to add in 1L there-necked flasks, sulfuric acid is cooled to -10 DEG C, is slowly added into dehydrogenation rosin acid 100g, tie up
Hold -10 DEG C~-5 DEG C 1 hour, then reaction solution is added drop-wise in 1.2Kg trash ices, drop finishes, and ice all after dissolving, filters, and uses
120ml cold water elutes filter cake；
Filter cake is added in 800ml water and is beaten 2 hours, is then filtered；
Filter cake after mashing is added in 800ml water, is heated to seething with excitement, solid it is complete it is molten after, cooling, water temperature is down to 0 DEG C~5 DEG C,
A large amount of solids are separated out, filters, the forced air drying 20 hours of 40 DEG C of filter cake, obtains sulfonation dehydrogenation rosin acid crude 94.4g；
2) sulfonation dehydrogenation rosin acid bismuth salt is refined：The thick sulfonation dehydrogenation rosin acids of 94.4g are added in 660ml ethyl acetate and added
Heat Quan Ronghou, cooling, adds 5ml water to flowing back, and has a large amount of solids to separate out quickly, is cooled to 0 DEG C~-10 DEG C, filters, it is wet to obtain 90g
Filter cake, wet cake is added in 265ml ethyl acetate, is heated to flow back complete molten, addition 2g activated carbons, the decolouring of 2g diatomite,
Filtering, filtrate are cooled to 0 DEG C~-10 DEG C, separate out a large amount of solids, filter, and a small amount of cold ethyl acetate elutes filter cake, 40 DEG C of gained filter cake
Vacuum drying 12 hours, obtains off-white powder 28.2g；
The water bismuth nitrates of 31.19g five are dissolved in 282ml glycerine: water=1: 3 in the mixed solvent, Quan Ronghou, filtering, then by 28.2g
Sulfonation dehydrogenation rosin acid is dissolved into 282ml 60% ethanol, Quan Ronghou, and the glycerine water solution of bismuth nitrate is instilled wherein, instead
30min is answered, is filtered, then is dried in vacuo 24 hours with 3.4L*3 mashing of pure water, 60 DEG C of filter cake, obtains off-white powder.
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