CN102417446B - Production method for zinc undecylenate - Google Patents
Production method for zinc undecylenate Download PDFInfo
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- CN102417446B CN102417446B CN201110337620.0A CN201110337620A CN102417446B CN 102417446 B CN102417446 B CN 102417446B CN 201110337620 A CN201110337620 A CN 201110337620A CN 102417446 B CN102417446 B CN 102417446B
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Abstract
The invention discloses a production method for zinc undecylenate. The production method comprises the following steps: adding glacial acetic acid and zinc oxide into purified water, thereby preparing a zinc acetate aqueous solution; dropwise adding an undecylenate ethanol solution into the zinc acetate aqueous solution; heating, keeping the temperature at 40-80 DEG C, and reacting for 1-2 hours; and filtering, washing, crushing and drying, thereby obtaining a white or light yellow powder zinc undecylenate product.
Description
Technical field
The present invention relates to a kind of production method of Zinc Undecylenate, specifically the production method of high quality Zinc Undecylenate.
Background technology
Zinc Undecylenate, phonetic name: Shiyixisuanxin, English name: Zinc Undecylenate, molecular formula C
22h
38o
4, structural formula [CH
2=CH (CH
2)
8cOO]
2zn, molecular weight 431.92.Fusing point 116-121 ℃.Proterties: white or micro-yellow amorphous powder.Water-soluble and ethanol hardly.Meet strong acid and be decomposed into undecylenic acid and corresponding zinc salt.Purposes: 1, aniorfic surfactant; The particularly assistant for emulsifying agent of cream kind makeup; 2, also can be used as emulsifying agent and sterilant, for example the sterilant of various makeup and perfumed soap.3, for medicine, antifungal drug, treatment is by fungus-caused tetter.
For 10 hendecenoic acid zinc salt.Containing C
22h
38o
4zn should be 98.0%～102.0%.
[proterties] this product is white amorphous powder.Almost insoluble in water or ethanol.Fusing point is 116～121 ℃.
Traditional Zinc Undecylenate production method: (1) is take undecylenic acid and zinc oxide as raw material, under stirring in water or alcohol-water blending agent, direct heating to back flow reaction generates Zinc Undecylenate, after filtration, washing, the dry Zinc Undecylenate dry product that obtains; (2) be take undecylenic acid and zinc sulfate as raw material, first zinc sulfate be dissolved in after water, directly add undecylenic acid to react to generate Zinc Undecylenate, after filtration, washing, the dry Zinc Undecylenate dry product that obtains; (3) < < Liaoning chemical industry > > 1992, the improvement of the gloomy undecylenic acid zinc technology of delivering of (4) 43～61 woodss is take zinc acetate, undecylenic acid and sodium hydroxide as raw material, first undecylenic acid is reacted with sodium hydroxide and generate undecylenic acid sodium, add again zinc acetate aqueous solution to carry out replacement(metathesis)reaction and generate Zinc Undecylenate, after filtration, washing, the dry Zinc Undecylenate dry product that obtains.The weak point of its existence is: A, method (1) raw material zinc oxide is the white powder of water insoluble and ethanol, this reaction is solid-liquid phase reaction, the Zinc Undecylenate generating is the white powder that is insoluble to second alcohol and water, the more difficult control of reaction end, the Zinc Undecylenate white powder that reaction process generates is often carried secretly and is enclosed with more unreacted zinc oxide and undecylenic acid, make reaction not exclusively, aftertreatment washing and dry more difficult, the undecylenic acid zinc powder obtaining is more coarse, finished product outward appearance not uniformly white is fine and smooth, finished product plucked, and there is part block, cause when producing medicine and skin protection cosmetics, drug distribution is inhomogeneous, B, method (2) is raw materials used is zinc sulfate, generates a certain amount of strong acid H in reaction process
2sO
4, to having relatively high expectations, and the vitriol in product is higher, does not meet medicinal or cosmetics quality standard, C, method (3) are raw materials used is that the one-tenth undecylenic acid sodium of zinc acetate and preparation all can be water-soluble, it in water, is liquid-liquid phase replacement(metathesis)reaction, react more complete, but owing to having used sodium hydroxide in technique, aftertreatment is more difficult, basic metal in the undecylenic acid zinc product obtaining and alkaline earth salt content overproof, and the product fusing point obtaining is only 115～116 ℃, lower than 116～121 ℃ of the fusing points of the drug standard, be more difficult to get the undecylenic acid zinc product that meets medicinal and cosmetics quality standard.
Summary of the invention
The object of this invention is to provide the production method of the highly purified Zinc Undecylenate that can overcome the deficiencies in the prior art part.
Concrete production stage and processing method are as follows:
Ratio of components:
Zinc oxide: Glacial acetic acid: water=1: 1.5～1.7: 8 (W/W)
Undecylenic acid: ethanol=1: 1～5 (W/W)
(1) preparation of zinc acetate solution:
By ratio of components, accurately take zinc oxide, again by zinc oxide: Glacial acetic acid: water=1: 1.5～1.7: 8 ratio of components drop into purified water, Glacial acetic acid, zinc oxide respectively in retort, and be under agitation heated to 80～100 ℃, reaction 1-2 hour, after zinc oxide is dissolved completely, zinc acetate aqueous solution is filtered, obtain water white zinc acetate solution, standby.
(2) preparation of undecylenic acid ethanolic soln:
Accurately taking content >=96.0% undecylenic acid fine work prepared by above-mentioned steps (1) drops in retort, again by undecylenic acid: ethanol=1: it is 80～95% ethanol that 1 weight ratio adds content, fully stir, and be heated to 40～80 ℃, obtain as clear as crystal undecylenic acid ethanolic soln.
(3) preparation of Zinc Undecylenate:
By in above-mentioned steps (2) undecylenic acid-ethanolic soln, under agitation, slowly splash in zinc acetate solution prepared by above-mentioned steps (1), within 30～60 minutes, dropwise, and be heated to 70～80 ℃ of reaction 1-2 hour, make it to generate completely white Zinc Undecylenate.
(4) filter: reactant is slowly put into whizzer rejection filter, be filtered dry after mother liquor, first with purified water washing several, wash away the water-soluble impurities such as the incomplete zinc acetate of reaction, use again 70～95% washing with alcohol secondary, wash away the oil-soluble impuritieses such as the incomplete undecylenic acid of reaction, material is dried.
(5) pulverize, dry: the block Zinc Undecylenate after drying is ground into 80～100 orders with pulverizer, is contained in drip pan, dry in baking oven, at 80 ± 2 ℃, be dried 2～4 hours, obtain the Zinc Undecylenate dry product of white or micro-yellow powder shape.
It is as follows that above-mentioned Zinc Undecylenate respectively walks chemical reaction:
Above-mentioned process using first generates zinc acetate soluble in water by water-fast zinc oxide and acetic acid reaction, directly be mixed into liquid-liquid phase with undecylenic acid ethanolic soln again and react and generate Zinc Undecylenate, reaction conditions is loose, is easy to control, reaction end is obvious, and aftertreatment is simple.In reaction mixture except Zinc Undecylenate, water, ethanol, also containing zinc acetate soluble in water, acetic acid and a small amount of water insoluble and be easy to the undecylenic acid impurity of ethanol, through ethanol and purified water, alternately wash and very easily remove, overcome the deficiency that traditional technology product impurity is many, yield is low, the undecylenic acid zinc product obtaining is pure white, fine and smooth, powder is even, reaches medicinal and cosmetics quality requirement completely.
Above-described undecylenic acid is to adopt three grades of molecule distillating method separating-purifyings to obtain highly purified undecylenic acid, containing C
11h
20o
2>=98% (g/g).
The about 3g of this product is got in [discriminating] (1), adds water 20ml and dilute sulphuric acid 25ml, with ether jolting extraction 2 times, each 25ml, merges ether extracted liquid, puts in water-bath and boils off after ether, get and leave over liquid 1ml, according to the test of the discriminating (1) under undecylenic acid item, aobvious identical reaction.
(2) get the about 0.1g of this product, add after water 10ml and strong ammonia solution 1ml dissolving, add sodium sulphite test solution number and drip, generate white precipitate.
(3) the infrared Absorption collection of illustrative plates of this product should with the collection of illustrative plates < < medicine infrared spectra collection > > nineteen ninety-five version contrasting, 18 figure are consistent for light clef.
[inspection] weight loss on drying is got this product, at 105 ℃, is dried to constant weight, and less loss weight must not be crossed 1.0% (appendix VIII L).
Basic metal and alkaline earth salt are got this product 1.5g, add water 50ml and hydrochloric acid 10ml, boil, with moistening filter paper, filter while hot, and with hot wash to the aobvious acid-reaction of washing lotion; Merging filtrate and washing lotion, put in 200ml measuring bottle, adds ammonia solution and make alkalize, then add ammonium sulfide test solution and make in right amount zinc precipitate completely, is diluted with water to scale, shakes up, and filters; Divide and get filtrate 100ml, add sulfuric acid 0.5ml, evaporate to dryness, and ignition to constant weight, leave over residue and must not cross 7.5mg.
[assay] gets the about 0.5g of this product, accurately weighed, add 1mol/L hydrochloric acid soln 10ml and water 10ml, boil after 10 minutes, filter while hot, filter residue hot wash, merging filtrate and washing lotion, let cool, 1 of the ethanolic soln that adds 0.025% methyl red, adds ammonia solution in right amount to the micro-yellow of solution, adds water and makes full dose be about 35ml, again ammonification-ammonium chloride buffer (pH10.0) 10ml and chromium black T indicator a little, with Calcium Disodium Versenate titrating solution (0.05mol/L), be titrated to solution and become pure blue from red-purple.Every 1ml Calcium Disodium Versenate titrating solution (0.05mol/L) is equivalent to the C of 21.60mg
22h
38o
4zn.
[classification] Cidex-7.
[storage] sealing is preserved.
[preparation] compound zinc undecylenate ointment
Compared with prior art, advantage of the present invention is:
1, the present invention has overcome undecylenic acid and zinc oxide direct reaction obtains Zinc Undecylenate processing method, reaction end is not obvious, in the undecylenic acid zinc powder generating, package clip is with more unreacted zinc oxide and undecylenic acid impurity, and aftertreatment washing difficulty, quality product are difficult to ensure the shortcomings such as card.
2, the present invention has overcome employing undecylenic acid and reacts with zinc sulfate and obtain in Zinc Undecylenate processing method, and to equipment corrosion, in large and product, sulfur impurity phosphate content exceeds standard seriously the sulfuric acid of generation, quality product is difficult to ensure the shortcomings such as card.
3, the invention solves employing and first undecylenic acid is first carried out to saponification reaction generation undecylenic acid sodium with sodium hydroxide solution, carry out in replacement(metathesis)reaction processing method with zinc acetate solution again, obtain undecylenic acid zinc product basic metal and alkaline-earth metal salts contg severe overweight, fusing point is on the low side, quality product is difficult to ensure the shortcomings such as card.
4, processing method of the present invention is simple to operation, and quality product is controlled.In reaction mixture except Zinc Undecylenate, water, ethanol, other impurity only have zinc acetate, acetic acid, undecylenic acid, and zinc acetate, acetic acid are soluble in water and undecylenic acid is dissolved in ethanol and is easily removed, the undecylenic acid zinc product obtaining is pure white, fine and smooth, powder is even, reaches medicinal and cosmetics quality requirement completely.
Accompanying drawing explanation
Fig. 1 is the process flow sheet that Zinc Undecylenate of the present invention is produced.
In Fig. 1, see, first add pure water to prepare zinc acetate aqueous solution in Glacial acetic acid and zinc oxide, and then undecylenic acid ethanolic soln is added drop-wise in zinc acetate aqueous solution, heating and thermal insulation reacted after 1～2 hour at 40～80 ℃, after filtration, washing, pulverize, dry, obtain white or micro-yellow powder shape undecylenic acid zinc product.
Embodiment
Embodiment 1
Ratio of components:
Zinc oxide: Glacial acetic acid: water=1: 1.5: 8 (W/W)
Undecylenic acid: ethanol=1: 1 (W/W)
By zinc oxide: Glacial acetic acid: water=1: ratio of components dropped into purified water 70.4kg, Glacial acetic acid 13.2kg, zinc oxide 8.8kg respectively in retort in 1.5: 8, and be under agitation heated to 80～100 ℃, react 1 hour, after zinc oxide is dissolved completely, zinc acetate aqueous solution is filtered, obtain water white zinc acetate solution, standby.Accurately taking content is that 96.0% undecylenic acid fine work 40kg drops in retort, again by undecylenic acid: ethanol=1: it is 95% ethanol 40kg that 1 weight ratio adds content, fully stir, and be heated to 70 ℃, obtain as clear as crystal undecylenic acid ethanolic soln, standby.By in undecylenic acid ethanolic soln, under agitation, slowly splash in the zinc acetate solution of above-mentioned preparation, within 30 minutes, dropwise, and be heated to 70～80 ℃ of reactions 1 hour, make it to generate completely white Zinc Undecylenate.Reactant is slowly put into whizzer rejection filter, be filtered dry after mother liquor, first with purified water washing several, wash away the water-soluble impurities such as the incomplete zinc acetate of reaction, use again 70～95% washing with alcohol secondary, wash away the oil-soluble impuritieses such as the incomplete undecylenic acid of reaction, material is dried.Block Zinc Undecylenate after drying is ground into 80～100 orders with pulverizer, is contained in drip pan, dry in baking oven, at 80 ± 2 ℃, be dried 4 hours, obtain white or pulverous Zinc Undecylenate dry product 44.2kg.
Embodiment 2
Ratio of components:
Zinc oxide: Glacial acetic acid: water=1: 1.6: 8 (W/W)
Undecylenic acid: ethanol=1: 2 (W/W)
By ratio of components, accurately take zinc oxide 9.2kg, again by zinc oxide: Glacial acetic acid: water=1: within 1.5: 8, ratio of components drops into purified water 70.4kg, Glacial acetic acid 14.72kg, zinc oxide 9.2kg respectively in retort, and be under agitation heated to 80～100 ℃, react 1.5 hours, after zinc oxide is dissolved completely, zinc acetate aqueous solution is filtered, obtain water white zinc acetate solution, standby.Accurately taking content is that 96.0% undecylenic acid fine work 40.0kg drops in retort, again by undecylenic acid: ethanol=1: it is 80% ethanol 80kg that 2 weight ratio adds content, fully stir, and be heated to 70 ℃, obtain as clear as crystal undecylenic acid ethanolic soln, standby.By in undecylenic acid ethanolic soln, under agitation, slowly splash in the zinc acetate solution of above-mentioned preparation, within 50 minutes, dropwise, and be heated to 70～80 ℃ of reactions 2 hours, make it to generate completely white Zinc Undecylenate.Reactant is slowly put into whizzer rejection filter, be filtered dry after mother liquor, first with purified water washing several, wash away the water-soluble impurities such as the incomplete zinc acetate of reaction, use again 90% washing with alcohol secondary, wash away the oil-soluble impuritieses such as the incomplete undecylenic acid of reaction, material is dried.Block Zinc Undecylenate after drying is ground into 80～100 orders with pulverizer, is contained in drip pan, dry in baking oven, at 80 ± 2 ℃, be dried 3 hours, obtain the Zinc Undecylenate dry product 44.5kg of white powder.
Embodiment 3
Ratio of components:
Zinc oxide: Glacial acetic acid: water=1: 1.7: 8 (W/W)
Undecylenic acid: ethanol=1: 4 (W/W)
By ratio of components, accurately take zinc oxide 9.6kg standby.Again by zinc oxide: Glacial acetic acid: water=1: within 1.7: 8, ratio of components drops into purified water 70.4kg, Glacial acetic acid 16.32kg, zinc oxide 9.6kg respectively in retort, and be under agitation heated to 80～100 ℃, react 2 hours, after zinc oxide is dissolved completely, zinc acetate aqueous solution is filtered, obtain water white zinc acetate solution, standby.Accurately taking content is that 96.0% undecylenic acid fine work 40.0kg drops in retort, again by undecylenic acid: ethanol=1: it is 80% ethanol 160kg that 2 weight ratio adds content, fully stir, and be heated to 70 ℃, obtain as clear as crystal undecylenic acid ethanolic soln, standby.By in undecylenic acid ethanolic soln, under agitation, slowly splash in the zinc acetate solution of above-mentioned preparation, within 50 minutes, dropwise, and be heated to 70～80 ℃ of reactions 1.5 hours, make it to generate completely white Zinc Undecylenate.Reactant is slowly put into whizzer rejection filter, be filtered dry after mother liquor, first with purified water washing several, wash away the water-soluble impurities such as the incomplete zinc acetate of reaction, use again 90% washing with alcohol secondary, wash away the oil-soluble impuritieses such as the incomplete undecylenic acid of reaction, material is dried.Block Zinc Undecylenate after drying is ground into 80～100 orders with pulverizer, is contained in drip pan, dry in baking oven, at 80 ± 2 ℃, be dried 3 hours, obtain the Zinc Undecylenate dry product 45.5kg of white powder.
Claims (3)
1. a production method for Zinc Undecylenate, adopting zinc oxide, Glacial acetic acid, undecylenic acid is raw material, it is characterized in that: its concrete production stage and processing method are as follows:
Ratio of components:
Zinc oxide: Glacial acetic acid: water=1:1.5～1.7:8, W/W,
Undecylenic acid: ethanol=1:1～5; W/W,
(1) preparation of zinc acetate solution:
By ratio of components, accurately take zinc oxide, again by zinc oxide: Glacial acetic acid: water=1:1.5～1.7:8 ratio of components drops into purified water, Glacial acetic acid, zinc oxide respectively in retort, and be under agitation heated to 80～100 ℃, reaction 1-2 hour, after zinc oxide is dissolved completely, zinc acetate aqueous solution is filtered, obtain water white zinc acetate solution, standby;
(2) preparation of undecylenic acid ethanolic soln: accurately take content in >=96.0% undecylenic acid fine work input retort, again by undecylenic acid: it is 80～95% ethanol that the weight ratio of ethanol=1:1～5 adds content, fully stir, and be heated to 40～80 ℃, obtain as clear as crystal undecylenic acid ethanolic soln;
(3) preparation of Zinc Undecylenate: by above-mentioned steps (2) undecylenic acid ethanolic soln, under agitation, slowly splash in the zinc acetate solution of above-mentioned steps (1), within 30～60 minutes, dropwise, and be heated to 70～80 ℃ of reaction 1-2 hour, make it to generate completely white Zinc Undecylenate;
(4) filter: reactant is slowly put into whizzer rejection filter, be filtered dry after mother liquor, first with purified water washing several, wash away the water-soluble impurities such as the incomplete zinc acetate of reaction, use again 70～95% washing with alcohol secondary, wash away the oil-soluble impuritieses such as the incomplete undecylenic acid of reaction, material is dried;
(5) pulverize, dry: the block Zinc Undecylenate after drying is ground into 80～100 orders with pulverizer, is contained in drip pan, dry in baking oven, at 80 ± 2 ℃, be dried 2～4 hours, obtain Zinc Undecylenate dry product.
2. the production method of Zinc Undecylenate according to claim 1, is characterized in that: described undecylenic acid is to adopt three grades of high purity undecylenic acids that molecule distillating method separating-purifying obtains, C
11h
20o
2weight content>=98%.
3. the production method of Zinc Undecylenate according to claim 1, is characterized in that: the product that described step (1) (2) (3) (4) (5) obtains is white or yellowish high quality Zinc Undecylenate.
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|---|---|---|---|
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| GB943282A (en) * | 1960-10-13 | 1963-12-04 | Peter James Shannon | Hair restorer |
| GB1373002A (en) * | 1972-01-25 | 1974-11-06 | Unilever Ltd | Process for the manufacture of zinc citrate |
| CN1059196C (en) * | 1997-12-30 | 2000-12-06 | 徐同香 | Prepn. tech. of zinc acetate |
| CN100502851C (en) * | 2005-07-08 | 2009-06-24 | 方南 | Formula and preparation method for compound ointment containing zinc undecylenate |
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Address after: No. 282 Donghuan Road, Liuzhou City, Guangxi Zhuang Autonomous Region Patentee after: Guangxi Yikang Pharmaceutical Co., Ltd. Address before: No. 282 Donghuan Road, Liuzhou City, Guangxi Zhuang Autonomous Region Patentee before: Guangxi Yikang Pharmaceutical Industry Co., Ltd. |