CN108640830A - A kind of preparation method of organic acid bismuth - Google Patents
A kind of preparation method of organic acid bismuth Download PDFInfo
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- CN108640830A CN108640830A CN201810381311.5A CN201810381311A CN108640830A CN 108640830 A CN108640830 A CN 108640830A CN 201810381311 A CN201810381311 A CN 201810381311A CN 108640830 A CN108640830 A CN 108640830A
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- organic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of preparation methods of organic acid bismuth, include the following steps：Acylate is made in organic acid；The organic salt obtained and five nitric hydrate bismuths, cosolvent are mixed, leads to nitrogen, is heated to reaction temperature and is reacted；Organic solvent is added, extracts organic phase；It is rinsed, is filtered using flushing water, distillation obtains organic acid bismuth.The organic acid bismuth preparation method of the present invention, purification extraction is carried out to product by the way that organic solvent is added, the various water-soluble substances in product are removed by washing, the insoluble matter in product is removed by filtering, the organic solvent and water in product are removed finally by vacuum distillation, finally obtains that color is shallow and the preferable organic acid bismuth of stability, reaction condition mitigates, production cost is low, with short production cycle, and bismuth source utilization rate is high, is suitble to produce in enormous quantities.
Description
Technical field
The invention belongs to fine chemistry industry auxiliary agent fields, are related to the preparation of organic bismuth catalyst, more particularly to organic acid bismuth
The preparation of catalyst.
Background technology
Organic acid bismuth is widely used in the accelerating agent of resins synthesis and the drier of paint as catalyst, relatively strong due to having
Catalysis characteristics, and it is environment-protecting and non-poisonous, be the optimal selection for replacing the poisoned catalysts such as lead, mercury, tin.But since the price of bismuth is opposite
Want much higher in lead, mercury, tin etc., and the synthesis technology of organo-bismuth requires height, while yield is relatively low, has further resulted in organic
The price of bismuth is more high than the price of the catalyst such as lead, mercury, tin.
The preparation method of the organic acid bismuth of the prior art has the following defects：Synthesis technology is complex, and synthesis condition is wanted
Ask higher, manufacturing cost is higher, and product yield is low etc..Currently, bismuth source used when the synthesis of organic acid bismuth is mainly：Metal
Bismuth, bismuth oxide and bismuth hydroxide.The method for preparing organic acid bismuth using bismuth metal as bismuth source：First by carboxylic acid or carboxylic acid anhydrides and gold
Belong to bismuth meal and hydrazine hydrate to be uniformly mixed, is heated to 80 DEG C or more, strict temperature control, while it is anti-with Bubbling method to be passed through air oxidation
It answers more than ten hour, this method, which exists, generates complex process, and synthesis condition is not easy to control, and the generation period is longer, and product yield is not
Ideal is not suitable for carrying out mass production.The method for preparing organic acid bismuth using bismuth oxide as bismuth source：Mainly utilize organic acid
It is reacted for a long time under the high temperature conditions with bismuth oxide and organic acid bismuth is made, the energy consumption of this method is big, and the production cycle is long, is produced into
This height, product colour is deeper, is unfavorable for long-term development of enterprise.The method for preparing organic acid bismuth as bismuth source using bismuth hydroxide：Directly
It is reacted with bismuth hydroxide using organic acid, this method is there are the utilization rate of bismuth hydroxide is low, and to of bismuth hydroxide
Grain size requirements are very stringent, are not suitable for mass production.
Invention content
Based on this, for the prior art, the technical problem to be solved by the present invention is to improve the profit in bismuth source in synthesis organic acid
With rate, simplification of flowsheet and operation mitigate reaction condition.
The purpose of the present invention is to provide a kind of production costs, and low, with short production cycle, reaction condition mitigates, is obtained organic
Sour bismuth stability is good, organic acid bismuth of light color preparation method.
The technical solution used in the present invention is：
A kind of preparation method of organic acid bismuth, includes the following steps：
1) acylate is made in organic acid；
2) organic salt obtained and five nitric hydrate bismuths, cosolvent are mixed, lead to nitrogen, be heated to reaction temperature
Degree is reacted；
3) organic solvent is added, extracts organic phase；
4) it is rinsed, is filtered using flushing water, distillation obtains organic acid bismuth.
In one of the embodiments, the organic acid be selected from isooctyl acid, neodecanoic acid, aphthenic acids, lauric acid, stearic acid,
It is one or more in ten dihydroxystearic acids；The cosolvent is in acetic acid, lactic acid, acetic anhydride, hydrochloric acid, nitric acid, sulfuric acid
It is one or more.
The degree that the dosage of the cosolvent accounts for whole system in one of the embodiments, is 0~70%；Institute
The molar ratio range for stating acylate and five nitric hydrate bismuths is (2~12)：1.
It is further preferred that the degree that the dosage of the cosolvent accounts for whole system is 15~55%；It is described to have
The molar ratio range of machine hydrochlorate and five nitric hydrate bismuths is (3~9)：1.
The acylate includes sodium salt, sylvite, lithium salts and ammonium salt in one of the embodiments,.
The organic solvent is selected from toluene, dimethylbenzene, trimethylbenzene, n-hexane, industrial naptha in one of the embodiments,
In it is one or more, the organic solvent be used for account for whole system degree be 15~75%
The flushing water is one in distilled water, deionized water, industrial water and tap water in one of the embodiments,
Kind；The distillation is vacuum distillation.
It is further preferred that the flushing water is distilled water or deionized water.
In one of the embodiments, the reaction temperature be 55~185 DEG C, the reaction time needed be 2~for 24 hours.
It is further preferred that the reaction temperature is 75~160 DEG C, the reaction time is 2.5~11h.
Compared with the prior art, beneficial effects of the present invention are：Purification extraction is carried out to product by the way that organic solvent is added, is led to
Washing is crossed to remove the various water-soluble substances in product, the insoluble matter in product is removed by filtering, finally by decompression
Distillation removes the organic solvent and water in product, finally obtains that color is shallow and the preferable organic acid bismuth of stability, and reaction condition is slow
With production cost is low, with short production cycle, and bismuth source utilization rate is high, and the utilization rate in bismuth source can reach 80% or more under normal circumstances, fits
It closes and produces in enormous quantities.
Specific implementation mode
First, illustrate a kind of preparation method of organic acid bismuth of the present invention.
A kind of preparation method of organic acid bismuth of the application, includes the following steps：
1) acylate is made in organic acid；
2) organic salt obtained and five nitric hydrate bismuths, cosolvent are mixed, lead to nitrogen, be heated to reaction temperature
Degree is reacted；
3) organic solvent is added, extracts organic phase；
4) it is rinsed, is filtered using flushing water, distillation obtains organic acid bismuth.
In a kind of preparation method of organic acid bismuth according to the application, it is preferable that the organic acid be selected from isooctyl acid,
It is one or more in neodecanoic acid, aphthenic acids, lauric acid, stearic acid, ten dihydroxystearic acids；The cosolvent be selected from acetic acid,
It is one or more in lactic acid, acetic anhydride, hydrochloric acid, nitric acid, sulfuric acid.
In a kind of preparation method of organic acid bismuth according to the application, it is preferable that the dosage of the cosolvent accounts for whole
The degree of a system is 0~70%；The molar ratio range of the acylate and five nitric hydrate bismuths is (2~12)：
1。
According to a kind of preparation method of organic acid bismuth of the application, it is preferable that the acylate include sodium salt,
Sylvite, lithium salts and ammonium salt.
According to a kind of preparation method of organic acid bismuth of the application, it is preferable that the organic solvent is selected from toluene, two
One or more in toluene, trimethylbenzene, n-hexane, industrial naptha, the percentage that the organic solvent is used for accounting for whole system contains
Amount is 15~75%.
According to a kind of preparation method of organic acid bismuth of the application, it is preferable that the flushing water is selected from distilled water, goes
It is a kind of in ionized water, industrial water and tap water；The distillation is vacuum distillation.
According to a kind of preparation method of organic acid bismuth of the application, it is preferable that the reaction temperature is 55~185
DEG C, the reaction time needed be 2~for 24 hours.
Secondly, illustrate a kind of embodiment of the preparation method of organic acid bismuth according to the application.
Embodiment 1
24g sodium hydroxides are dissolved in 50g water, then 105g neodecanoic acids are added again and are reacted, 55g five then is added to it
Nitric hydrate bismuth and 27.5g cosolvent acetic acid, stir evenly, and logical nitrogen is simultaneously warming up to 85 DEG C, insulation reaction 5h, appropriate reduction temperature
Toluene is added in degree, and stratification extracts organic phase, then washes to organic phase, be filtered to it after washing,
Then it is evaporated under reduced pressure out toluene and water again, finally obtains more full-bodied light yellow transparent liquid.
Experimental example 2
24g sodium hydroxides are dissolved in 50g water, then 105g neodecanoic acids are added again and are reacted, 40g five then is added to it
Nitric hydrate bismuth and 20g cosolvent acetic acid, stir evenly, and logical nitrogen is simultaneously warming up to 85 DEG C, insulation reaction 5h, appropriate reduction temperature
Toluene is added in degree, and stratification extracts organic phase, then washes to organic phase, be filtered to it after washing,
Then it is evaporated under reduced pressure out toluene and water again, finally obtains more full-bodied light yellow transparent liquid.
Experimental example 3
24g sodium hydroxides are dissolved in 50g water, then 89g isooctyl acids are added again and are reacted, 45g five then is added to it
Nitric hydrate bismuth and 22.5g cosolvent acetic acid, stir evenly, and logical nitrogen is simultaneously warming up to 85 DEG C, insulation reaction 5h, appropriate reduction temperature
Toluene is added in degree, and stratification extracts organic phase, then washes to organic phase, be filtered to it after washing,
Then it is evaporated under reduced pressure out toluene and water again, finally obtains more full-bodied light yellow transparent liquid.
Experimental example 4
25.2g lithium hydroxides are dissolved in 50g water, then 105g neodecanoic acids are added again and are reacted, 45g then is added to it
Five nitric hydrate bismuths and 22.5g cosolvent acetic acid, stir evenly, and logical nitrogen is simultaneously warming up to 85 DEG C, insulation reaction 5h, appropriate reduction
Temperature, is added toluene, and stratification extracts organic phase, then washes to organic phase, carried out to it after washing
Filter, is then evaporated under reduced pressure out toluene and water, finally obtains more full-bodied light yellow transparent liquid again.
Experimental example 5
By the direct neutralization reaction of ammonium hydroxide 105g neodecanoic acids of 40.8g25%, then to its be added five nitric hydrate bismuths of 55g and
27.5g cosolvent acetic acid, stirs evenly, and logical nitrogen is simultaneously warming up to 85 DEG C, insulation reaction 5h, suitably reduces temperature, toluene is added,
Stratification extracts organic phase, then washes to organic phase, be filtered to it after washing, then depressurize steaming again
Toluene and water are distillated, finally obtains more full-bodied yellow to buff transparency liquid.
Several embodiments of the invention above described embodiment only expresses, the description thereof is more specific and detailed, but simultaneously
Cannot the limitation to the scope of the claims of the present invention therefore be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention
Protect range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of preparation method of organic acid bismuth, which is characterized in that include the following steps：
A) acylate is made in organic acid；
B) organic salt obtained and five nitric hydrate bismuths, cosolvent are mixed, lead to nitrogen, be heated to reaction temperature into
Row reaction；
C) organic solvent is added, extracts organic phase；
D) it is rinsed, is filtered, the product obtained after distillation is organic acid bismuth using flushing water.
2. a kind of preparation method of organic acid bismuth according to claim 1, which is characterized in that the organic acid is selected from different pungent
It is one or more in acid, neodecanoic acid, aphthenic acids, lauric acid, stearic acid, ten dihydroxystearic acids；The cosolvent is selected from second
It is one or more in acid, lactic acid, acetic anhydride, hydrochloric acid, nitric acid, sulfuric acid.
3. a kind of preparation method of organic acid bismuth according to claim 2, which is characterized in that the dosage of the cosolvent accounts for whole
The degree of a system is 0~70%；The molar ratio range of the acylate and five nitric hydrate bismuths is (2~12)：
1。
4. a kind of preparation method of organic acid bismuth according to claim 1, which is characterized in that the acylate includes sodium
Salt, sylvite, lithium salts and ammonium salt.
5. a kind of preparation method of organic acid bismuth according to claim 1, which is characterized in that the organic solvent is selected from first
One or more in benzene, dimethylbenzene, trimethylbenzene, n-hexane, industrial naptha, the organic solvent is used for accounting for the percentage of whole system
It is 15~75% than content.
6. a kind of preparation method of organic acid bismuth according to claim 1, which is characterized in that the flushing water is selected from distillation
It is a kind of in water, deionized water, industrial water and tap water；The distillation is vacuum distillation.
7. a kind of preparation method of organic acid bismuth according to claim 1, which is characterized in that the reaction temperature be 55~
185 DEG C, the reaction time needed be 2~for 24 hours.
8. a kind of preparation method of organic acid bismuth according to claim 6, which is characterized in that the reaction temperature be 75~
160 DEG C, the reaction time is 2.5~11h.
9. a kind of preparation method of organic acid bismuth according to claim 2, which is characterized in that the dosage of the cosolvent accounts for whole
The degree of a system is 15~55%；The molar ratio range of the acylate and five nitric hydrate bismuths is (3~9)：
1。
10. a kind of preparation method of organic acid bismuth according to claim 5, which is characterized in that the flushing water is distilled water
Or deionized water.
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| CN114702637A (en) * | 2022-04-01 | 2022-07-05 | 国科广化韶关新材料研究院 | Preparation method and application of environment-friendly polyurethane catalyst |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114702637A (en) * | 2022-04-01 | 2022-07-05 | 国科广化韶关新材料研究院 | Preparation method and application of environment-friendly polyurethane catalyst |
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Application publication date: 20181012 |