CN103601632A - Synthetic method for stannous stearate - Google Patents
Synthetic method for stannous stearate Download PDFInfo
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- CN103601632A CN103601632A CN201310629699.3A CN201310629699A CN103601632A CN 103601632 A CN103601632 A CN 103601632A CN 201310629699 A CN201310629699 A CN 201310629699A CN 103601632 A CN103601632 A CN 103601632A
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Abstract
A disclosed synthetic method for stannous stearate comprises the following steps: (1) performing a saponification reaction on stearic acid and a sodium hydroxide solution, cooling the saponification liquid to 60 DEG C or less; and (2) dropwise adding an acid aqueous solution of a soluble stannous salt with a mass content of 5-10% into the saponification liquid with stirring, performing a metathetical reaction at 55-60 DEG C until the reaction is in a saturated state, stopping stirring, adding cold water to cool to 45-50 DEG C for reducing viscosity, then stirring again until the metathetical reaction is carried out completely, performing centrifugation, dewatering, washing and drying to obtain the stannous stearate product. By employing a hydrochloric acid aqueous solution of stannous chloride for the metathetical reaction, the synthetic method helps to prevent solid precipitation phenomenon in the aqueous solution stannous chloride, generated stannous stearate is not easy to oxidize, so that the metathesis reaction is smoothly completed, and the good-color high-purity stannous stearate product is obtained.
Description
Technical field
The present invention relates to stearate preparing technical field, be specifically related to the synthetic method of the sub-tin of a kind of stearic acid.
Background technology
The sub-tin of stearic acid is as a kind of thermo-stabilizer and lubricant, in high-end resin is synthetic, be used widely, but physico-chemical property and the preparation method of the sub-tin of relevant stearic acid almost do not have bibliographical information, domestic Ye Wuci manufacturer, product relies on external import completely, therefore causes holding at high price of the sub-tin of stearic acid.And relevant for the preparation of stearate series products, take saponification, replacement(metathesis)reaction as main, the reaction process of its production is substantially similar, wherein the saponification reaction stage is all to take water as medium, by stearic acid, sodium hydroxide saponification reaction 30～40 minutes at 85～95 ℃, make reacting liquid pH value at 9～10, obtain the saponification liquor of clear.When replacement(metathesis)reaction, be all that saponification liquor is cooled to below 80 ℃, in saponification liquor, add dilute metal salts solution, thereby generate corresponding stearate.(for example add calcium chloride water and generate calcium stearate, add zinc sulfate solution and generate Zinic stearas etc.).
And during with the sub-tin of this produced in conventional processes stearic acid, in replacement(metathesis)reaction process, after adding the tin protochloride aqueous solution, often reaction is difficult, be difficult to carry out, and product color is poor, quality is low, is difficult to reach production and application requirement, therefore restrict the suitability for industrialized production of the sub-tin of stearic acid, further limited the application of the sub-tin of stearic acid.
Summary of the invention
Technical problem to be solved by this invention is: for the deficiency of prior art existence, provide the synthetic method of the sub-tin of a kind of stearic acid, the method production technique is simple, easily controls, and is easy to realize suitability for industrialized production.
For solving the problems of the technologies described above, technical scheme of the present invention is:
A synthetic method for the sub-tin of stearic acid, comprises the following steps:
(1) stearic acid and sodium hydroxide solution are first carried out to saponification reaction, then saponification liquor is cooled to below 60 ℃.
(2) under whipped state, to being added dropwise to the acidic aqueous solution that mass content is 5～10% solubility tin salt in the saponification liquor of step (1), at 55～60 ℃, carry out replacement(metathesis)reaction, the state until reaction reaches capacity, form the sub-tin solid of white stearic acid of adhesion shape, stop stirring, add cold water and cool to 45～50 ℃, reduce degree of adhesion, then restart stirring, until reaction solution occur to drip a clear phenomenon, (dripping a clear phenomenon refers to the container reaction solution that takes a morsel, by container lean, water is separated with solid, and water is the thorough clearly phenomenon oozing), if do not drip the acidic aqueous solution that clearly suitably drips again solubility tin salt, until drip clear, replacement(metathesis)reaction is carried out completely, through centrifugal, dehydration, repeatedly wash and be dried and obtain the sub-tin product of stearic acid.
Wherein, described mass content is that the acidic aqueous solution of 5～10% solubility tin salt is in water, first to add the hydrochloric acid of water weight 2～5%, the mass concentration of described hydrochloric acid is 36～38%, and then add solubility tin salt, the acidic aqueous solution of the solubility tin salt that the mass content being mixed with is 5～10%.
Preferably, described solubility tin salt is tin protochloride.
Wherein, in step (1), during described saponification reaction, the aqueous sodium hydroxide solution of 1～5wt% is heated to 85～95 ℃, under whipped state, slowly add stearic acid to carry out saponification reaction, reaction process is measured the pH value of saponification liquor at any time, when saponification liquor reaches pH value that precision test paper measures 9～10, stop adding stearic acid, maintain the temperature at 85～95 ℃ and continue reaction, the pH value of repetition measurement saponification liquor, if pH value is greater than 10, add stearic acid and continue reaction, if pH value is less than 9, add sodium hydroxide solution and continue reaction, the pH value that maintains reaction solution is 9～10, continue stirring reaction 30～40 minutes, saponification reaction finishes, cool to below 60 ℃.
Owing to having adopted technique scheme, the invention has the beneficial effects as follows:
The present invention adopts saponification, replacement(metathesis)reaction method to prepare the sub-tin of stearic acid, because oxidizing reaction very easily occurs the sub-tin of stearic acid, therefore in existing saponification replacement(metathesis)reaction, not to generate white depositions but generation black precipitate or the milk of thickness, this is because the sub-tin of undersaturated stearic acid that one generates is very easily oxidized, and change color, the sub-tin facile hydrolysis of its dichloride, meets water and generates white stannic hydroxide solid, therefore causes replacement(metathesis)reaction to be difficult to carry out.The inventor is devoted for years in the research and development of stearate product, the theoretical analysis and experimental study, finally determine in replacement(metathesis)reaction process, use the aqueous hydrochloric acid of tin protochloride to carry out replacement(metathesis)reaction, prevented the problem that the aqueous solution of tin protochloride has solid precipitation to separate out, the sub-tin of stearic acid generating is also difficult for occurring oxidative phenomena, and hydrochloric acid is not participated in reaction in replacement(metathesis)reaction process, thereby complete smoothly replacement(metathesis)reaction, also therefore obtain the sub-tin product of stearic acid that color and luster is good, purity is high.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.
Embodiment 1
Stearic acid and sodium hydroxide solution are first carried out to saponification reaction, then saponification liquor is cooled to below 60 ℃.
Under whipped state, to being added dropwise to the acidic aqueous solution that mass content is 5% solubility tin salt in above-mentioned saponification liquor, at 60 ℃, carry out replacement(metathesis)reaction, the state until reaction reaches capacity, form the sub-tin solid of white stearic acid of adhesion shape, stop stirring, add cold water and cool to 45 ℃, reduce degree of adhesion, then restart stirring, until reaction solution occur to drip a clear phenomenon, (dripping a clear phenomenon refers to the container reaction solution that takes a morsel, by container lean, water is separated with solid, and water is the thorough clearly phenomenon oozing), if do not drip the acidic aqueous solution that clearly suitably drips again solubility tin salt, until drip clear, replacement(metathesis)reaction is carried out completely, through centrifugal, dehydration, repeatedly wash and be dried and obtain the sub-tin product of white stearic acid.
Embodiment 2
Stearic acid and sodium hydroxide solution are first carried out to saponification reaction, then saponification liquor is cooled to 55 ℃.
In water, first add the hydrochloric acid of water weight 2%, the mass concentration of described hydrochloric acid is 38%, and then add tin protochloride, the acidic aqueous solution of the tin protochloride that the mass content that is mixed with tin protochloride is 5%, under whipped state, to the acidic aqueous solution that is added dropwise to tin protochloride in above-mentioned saponification liquor, at 58 ℃, carry out replacement(metathesis)reaction, the state until reaction reaches capacity, form the sub-tin solid of white stearic acid of adhesion shape, stop stirring, add cold water and cool to 48 ℃, reduce degree of adhesion, then restart stirring, until reaction solution occur to drip a clear phenomenon, (dripping a clear phenomenon refers to the container reaction solution that takes a morsel, by container lean, water is separated with solid, and water is the thorough clearly phenomenon oozing), if do not drip the acidic aqueous solution that clearly suitably drips again tin protochloride, until drip clear, replacement(metathesis)reaction is carried out completely, through centrifugal, dehydration, repeatedly wash and be dried and obtain the sub-tin product of white stearic acid.
Embodiment 3
The aqueous sodium hydroxide solution of 2wt% is heated to 85 ℃, under whipped state, slowly add stearic acid to carry out saponification reaction, reaction process is measured the pH value of saponification liquor at any time, when saponification liquor reaches pH value that precision test paper measures 9～10, stop adding stearic acid, maintain the temperature at 85 ℃ and continue reaction, the pH value of repetition measurement saponification liquor, if pH value is greater than 10, add stearic acid and continue reaction, if pH value is less than 9, add sodium hydroxide solution and continue reaction, the pH value that maintains reaction solution is 9～10, continue stirring reaction 30 minutes, saponification reaction finishes, saponification liquor is cooled to 58 ℃.
In water, first add the hydrochloric acid of water weight 5%, the mass concentration of described hydrochloric acid is 36%, and then add tin protochloride, the mass content being mixed with is the acidic aqueous solution of 10% tin protochloride, under whipped state, to the acidic aqueous solution that is added dropwise to tin protochloride in above-mentioned saponification liquor, at 53 ℃, carry out replacement(metathesis)reaction, the state until reaction reaches capacity, form the sub-tin solid of white stearic acid of adhesion shape, stop stirring, add cold water and cool to 43 ℃, reduce degree of adhesion, then restart stirring, until reaction solution occur to drip a clear phenomenon, (dripping a clear phenomenon refers to the container reaction solution that takes a morsel, by container lean, water is separated with solid, and water is the thorough clearly phenomenon oozing), if do not drip the acidic aqueous solution that clearly suitably drips again tin protochloride, until drip clear, replacement(metathesis)reaction is carried out completely, through centrifugal, dehydration, repeatedly wash and be dried and obtain the sub-tin product of white stearic acid.
Embodiment 4
The aqueous sodium hydroxide solution of 3wt% is heated to 90 ℃, under whipped state, slowly add stearic acid to carry out saponification reaction, reaction process is measured the pH value of saponification liquor at any time, when saponification liquor reaches pH value that precision test paper measures 9～10, stop adding stearic acid, maintain the temperature at 90 ℃ and continue reaction, the pH value of repetition measurement saponification liquor, if pH value is greater than 10, add stearic acid and continue reaction, if pH value is less than 9, add sodium hydroxide solution and continue reaction, the pH value that maintains reaction solution is 9～10, continue stirring reaction 40 minutes, saponification reaction finishes, saponification liquor is cooled to below 60 ℃.
In water, first add the hydrochloric acid of water weight 3%, the mass concentration of described hydrochloric acid is 37%, and then add tin protochloride, the mass content being mixed with is the acidic aqueous solution of 8% tin protochloride, under whipped state, to the acidic aqueous solution that is added dropwise to tin protochloride in above-mentioned saponification liquor, at 56 ℃, carry out replacement(metathesis)reaction, the state until reaction reaches capacity, form the sub-tin solid of white stearic acid of adhesion shape, stop stirring, add cold water and cool to 46 ℃, reduce degree of adhesion, then restart stirring, until reaction solution occur to drip a clear phenomenon, (dripping a clear phenomenon refers to the container reaction solution that takes a morsel, by container lean, water is separated with solid, and water is the thorough clearly phenomenon oozing), if do not drip the acidic aqueous solution that clearly suitably drips again tin protochloride, until drip clear, replacement(metathesis)reaction is carried out completely, through centrifugal, dehydration, wash and be dried for three times and obtain the sub-tin product of white stearic acid.
Embodiment 5
The aqueous sodium hydroxide solution of 4wt% is heated to 92 ℃, under whipped state, slowly add stearic acid to carry out saponification reaction, reaction process is measured the pH value of saponification liquor at any time, when saponification liquor reaches pH value that precision test paper measures 9～10, stop adding stearic acid, maintain the temperature at 92 ℃ and continue reaction, the pH value of repetition measurement saponification liquor, if pH value is greater than 10, add stearic acid and continue reaction, if pH value is less than 9, add sodium hydroxide solution and continue reaction, the pH value that maintains reaction solution is 9～10, continue stirring reaction 35 minutes, saponification reaction finishes, saponification liquor is cooled to 60 ℃.
In water, first add the hydrochloric acid of water weight 4%, the mass concentration of described hydrochloric acid is 36%, and then add tin protochloride, the mass content being mixed with is the acidic aqueous solution of 6% tin protochloride, under whipped state, to the acidic aqueous solution that is added dropwise to tin protochloride in above-mentioned saponification liquor, at 60 ℃, carry out replacement(metathesis)reaction, the state until reaction reaches capacity, form the sub-tin solid of white stearic acid of adhesion shape, stop stirring, add cold water and cool to 50 ℃, reduce degree of adhesion, then restart stirring, until reaction solution occur to drip a clear phenomenon, (dripping a clear phenomenon refers to the container reaction solution that takes a morsel, by container lean, water is separated with solid phase prod, and water is the thorough clearly phenomenon oozing), if do not drip the acidic aqueous solution that clearly suitably drips again tin protochloride, until drip clear, replacement(metathesis)reaction is carried out completely, through centrifugal, dehydration, repeatedly wash and be dried and obtain the sub-tin product of white stearic acid.
The quality index of the sub-tin of stearic acid prepared by above-described embodiment 1-5 sees the following form.
| Project | Outward appearance | Ignition residue (wt%) | Free acid content (wt%) | Tin content (wt%) |
| Embodiment 1 | White | 22.2 | 21.5 | 17.9 |
| Embodiment 2 | White | 22.5 | 22.3 | 18.1 |
| Embodiment 3 | White | 23.09 | 15.1 | 18.5 |
| Embodiment 4 | White | 22.55 | 16.4 | 18.0 |
| Embodiment 5 | White | 22.89 | 15.5 | 17.7 |
Claims (4)
1. a synthetic method for the sub-tin of stearic acid, is characterized in that comprising the following steps:
(1) stearic acid and sodium hydroxide solution are carried out to saponification reaction, then saponification liquor is cooled to below 60 ℃;
(2) under whipped state, to being added dropwise to the acidic aqueous solution that mass content is 5～10% solubility tin salt in the saponification liquor of step (1), at 55～60 ℃, carry out replacement(metathesis)reaction, the state until reaction reaches capacity, form the sub-tin solid of white stearic acid of adhesion shape, stop stirring, add cold water and cool to 45～50 ℃, reduce degree of adhesion, then restart stirring, until reaction solution occurs dripping clear phenomenon, replacement(metathesis)reaction is carried out completely, through centrifugal, dehydration, washing, obtain the sub-tin product of stearic acid.
2. the synthetic method of the sub-tin of stearic acid as claimed in claim 1, it is characterized in that: the acidic aqueous solution of the solubility tin salt that described mass content is 5～10% is in water, first to add the hydrochloric acid of water weight 2～5%, the mass concentration of described hydrochloric acid is 36～38%, and then add solubility tin salt, the acidic aqueous solution of the solubility tin salt that the mass content being mixed with is 5～10%.
3. the synthetic method of the sub-tin of stearic acid as claimed in claim 2, is characterized in that: described solubility tin salt is tin protochloride.
4. the synthetic method of the sub-tin of the stearic acid as described in claim 1,2 or 3, it is characterized in that: in step (1), during described saponification reaction, the aqueous sodium hydroxide solution of 1～5wt% is heated to 85～95 ℃, under whipped state, slowly add stearic acid to carry out saponification reaction, when saponification liquor pH value reaches 9～10, stop adding stearic acid, maintain the temperature at 85～95 ℃, the pH value that maintains reaction solution is 9～10, continue stirring reaction 30～40 minutes, saponification reaction finishes, and cools to below 60 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109795058A (en) * | 2019-02-11 | 2019-05-24 | 贵州长田水晶胶粘剂有限公司 | Remover in rubber |
| CN111003783A (en) * | 2019-12-30 | 2020-04-14 | 南通新邦化工科技有限公司 | Method for reducing PH value of wastewater in stearate production |
| CN112574025A (en) * | 2019-09-27 | 2021-03-30 | 中国科学院大连化学物理研究所 | Synthesis method of stannous ricinoleate |
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|---|---|---|---|---|
| CN1535946A (en) * | 2003-03-31 | 2004-10-13 | 日本油脂株式会社 | Tin salt of low melting point carboxylate and its production method |
| CN102492235A (en) * | 2011-11-22 | 2012-06-13 | 山东瑞丰高分子材料股份有限公司 | Epoxidized soybean oleic acid calcium zinc composite stabilizing agent for PVC (polyvinyl chloride) and its preparation method |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1535946A (en) * | 2003-03-31 | 2004-10-13 | 日本油脂株式会社 | Tin salt of low melting point carboxylate and its production method |
| CN102492235A (en) * | 2011-11-22 | 2012-06-13 | 山东瑞丰高分子材料股份有限公司 | Epoxidized soybean oleic acid calcium zinc composite stabilizing agent for PVC (polyvinyl chloride) and its preparation method |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109795058A (en) * | 2019-02-11 | 2019-05-24 | 贵州长田水晶胶粘剂有限公司 | Remover in rubber |
| CN112574025A (en) * | 2019-09-27 | 2021-03-30 | 中国科学院大连化学物理研究所 | Synthesis method of stannous ricinoleate |
| CN112574025B (en) * | 2019-09-27 | 2022-07-08 | 中国科学院大连化学物理研究所 | A kind of synthetic method of stannous ricinoleate |
| CN111003783A (en) * | 2019-12-30 | 2020-04-14 | 南通新邦化工科技有限公司 | Method for reducing PH value of wastewater in stearate production |
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