CN105315151B - A kind of preparation method of neodymium caprate - Google Patents
A kind of preparation method of neodymium caprate Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
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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
- C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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Abstract
The present invention relates to the preparation techniques field of carboxylic acid neodymium, there is provided a kind of safe and environment-friendly, low consumption, time-consuming, low production cost, the preparation method of the neodymium caprate prepared under low temperature, normal pressure, comprise the following steps：(1) dissolving of neodymia；(2) precipitate；(3) saponification；(4) extract；(5) removal of impurity；(6) tank is entered.
Description
The application is that patent application day is on December 05th, 2013, Application No. 2013106448125, and patent name is：
A kind of divisional application of the preparation method of neodymium caprate.
Technical field
The present invention relates to the preparation techniques field of carboxylic acid neodymium, more particularly to a kind of preparation method of neodymium caprate.
Background technology
The carboxylate of neodymium is major catalyst with good catalysis activity in synthesizing rare-earth butadiene rubber.Butadiene rubber
It is second largest synthetic rubber kind that current production rate is only second to benzene rubber, because it has splendid wearability, preferable resilience
And preferably fatigue performance and turn into one of topmost material of Tire production.Simultaneously with auto industry and highway
Develop rapidly, the requirement of requirement and structural behaviour to butadiene rubber is also constantly lifted.Therefore, make great efforts to improve existing catalytic body
It is and researches and develops new catalyst and explore its inherent mechanism, is made joint efforts as vast researcher and Chemical Manufacture enterprise
Direction.
Neodymium caprate is one kind of rare earth carboxylate, and at present, domestic neodymium caprate is mainly imported product, its preparation method
Mainly there are decomposition method and extraction.The Changchun applied chemistry study of the Chinese Academy of Sciences develops a kind of rare earth carboxylates
Manufacture method, and it is documented in page 381 in the rare earth catalyst synthetic rubber collected works of Chinese science publishing house publication in 1980 extremely
In page 387, it is a kind of direx process, mainly adds concentrated hydrochloric acid in three neodymia, with after producing neodymium chloride, then and
Ammonium hydroxide, aphthenic acids mixing, produce neodymium caprate solution.Being neutralized with ammoniacal liquor makes the pH of solution in neutrality, then through settling water
Phase and separation of oil, last redistillation can be obtained neodymium caprate solution.The neodymium caprate as obtained in the chemistry institute of Changchun, its
Between 0.45/1~0.8/1, moisture content of its residual exists the mol ratio of the free acid RCOOH of Nd chemical combination (i.e. and) and lanthanide series metal
Between 78~425ppm, neodymium caprate thus obtained by method is, it is necessary to by the steps such as extraction, filtering, therefore its synthesis step
The production equipment of needs is more, additionally, sodium metal can be remained in the product, therefore product needed is caused again by purification step
Yield declines.
The content of the invention
Therefore, for above content, the present invention provides a kind of safe and environment-friendly, low consumption, time-consuming, low production cost,
The preparation method of the neodymium caprate prepared under low temperature, normal pressure.
To reach above-mentioned purpose, the present invention is achieved by the following technical solutions：A kind of preparation method of neodymium caprate,
Comprise the following steps：
(1) dissolving of neodymia：After by neodymia dissolving with hydrochloric acid, the removal of impurity is hydrolyzed under the conditions of pH=4~5, obtained
NdCl3Solution；
(2) precipitate：NdCl after step (1) is dissolved3Solution left standstill is precipitated, filtering, the NdCl for being clarified3Solution；
(3) saponification：Neodecanoic acid and hexane are prepared in addition reaction vessel in proportion, is sufficiently mixed, then added
Ammoniacal liquor, carries out saponification 30~35 minutes at 55~65 DEG C；
(4) extract：Step (2) is added into step (3) hybrid reaction more than 10 minutes by a certain percentage, split-phase is stood；
(5) removal of impurity：Step (4) lower floor water is mutually removed, is recycled, upper strata finished product is further filtered, and the removal of impurity is complete
Into；
(6) tank is entered：Product after purification is entered into tank, that is, required neodymium caprate solution is obtained.
Further improving is：Neodymia purity in the step (1) is 99%.
Further improving is：The concentration of the neodymium caprate in the step (6) is 0.3mol/L.
Further improving is：The consumption of the neodymia in the step (1) is 20~25 weight portions, the deionized water
It is 130~150 weight portions, the weight portion of hydrochloric acid 40~50, the weight portion of neodecanoic acid 150~180, the weight portion of n-hexane 160~200,
The weight portion of ammoniacal liquor 40~50.
Further improving is：The consumption of the neodymia in the step (1) is 22~25 weight portions, the deionized water
It is 140~150 weight portions, the weight portion of hydrochloric acid 45~50, the weight portion of neodecanoic acid 165~180, the weight portion of n-hexane 180~200,
The weight portion of ammoniacal liquor 45~50.
Further improving is：The concentration of the neodymium caprate in the step (6) is 0.5mol/L.
Further improving is：The consumption of the neodymia in the step (1) is 35~45 weight portions, the deionized water
It is 150~180 weight portions, the weight portion of hydrochloric acid 50~60, the weight portion of neodecanoic acid 160~190, the weight portion of n-hexane 180~210,
The weight portion of ammoniacal liquor 80~100.
Further improving is：The consumption of the neodymia in the step (1) is 40~45 weight portions, the deionized water
It is 165~180 weight portions, the weight portion of hydrochloric acid 55~60, the weight portion of neodecanoic acid 175~190, the weight portion of n-hexane 195~210,
The weight portion of ammoniacal liquor 90~100.
Further improving is：In the step (1), in the course of dissolution of neodymia, dissolved using mixer, institute
State the electrical conductivity of deionized water<10us/cm, resistivity >=15M Ω.
By using preceding solution, the beneficial effects of the invention are as follows：The present invention is by using atmospheric low-temperature and control
Saponification rate can arbitrarily control free acid concentration, using saponification cross current solvent extraction technique, may be such that Nd3+Utilization rate reach 100%, system
The neodymium caprate quality for obtaining is good.There is good catalysis activity for diene stereospecfic polymerization.With traditional heating interrupted extraction method
Compare, the production equipment of input of the present invention is less, the electric energy of required consumption is also less, by controlling saponification rate, can improve
Nd3+Utilization rate and free acid concentration.
Specific embodiment
Describe embodiments of the present invention in detail below with reference to specific embodiment, how skill is applied to the present invention whereby
Art means solve technical problem, and reach the implementation process of technique effect and can fully understand and implement according to this.
If not specializing, the conventional hand that the technological means employed in embodiment is well known to those skilled in the art
Section, the reagent and product for being used also are available commercial.The source of agents useful for same, trade name and it is necessary to list it
Constituent person, indicates when occurring first.
Embodiment one
A kind of preparation method of neodymium caprate, by taking the neodymium caprate for preparing 0.3mol/L as an example, comprises the following steps：
(1) dissolving of neodymia：Be 99% by purity, the neodymia of 22 weight portions at normal temperatures with 140 weight portions go from
Sub- water and 45 weight portion dissolving with hydrochloric acid, dissolving is stirred using mixer, obtains neodymium chloride solution, described deionized water
Electrical conductivity<10us/cm, resistivity >=15M Ω；
(2) precipitate：Neodymium chloride after step (1) has been processed is staticly settled, and filtering, the neodymium chloride clarified is molten
Liquid；
(3) saponification：The weight portion of neodecanoic acid 170 and the weight portion of n-hexane 200 are added in reaction vessel, is sufficiently mixed
Uniformly, the weight portion of ammoniacal liquor 40 is added, saponification 30min is carried out under 60 DEG C, normal pressure；
(4) extract：Step (2) added into step (3) extractive reaction, addition be overall reaction can extraction quantity 80% carry out
Cross current solvent extraction, Nd3+Extraction yield be 100%, raffinate water is mutually discarded；The oxygen obtained in excessive step (2) is added for the second time
Change neodymium solution, make the NH in organic phase4 +With Nd3+Reaction is complete, and second raffinate water is mutually recycled, and makes total Nd3+Utilization rate
Be 100%, and free acid and neodymium caprate ratio<0.5；
(5) removal of impurity is separated：Product lower floor water after step (4) treatment is mutually extracted out, circulating and recovering, upper strata finished product enters one
Step filtering, removal of impurities is completed；
(6) tank is entered：Complete product will be purified and enter tank, that is, required neodymium caprate solution is obtained, the product is to polymerization fourth
Diene, the good catalytic activity with stereospecfic polymerization.
Embodiment two
A kind of preparation method of neodymium caprate, by taking the neodymium caprate for preparing 0.5mol/L as an example, comprises the following steps：
(1) dissolving of neodymia：Be 99% by purity, the neodymia of 40 weight portions at normal temperatures with 165 weight portions go from
Sub- water and 55 weight portion dissolving with hydrochloric acid, dissolving is stirred using mixer, obtains neodymium chloride solution, described deionized water
Electrical conductivity<10us/cm, resistivity >=15M Ω；
(2) precipitate：Neodymium chloride after step (1) has been processed is staticly settled, and filtering, the neodymium chloride clarified is molten
Liquid；
(3) saponification：The weight portion of neodecanoic acid 175 and the weight portion of n-hexane 195 are added in reaction vessel, is sufficiently mixed
Uniformly, the weight portion of ammoniacal liquor 90 is added, saponification 35min is carried out under 60 DEG C, normal pressure；
(4) extract：Step (2) added into step (3) extractive reaction, addition be overall reaction can extraction quantity 80% carry out
Cross current solvent extraction.Nd3+Extraction yield be 100%, raffinate water is mutually discarded；The oxygen obtained in excessive step (2) is added for the second time
Change neodymium solution, make the NH in organic phase4 +With Nd3+Reaction is complete, and second raffinate water is mutually recycled, and makes total Nd3+Utilization rate
Be 100%, and free acid and neodymium caprate ratio<0.5；
(5) removal of impurity is separated：Product lower floor water after step (4) treatment is mutually extracted out, circulating and recovering, upper strata finished product enters one
Step filtering, removal of impurities is completed；
(6) tank is entered：Complete product will be purified and enter tank, that is, required neodymium caprate solution is obtained, the product is to polymerization fourth
Diene, the good catalytic activity with stereospecfic polymerization.
Wherein, the reaction of step (1) is as follows：
Nd2O3+6HCl→2NdCl3+3H2O；
Chemical name：Neodymium caprate (also known as 2,5- dimethyl -2- ethyl-hexanoics neodymium) Neodymium
neodecanoate；
Its molecular formula：[(CH3)2-CH-CH2-CH2-C-(CH3)(C2H5)–COO]3Nd
Structural formula is：
R1、R2, be C2H5, R3It is (CH3)2-CH-CH2-CH2-.In the present invention, neodymia, hydrochloric acid, deionized water, new
The consumption of capric acid, n-hexane and ammoniacal liquor is to be adjusted configuration according to the concentration requirement of obtained neodymium caprate, embodiment one and
Ratio in embodiment two is weight percentage.In embodiment one, neodymia：Hydrochloric acid：Deionized water：Neodecanoic acid：N-hexane：
Ammoniacal liquor=22：45：140：170：200：40, neodymia in embodiment two：Hydrochloric acid：Deionized water：Neodecanoic acid：N-hexane：Ammoniacal liquor
=45：55：165：175：195：90.When the concentration of neodymium caprate is 0.3mol/L, neodymia：Hydrochloric acid：Deionized water：The new last of the ten Heavenly stems
Acid：N-hexane：Ammoniacal liquor=20~25：40~50：130~150：150~180：160~200：40~50, when neodymium caprate
When concentration is 0.5mol/L, neodymia：Hydrochloric acid：Deionized water：Neodecanoic acid：N-hexane：Ammoniacal liquor=35~45：50~60：150~
180：160~190：180~210：80~100, the purpose of the present invention can be all realized in above parameter area.
The neodymium chloride of prioritizing selection Ganzhou Shang Yuan new materials company production of the present invention, the neodymia produced using other companies
The object of the invention can equally be realized.
Obtain the results are shown in Table 1 with neodymium caprate polymerized butadiene obtained in this method.
The neodymium caprate catalytic polymerization butadiene of table 1.
| Reactivity 1% | Polybutadiene viscosity/(dl/g) | Along Isosorbide-5-Nitrae | 1,2 | Anti- Isosorbide-5-Nitrae |
| 96.1 | 7 | 97.9 | 0.9 | 1.2 |
| 96.2 | 7 | 97.9 | 0.9 | 1.2 |
| 95.5 | 6.9 | 97.8 | 0.9 | 1.3 |
| 95.6 | 7.1 | 97.9 | 0.9 | 1.2 |
Wherein, along Isosorbide-5-Nitrae, 1,2, anti-Isosorbide-5-Nitrae refer both to its respective polybutadiene content.
Conclusion：(1) as shown in Table 1, the neodymium caprate polymerized butadiene for being prepared with the method has good directional catalyzing
Activity；
(2) polymerization process is steady, it is easy to manipulate, and reaction rate is very fast；
(3) latex stable performance, the SBR-1500 of preparation, SBR-1502, SBR-1712 properties of product are preferable.
The present invention entirely reaches stunt matter by atmospheric low-temperature and cross current solvent extraction technique, obtained neodymium caprate product quality
Amount standard, compared with extraction is had a rest in traditional heating, the utilization rate of neodymium metal is higher, and the production equipment of input is less, required to disappear
The electric energy of consumption is also less, can arbitrarily control free acid concentration according to saponification rate in addition, effectively prevent in production process and block occurs
Shape is precipitated, clogging, the time required to shortening production, improves productivity ratio.
Described above, only using the embodiment of this origination techniques content, any those skilled in the art are with this wound
Make done modification, change, all belong to the scope of the claims of this creation opinion, and be not limited to those disclosed embodiments.
Claims (2)
1. a kind of preparation method of neodymium caprate, it is characterised in that comprise the following steps：
(1) dissolving of neodymia：After by neodymia deionized water and dissolving with hydrochloric acid, removal of impurities is hydrolyzed under the conditions of pH=4~5
Matter, obtains NdCl3Solution；
(2) precipitate：NdCl after step (1) is dissolved3Solution left standstill is precipitated, filtering, the NdCl for being clarified3Solution；
(3) saponification：Neodecanoic acid and hexane are prepared in addition reaction vessel in proportion, are sufficiently mixed, then add ammoniacal liquor,
Saponification is carried out at 55~65 DEG C 30~35 minutes；
(4) extract：(2) are added into step (3) hybrid reaction more than 10 minutes by a certain percentage, split-phase is stood；
(5) removal of impurity：Step (4) lower floor water is mutually removed, is recycled, upper strata finished product is further filtered, the removal of impurity is completed；
(6) tank is entered：Product after purification is entered into tank, that is, required neodymium caprate solution is obtained；
The concentration of the neodymium caprate in the step (6) is 0.3mol/L；
The consumption of the neodymia is 22~25 weight portions, and the deionized water is 140~150 weight portions, the weight of hydrochloric acid 45~50
Amount part, the weight portion of neodecanoic acid 165~180, the weight portion of n-hexane 180~200, the weight portion of ammoniacal liquor 45~50；
Step (4) extraction detailed process be：Step (2) addition step (3) extractive reaction, addition can be extracted for overall reaction
The 80% of amount carries out cross current solvent extraction, Nd3+Extraction yield be 100%, raffinate water is mutually discarded；Excessive step is added for the second time
(2) neodymium chloride solution obtained in, makes the NH in organic phase4 +With Nd3+Reaction is complete, and second raffinate water is mutually recycled, and is made
Total Nd3+Utilization rate is 100%, and free acid and neodymium caprate ratio<0.5.
2. the preparation method of neodymium caprate according to claim 1, it is characterised in that：The saponification be 60 DEG C,
30min is reacted under normal pressure.
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| EP1055659A1 (en) * | 1999-05-27 | 2000-11-29 | Petroflex Industria e Comercio S/A | Process for the preparation of neodymium neodecanoate and use thereof as catalytic component for the solution polymerisation of butadiene |
| RU2297407C1 (en) * | 2006-03-09 | 2007-04-20 | Открытое акционерное общество "Нижнекамскнефтехим" | Liquid rare-earth element carboxylate composition, process of preparing this composition, and polymerization process |
| CN101456806A (en) * | 2007-12-13 | 2009-06-17 | 中国科学院兰州化学物理研究所 | Method for preparing bismuth carboxylate |
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- 2013-12-05 CN CN201310644812.5A patent/CN103613496B/en active Active
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| EP1055659A1 (en) * | 1999-05-27 | 2000-11-29 | Petroflex Industria e Comercio S/A | Process for the preparation of neodymium neodecanoate and use thereof as catalytic component for the solution polymerisation of butadiene |
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| CN103613496B (en) | 2015-12-30 |
| CN105315151A (en) | 2016-02-10 |
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| CN105348073A (en) | 2016-02-24 |
| CN103613496A (en) | 2014-03-05 |
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Effective date of registration: 20230810 Address after: Room 1601, 1st Floor, Building 26, Phase 2, Yuanchang Jinxiu No.1, No. 8 Hefu Road, Hechi Community, Shanyao Street, Quangang District, Quanzhou City, Fujian Province, 362114 Patentee after: Fujian Juchuangxin Material Technology Co.,Ltd. Address before: No. 8 Zengcuo'an North Road, Siming District, Xiamen City, Fujian Province, 361001 Patentee before: Huang Huishan |