JP2000063386A - Manufacture of carboxylate of lanthanide metal, and its use as catalyst for polymerization of dienic monomer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a carboxylate of a lanthanide metal in high yield by which the manufacturing process of the carboxylate of the lanthanide metal is simplified and the reaction time is effectively shortened. SOLUTION: The method of manufacturing a carboxylate of a lanthanide metal of the formula Ln(RCOO)3 (Ln is a lanthanide metal element having an atomic number from 57 to 71; R is a 1-19C hydrocarbon group) comprises compounding (A) a lanthanide metal (Ln) compound selected from an oxide or a carbonate of the lanthanide metal (Ln), (B) a 2-20C carboxylic acid, (C) water, and (D) an inert solvent so that the molar ratio of the water (C) to the lanthanide metal (Ln) may be larger than 5:1, and reacting them within the temperature range of 0-300 deg.C.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a lanthanide metal carboxylate and its use as a catalyst for polymerization of a diene monomer.

[0002]

2. Description of the Related Art A method for producing a lanthanide metal carboxylate such as neodymium carboxylate is already known. For example, USP No. 4,520,177 reacts a solution of neodymium chloride with sodium versatate to produce neodymium versatate (Nd (versata
te) ₃ ) is disclosed. The obtained crude neodymium versatate is purified by extracting with toluene, separating the toluene solution and drying. Besides, Changchun Institute of Applied Chemistry (CIA)
(C Changchun, Jilin, China) in 1980, <Synthetic Rubber Catalyzed and Polymerized by Lanthanide Conjugate Catalyst>
Pages 381-387 of the neodymium trinaphthenate (ne
odymium trinaphthenate) is disclosed. According to this disclosure, a method for producing neodymium tri naphthenate, concentrated hydrogen chloride solution in neodymium oxide (Nd ₂ O ₃₎ was added, generate neodymium chloride (NdCl _3),
It is mixed with ammonium hydroxide and naphthenic acid to obtain a solution of neodymium trinaphthenate. The solution containing the oily phase (solvent) thus obtained and the aqueous phase is neutralized with ammonium hydroxide, and after standing to separate the oily phase and the aqueous phase, the separated oily phase To obtain purified neodymium trinaphthenate.
In this purified neodymium trinaphthenate solution,
Free carboxylic acid (ie not bound to neodymium metal)
The molar ratio of RCOOH) to neodymium is 0.45 / 1 to 0.8
/ 1, and the water content is 78 to 425 ppm. The resulting neodymium trinaphthenate is used, in combination with an alkylaluminum chloride compound and an organoaluminum compound, in a catalyst system for polymerizing butadiene. In this catalyst system, the molar ratio of free acid to neodymium is 0.71 / 1 to 0.8 / 1 and the water content is 138 to 287 ppm. When the catalyst system thus obtained is used, good conversion can be obtained in the polymerization of the diene monomer.

The above-mentioned USP No. 4,520,177 and the method for producing neodymium carboxylate proposed by Changchun Institute of Applied Chemistry still have some drawbacks. That is, in the case of USP No. 4,520,177, extraction and filtration steps are required, and sometimes it is necessary to further purify the metal carboxylate to further remove sodium ions. On the other hand, the method of the Changchun Institute is too complicated in process, requires the steps of NdCl ₃ production and neutralization, and both of the above production methods are uneconomical.

USP No. 5,220,045 is a method for producing neodymium versatate (NdV ₃ ) by introducing ammonia into an aqueous mixture of neodymium nitrate solution, versatic acid and cyclohexane, and stirring strongly at room temperature. Is disclosed. After the reaction is complete, the mixture is filtered with distilled water to remove unreacted material and the cyclohexane phase is distilled. In other words, it requires an extraction step with water, which is more complicated. In addition, there is a drawback that neodymium nitrate (Nd (NO) ₃ ) must be manufactured in advance from neodymium oxide.

[0005]

DISCLOSURE OF THE INVENTION As described above, in view of the drawbacks that the manufacturing method in the prior art is too complicated in process and the yield of lanthanide metal carboxylate is not sufficient, the present invention provides a lanthanide having a high yield. An object of the present invention is to provide a method for producing a metal carboxylate.

Another object of the present invention is to provide a production method in which the reaction time is effectively shortened by simplifying the production process of the lanthanide metal carboxylate and by rapidly clarifying the oily phase and the aqueous phase. To provide.

[0007]

DISCLOSURE OF THE INVENTION The present inventors have found that a lanthanide-based metal carboxylate solution produced by directly reacting a lanthanide-based metal oxide or carbonate with a carboxylic acid under the condition that a large amount of water is present. It was found that the lanthanide metal carboxylate can be obtained in high yield by clarifying and separating the oily phase from the aqueous phase and removing the residual water present in the oily phase. According to the present invention, the lanthanide-based metal carboxylate can be easily produced with good yield.

That is, the present invention provides the formula Ln (RCOO) ₃ (wherein Ln represents a lanthanide metal element having an atomic number of 57 to 71, and R is a hydrocarbon group having 1 to 19 carbon atoms). Represents a lanthanide metal carboxylate represented by
(A) Lanthanide metal (Ln) compound selected from lanthanide metal oxides or carbonates, (B) carboxylic acid having 2 to 20 carbon atoms, (C) water, and (D)
Inert solvent and lanthanide metal (Ln) of water (C)
Blended in a molar ratio such that the ratio to
The present invention provides a method for producing a lanthanide-based metal carboxylate, which is characterized by reacting and producing in a temperature range of 0 to 300 ° C.

The lanthanide metal carboxylate produced by the production method of the present invention is suitable for use as a catalyst in the polymerization reaction of a diene monomer, and can improve the conversion rate of the monomer.

The lanthanide-based metal is a metal having an atomic number of 57 to 71 and includes, for example, cerium (Ce), praseodymium (Pr), neodymium (Nd) and gadolinium (G).
d), lanthanum (Ln), samarium (Sm) and the like. The lanthanide metal compound (A) suitable for the method of the present invention, that is, the lanthanide metal oxides and carbonates include neodymium oxide, praseodymium oxide, cerium oxide,
Examples thereof include lanthanum oxide, gadolinium oxide, neodymium carbonate, praseodymium carbonate, cerium carbonate, lanthanum carbonate and gadolinium carbonate. The lanthanide-based metal compound (A) used in the present invention may be composed of one of the above metal compounds or a mixture thereof, and a lanthanide oxide metal compound, particularly neodymium oxide is preferable. This is based on the fact that the lanthanide oxide-based metal compound is easily available, and the lanthanide-based metal carboxylate thus produced has a large activity when used as a catalyst for the polymerization of the diene-based monomer.

The carboxylic acid used in the present invention has 2 to 20 carbon atoms and is selected from the group consisting of an aliphatic carboxylic acid, a cycloaliphatic carboxylic acid and an aromatic carboxylic acid satisfying the following formula.

Formula R—COOH In the formula, R represents a hydrocarbon group such as an alkyl group having 1 to 19 carbon atoms, a cycloalkyl group, an aromatic hydrocarbon group or an alkylaryl group.

Examples of such carboxylic acid include acetic acid, propionic acid, n-butyric acid, isobutyric acid, valeric acid, pivalic acid, hexanecarboxylic acid, 2-hexanecarboxylic acid, cyclohexanecarboxylic acid, 3-cyclohexylpropionic acid, and 2
-Ethylhexanecarboxylic acid, 2-methyl-2-ethylpentanoic acid, 2,2-dimethylhexanoic acid, 2-methyl-2-ethylhexanoic acid, 2,2-diethylhexanoic acid, 2-ethyl-2-propylhexane Acid, 2-ethyl-2-butylhexanoic acid, 2,2-diethylheptanoic acid, 2,2-diethyloctanoic acid, 2-methyl-2-butyloctanoic acid, 1-heptanoic acid, 1-octanecarboxylic acid, 1-nonanecarboxylic acid, versatic acid (ie neodecanoic acid having the formula C ₉ H ₁₉ COOH), lauric acid,
Examples thereof include myristic acid, palmitic acid, stearic acid, oleic acid, benzoic acid, naphthenic acid, phenylacetic acid, triphenylacetic acid, disproportionated rosin acid and tricyclohexylacetic acid, and among them, versatic acid and naphthenic acid are preferable. The above carboxylic acids may be used alone or as a mixture of two or more.

The molar ratio of the carboxylic acid (B) having 2 to 20 carbon atoms and the lanthanide metal (RCOOH / Ln) is 2/1 to 100/1, preferably 2/1 to 20.
/ 1, more preferably 3/1 to 10/1.

In the present invention, the molar ratio of the water (C) to the lanthanide-based metal (H ₂ O / Ln) must be larger than 5/1. That is, in the present invention, excess water must be used with respect to the lanthanide-based metal.
If the molar ratio of H ₂ O / Ln is less than 5/1, the reaction is not complete and the yield is low. In addition, the oily phase and the aqueous phase are suspended in each other, and the oily phase is hard to separate from the aqueous phase, which takes time. In the present invention, if necessary, an acid such as hydrogen chloride may be added to water to facilitate the reaction.

Suitable inert solvents (D) for use in the process of the present invention are inert hydrocarbons having 4 to 20 carbon atoms, preferably aliphatic carbon atoms having 4 to 10 carbon atoms. It is selected from the group consisting of hydrogen, cycloaliphatic hydrocarbons and aromatic hydrocarbons. Examples thereof include butane, pentane, hexane, heptane, octane (all of which include isomers), cyclohexane, cyclodecane, and toluene, with n-hexane and cyclohexane being particularly preferable. The above-mentioned inert solvent is used alone or as a mixture of a plurality thereof. The preferred mixing ratio of the inert solvent (D) to the reaction system may be determined by an appropriate preliminary test, but is usually about 780 by weight with respect to the lanthanide metal (Ln) compound (A).
/ 1-1 / 1, preferably about 390 / 1-2.6 / 1.

In carrying out the method of the present invention, the lanthanide-based metal compound is added to the stirred reactor under the condition that the molar ratio of water (C) and lanthanide-based metal (H ₂ O / Ln) is larger than 5/1. (A), a C _{2 to} C ₂₀ carboxylic acid (B),
Water (C) and an inert solvent (D) are added, and the mixture is stirred and mixed at a temperature range of 0 to 300 ° C., preferably 25 to 160 ° C. for 0.1 to 8 hours to react. After completion of the reaction, the reaction product, that is, the formed metal carboxylate (L) is used to settle the two-phase mixed solution and separate it into an upper oily phase and a lower aqueous phase.
The mixed solution containing n (RCOO) ₃ ) is allowed to stand for a few minutes to 2 hours. The oily phase will then separate from the aqueous phase and the two-phase interface will be clearly visible. Then, the aqueous phase is removed, and the oily phase consisting of a solution of a lanthanide metal carboxylate (Ln (RCOO) ₃ ) in an inert solvent is distilled until its water content is 2000 ppm (relative to the oily phase) or less. The lanthanide-based metal carboxylate can be obtained as an inert solvent solution.

For use as a catalyst in the polymerization of a diene monomer, the water content of the lanthanide metal carboxylate solution obtained by the method of the present invention is 2000 pp as described above.
m or less, preferably 1500 ppm or less, more preferably 1000 pp
Distill to less than m. If the water content is more than 2000 ppm, the activity of the diene-based monomer as a catalyst during polymerization will decrease, and as a result, the conversion rate of the diene-based monomer will decrease.

Examples of the diene monomer to be polymerized using the lanthanide metal carboxylate obtained by the method of the present invention as a catalyst include, for example, butadiene, isoprene, 2-phenylbutadiene, and 2,3-dimethylbutadiene. , 1,3-hexadiene and 1,3-octadiene.

The lanthanide metal carboxylate (1) produced by the method of the present invention is combined with a halogenated alkylaluminum compound (2) and an organoaluminum compound (3) for diene monomer polymerization. It can be the catalyst system used.

Alkyl aluminum halide compounds (2) suitable for the catalyst system include those represented by the general formulas R ² AlX ₂ and R ² ₃
Selected from the group consisting of compounds represented by Al ₂ X ₃ or R ² ₂ AlX (wherein R ² is a hydrocarbon group having 1 to 12 carbon atoms, X is Cl, Br, F or I). be able to. A typical example of the hydrocarbon group represented by R ² is a linear or branched aliphatic hydrocarbon group. Examples of suitable alkylaluminum halide compound (2) include, but are not limited to, dioctylaluminum chloride, octylaluminum sesquichloride, octylaluminum dichloride, didecylaluminum chloride, decylaluminum sesquichloride, and dichloride. Decyl aluminum, didodecyl aluminum chloride, sesquichloride dodecyl aluminum chloride, dodecyl aluminum dichloride, dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum iodide, diethyl aluminum fluoride, di-n-propyl aluminum chloride, chloride Di-n-butyl aluminum, di-isobutyl aluminum chloride (DIBAC), methyl aluminum dichloride, ethyl aluminum dichloride, isobutyl aluminum dichloride Um, sesqui methyl aluminum chloride, sesqui-ethyl aluminum chloride, is like sesqui-isobutyl aluminum chloride and their homologues, and the compounds may be used alone or in mixtures thereof. Among the alkylaluminum halide compounds (2) used in the catalyst system, di-isobutylaluminum chloride (DIBAC) is most preferred. When the alkylaluminum halide compound (2) is used in the catalyst system, it is usually used as a solution of the alkylaluminum halide compound (2) by adding an appropriate solvent.

The organoaluminum compound (3) used in the catalyst system is the same as the compound represented by the formula AlR ³ R ⁴ R ⁵ (in the formula, R ³ , R ⁴ and R ⁵ are hydrogen at the same time). Are different, eg hydrogen, or C ₁ -C ₈ hydrocarbon groups)
Is. Examples will be given below, but the examples are not limited to those shown here. This compound is, for example, diethyl aluminum hydride, dipropyl aluminum hydride, diisopropyl aluminum hydride, dibutyl aluminum hydride, diisobutyl aluminum hydride (DIBAH),
Dipentyl aluminum hydride, dihexyl aluminum hydride, trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, triisopropyl aluminum, tri-n-butyl aluminum,
Examples thereof include triisobutylaluminum, trihexylaluminum, tricyclohexylaluminum and their homologs, and the above compounds may be used alone or in a mixture thereof. Preferred examples of the organoaluminum compound (3) used in the catalyst system are diethylaluminum hydride, diisopropylaluminum hydride and diisobutylaluminum hydride (DIBAH), and diisobutylaluminum hydride (DIBAH) is most preferred. In addition to the alkylaluminum halide compound (2) and the organoaluminum compound (3), aluminum halide such as aluminum chloride, aluminum bromide and the like can be added to the catalyst system.

In order to obtain a high conversion rate in the polymerization of the diene monomer, it is desirable to limit the mixing ratio of the catalyst system components (1), (2) and (3). That is, the molar ratio of the lanthanide metal carboxylate (1) to the sum of the alkylaluminum halide compound (2) and the organoaluminum compound (3) (1) / [(2) + (3)] is 1: 1.5. Up to 1: 100, preferably 1: 1.5 to 1: 6
The molar ratio [(1) / (2)] of the lanthanide metal carboxylate (1) and the alkylaluminum halide compound (2) is 1: 0.5 to 1:10, preferably 1: 1. To 1: 5, and the molar ratio [(1) / (3)] of the lanthanide metal carboxylate (1) and the organoaluminum compound (3) is from 1: 1 to 1:50, preferably 1 :. It ranges from 2 to 1:20.

In the present invention, an inert hydrocarbon can be used as a medium in the polymerization, if necessary. Examples thereof include aliphatic hydrocarbons, cycloaliphatic hydrocarbons, aromatic hydrocarbons and mixtures thereof. In particular, C _{4 to} C ₈ saturated aliphatic hydrocarbons, C _{5 to} C ₁₀
Are suitable cycloaliphatic saturated hydrocarbons, C _{6 to} C ₉ aromatic hydrocarbons, C _{4 to} C ₈ monoolefin hydrocarbons or mixtures thereof. Examples thereof will be given below, but the present invention is not limited to these examples. That is, examples of the hydrocarbon include butane, pentane, hexane, heptane, cyclopentane, cyclohexane, benzene, toluene, xylene, butene-1 and pentene-1.
However, it is preferred to use a polymerization medium that does not contain aromatic hydrocarbons for the polymerization. That is, in polymerization, C _{4 to} C ₈
Aliphatic hydrocarbons, cyclic aliphatic hydrocarbons C ₅ -C _10,
If the mono-olefinic hydrocarbons and hydrocarbon selected from the group consisting of mixtures thereof C ₄ -C ₈ a polymerization medium, because the activity of the catalyst system is improved. Above all,
It is desirable to use an inert hydrocarbon of either hexane or cyclohexane as the polymerization medium.

In producing the catalyst system, component (1),
(2) and (3) can be mixed in any order with stirring with a suitable solvent. The temperature for preparing the catalyst system can be selected within a range generally limited by the melting point and boiling point of the solvent used. -20 ℃ to 120 ℃
The temperature range of is appropriate. The catalyst system is prepared by adding the respective components separately, or by adding the organoaluminum compound (3) and the lanthanide metal carboxylate (1) to the polymerization reaction mixture and mixing them, followed by the alkylaluminum halide compound. It is also possible to add (2).
If necessary, add the organoaluminum compound (3) and lanthanide metal before adding it to the polymerization mixture of the diene monomer.
The carboxylic acid salt (1) may be premixed.

When preparing the catalyst system, an appropriate amount of the conjugated diene can be added so as to improve the activity of the catalyst system and shorten the induction time for initiating the polymerization. The conjugated diene may be added at any time in the order of addition. Quantitatively, the molar ratio of the lanthanide metal carboxylate to the conjugated diene is 1: 0 to 1: 1000, preferably 1: 0.5 to 1: 500, and more preferably 1: 2 to 1: 100. Examples of the conjugated diene include isoprene, butadiene, 1,3-pentadiene and the like.

The conjugated diene-based monomer is added before or after adding the catalyst component, or in the middle of adding one component of the catalyst and another component. The conjugated diene-based monomer can be added in a predetermined amount at once, or can be added gradually. The polymerization reaction is one with a stirrer,
Alternatively, a series of reactors is used. To remove residual catalyst activity, deactivators such as water and alcohol are added when the expected conversion is reached. Then, the polymerization mixture is distilled and dried to obtain a polybutadiene rubber.

By the polymerization reaction of butadiene using the lanthanide metal carboxylate (1) produced by the method of the present invention as a catalyst, a high content of 1,4-cis-polybutadiene rubber can be easily obtained. Generally, the content of 1,4-cis-polybutadiene rubber obtained will be greater than 95%.

[0029]

EXAMPLES Next, the present invention will be described based on Examples and Comparative Examples.
Further details will be described. Examples 1 to 7 show production examples of lanthanide-based metal carboxylates by the method of the present invention, and Examples 8 and 9 are diene-based mono-monomers using the lanthanide-based metal carboxylates produced by the method of the present invention. 1 shows an example of body polymerization.

Example 1 0.500 kg (1.46 mols) of neodymium oxide (Nd ₂ O ₃ , purity 99%) and versatic acid (acid value 32)
4, trade name versatic acid, Shell Chem
icals) 2.100 kg (12.16 mols) and well mixed with n-hexane 3.700 kg (42.67 mols) and water 2.
The mixture solution obtained by adding 100 kg (116.7 mols) was put into a reactor having a capacity of 20 liters and reacted at 95 ° C. for 2.5 hours. Then, in order to separate the upper oily phase and the lower aqueous phase, the reaction mixture solution was allowed to stand for 30 minutes. There were no neodymium oxide precipitates at the bottom of the reactor, and both the upper oily phase and the lower aqueous phase were clear and clear. Therefore, except for the lower aqueous phase, the remaining neodymium verteate [Nd (ver
The upper oily phase containing satate) ₃ ] and n-hexane was distilled with a distiller to obtain neodymium versatate [Nd (versata
te) ₃ ] was obtained as an n-hexane solution. The solution of neodymium versatate [Nd (versatate) ₃ ] thus obtained was 12
Containing 0 ppm of water, neodymium versatate [Nd (versa
The yield of tate) ₃ ] was 99.5%.

Example 2 The amount of water was 1.050 kg (58.3 mol)
s) and the reaction of Example 1 was repeated. After the reaction was completed, the reaction mixture solution was allowed to stand for 60 minutes to clarify the separation of the upper oily phase and the lower aqueous phase. There were no neodymium oxide precipitates at the bottom of the reactor. The solution of neodymium versatate [Nd (versatate) ₃ ] thus obtained contained 220 ppm of water after being distilled, and the yield of neodymium versatate [Nd (versatate) ₃ ] was 95%. .

[Example 3] The amount of water used was 3.47 kg (193 mol).
s) and the reaction of Example 1 was repeated. Therefore,
The molar ratio of water and lanthanide-based metal (H ₂ O / Ln) is 66 /
It becomes 1. After the reaction was completed, the reaction mixture solution was allowed to stand for 30 minutes to clarify the separation of the upper oily phase and the lower aqueous phase. No neodymium oxide precipitate remained at the bottom of the reactor. Thus obtained neodymium Bell satellites - DOO [Nd (versatate) _3] solution contains moisture 280ppm after being distilled, neodymium Bell satay - DOO [Nd (versatate) _3]
Yield was 99.5%.

Example 4 The reaction of Example 1 was repeated except that the amount of versatatic acid added was
It was reduced to 1.44 kg (8.76 mols). Similarly, after the reaction was completed, the reaction mixture solution was allowed to stand for 30 minutes in order to clarify and separate the upper oily phase and the lower aqueous phase. No precipitate of neodymium oxide remained at the bottom of the reaction tank. Neodymium versatate thus obtained [Nd (versatate) ₃ ]
After distilling, the solution contained 150 ppm of water, and the yield of neodymium versatate [Nd (versatate) ₃ ] was 98%.

Example 5 The reaction of Example 1 was repeated, except that the amount of versatatic acid added was
The amount was increased to 3.000 kg and the molar ratio of versatic acid to neodymium oxide was set to 6/1. Similarly, after the reaction was completed, the reaction mixture solution was allowed to stand for 30 minutes in order to clarify and separate the upper oily phase and the lower aqueous phase. No precipitate of neodymium oxide remained at the bottom of the reaction tank. The resulting solution of neodymium versatate [Nd (versatate) ₃ ] contained 450 ppm of water after being distilled,
The yield of (versatate) ₃ ] was 99.5%.

Example 6 The reaction of Example 1 was repeated, except that the same composition was added and a hydrogen chloride solution (35.5%) was added.
ml to the reaction tank and the reaction at a temperature of 80 ° C at 4.0
I made it happen on time. After the reaction was completed, the reaction mixture solution was mixed with 60% to clarify the separation of the upper oily phase and the lower aqueous phase.
Let stand for a minute. No precipitate of neodymium oxide remained at the bottom of the reaction tank. The obtained neodymium Bell satellites - DOO solution of [Nd (versatate) _3] contains 500ppm of moisture after the distillation, neodymium Bell satay - DOO [Nd (versatate) _3]
Yield was 99%.

Example 7 Neodymium oxide (Nd ₂ O ₃ ) 0.1
70 kg (0.5 mols) and acid value of 300 naphthenic acid
d) 0.760 kg (4.07 mols) and n-hexane 3.400 kg (43.7 m)
ols) and 1.410 kg (78.3 mols) of water were placed in a 20 liter reactor and reacted at 150 ° C. for 3 hours while stirring. Thereafter, the reaction mixture solution was allowed to stand for 1.5 hours in order to clarify and separate the upper oily phase and the lower aqueous phase. Then, except for the lower aqueous phase, neodymium naphthenate (Nd (Na
The upper oily phase containing ph) ₃ ) and n-hexane was distilled. The solution of Nd (Naph) ₃ thus obtained is 500
It contained ppm water and the yield of Nd (Naph) ₃ was 90%.

Comparative Example 1 The reaction of Example 1 was repeated, but the amount of water added was reduced to 0.017 kg (0.9 mol). Therefore, the molar ratio of water to lanthanide-based metal (H ₂ O / Ln) is
It becomes 0.31 / 1. After reacting for 2.5 hours, the reaction mixture solution was allowed to stand for 15 hours in order to clarify and separate the upper oily phase and the lower aqueous phase. However, even if the separation time was extended, both the oily phase and the aqueous phase were turbid, and a precipitate of Nd ₂ O ₃ was found at the bottom of the reaction tank, indicating that the reaction was not completed. Suspended Nd _{2 in} oily phase
In order to remove precipitates such as O ₃ , the oily phase had to be isolated in the suspension by processing in a high speed centrifuge. Then, the oily phase is distilled to remove water, and N
d (versatate) ₃ was obtained. Thus obtained Nd (versata
The solution of te) ₃ contained 280 ppm of water, and the yield of Nd (Naph) ₃ was 78%.

[Comparative Example 2] The amount of water is 0.0072 kg (0.4 mol).
The reaction was carried out under the same conditions as in Example 4, except that the amount was reduced to 10. Therefore, the molar ratio of water to the lanthanide-based metal (H ₂
O / Ln) is 0.14 / 1. Even when the separation time was extended to 12 hours, both the upper oily phase and the lower aqueous phase became cloudy, and Nd ₂ O ₃ precipitates were also found at the bottom of the reaction tank. The oily phase had to be processed in a high speed centrifuge to remove the Nd ₂ O ₃ suspended in the oily phase. Then, an Nd (versatate) ₃ solution having a water content of 10200 ppm when not distilled was produced, and the yield of Nd (Naph) ₃ was 45%. The thus obtained solution of Nd (versatate) ₃ was used as a catalyst for the polymerization of the butadiene monomer by the method described in Example 8, and it was impossible to polymerize because the catalyst contained too much water. It has been found.

[Embodiment 8] N produced according to Embodiment 1
A solution of d (versatate) ₃ in n-hexane [Nd (versatate) ₃
Containing 0.256 mol] 14.900 kg and di-isobutylaluminum hydride (DIBAH) in n-hexane 6
A catalyst system solution was prepared by mixing 6.270 kg (containing 83.6 mols of DIBAH) and 20.54 kg of a solution of di-isobutylaluminum chloride (DIBAC) in n-hexane (containing 20.9 mols of DIBAC) with stirring. . 10.73 kg (198 mols) of 1,3-butadiene monomer purified to a water content of 2 ppm or less by distillation was equipped with a stirrer and a cooling system.
Place in a 200 L reactor. Next, n-hexane 82.23 kg (9
54 mols) and 0.678 kg of the above catalyst system solution are charged to the reactor. In addition, n used in the production and polymerization process of the above catalyst system
-Hexane has been previously distilled to a water content of less than 2 ppm. The reaction was carried out at a temperature of 90 ° C. with stirring for 100 minutes. After the reaction was complete, the solution was evaporated to dryness.
The rubber product thus obtained was 98% polybutadiene with a cis-1,4 configuration. The conversion rate of butadiene monomer is 95%, and the Mooney viscosity (Mooney
viscosity) was 40.

[Embodiment 9] N produced according to Embodiment 4
40.27 kg of d (versatate) ₃ solution [containing 0.7 mol of Nd (versatate) ₃ ], 55.27 kg of di-isobutylaluminum hydride (DIBAH) solution (containing 70 mols of DIBAH) and di-isobutylaluminum chloride (DIBA)
C. 20.54 kg of n-hexane (containing 20.9 mols of DIBAC) was mixed and stirred to prepare a catalyst system solution. Then, 10.73 kg (198 mols) of 1,3-butadiene monomer was put into a 200 L reactor equipped with a stirrer and a cooling system, and then 82.23 kg (954 mols) of n-hexane and 0.71 of a catalyst system solution.
and kg were placed in the reactor. The butadiene monomer and n-hexane used in the production and polymerization of the above catalyst system are
The water content was previously distilled to a content of 2 ppm or less.
The reaction was carried out at a temperature of 95 ° C. with stirring for 110 minutes, after the reaction was complete, the solution was evaporated to dryness. The rubber product thus obtained was 98% polybutadiene with a cis-1,4 configuration. The conversion of butadiene monomer is 94%, and the Mooney viscosity of polybutadiene is 42.
Met.

Reaction components of Examples 1-7 and Comparative Examples 1 and 2,
Table 1 shows the respective amounts, reaction conditions and product properties.

According to the method of the present invention as disclosed in the above Examples and Comparative Examples, an excess amount of water is added to the lanthanide metal (Ln), that is, the molar ratio of water (C) to the lanthanide metal (Ln) is set. It has been found that when added to lanthanide metal oxides greater than 5/1, the reaction is sufficiently complete and the reaction mixture can separate into a clear oily phase and an aqueous phase in a short period of time. Therefore, further centrifugation of the oily phase can be omitted.

According to the method of the present invention, a lanthanide metal carboxylate can be produced with a high yield by a relatively simple procedure, and the lanthanide metal carboxylate produced by the present invention can be used as a catalyst. When used for the polymerization of a diene-based monomer, the polymerization rate is significantly improved.

It should be noted that, as is apparent from the above description, many modifications and changes can be made without departing from the scope and spirit of the present invention.

[0045]

[Table 1]

[Procedure amendment]

[Submission date] September 1, 1999 (1999.9.1)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Correction content]

[Claims]

4. The manufacturing method according to claim 1, wherein the lanthanide-based metal (Ln) is neodymium (Nd).

The molar ratio of 5. The carboxylic acid (B) and lanthanide series metal (Ln) is 2: 1 to 100: The process according to any one of 1 and is according to claim 1-4.

6. the molar ratio of the carboxylic acid (B) and the lanthanide series metals (Ln) is 3: 1 to 10: 5. 1
The manufacturing method described in.

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Claims (8)

[Claims] 1. A lanthanide metal (Ln) compound selected from lanthanide metal oxides or carbonates, (B) a carboxylic acid having 2 to 20 carbon atoms, and (C) water. , (D) an inert solvent are mixed in a molar ratio such that the ratio of water (C) to the lanthanide metal (Ln) is larger than 5: 1, and the mixture is reacted in a temperature range of 0 to 300 ° C. A lanthanide represented by the formula Ln (RCOO) ₃ (wherein Ln represents a lanthanide-based metal element having an atomic number of 57 to 71, and R represents a hydrocarbon group having 1 to 19 carbon atoms). Method for producing base metal carboxylate. 2. The production method according to claim 1, wherein the molar ratio of water (C) to lanthanide-based metal (Ln) is 5: 1 to 200: 1. 3. The production method according to claim 2, wherein the molar ratio of water (C) to lanthanide-based metal (Ln) is 15: 1 to 80: 1. 4. After the reaction is complete, the oily phase is separated from the aqueous phase of the reaction product, and the water content of this oily phase is 2000.
The method according to any one of claims 1 to 3, wherein the oily phase is distilled to a ppm (based on the oil phase) or less to obtain a solution of a lanthanide metal carboxylate in an inert solvent. 5. The manufacturing method according to claim 1, wherein the lanthanide-based metal (Ln) is neodymium (Nd). 6. The production method according to claim 1, wherein the carboxylic acid (B) is naphthenic acid or versatic acid. 7. The production method according to claim 1, wherein the molar ratio of the carboxylic acid (B) and the lanthanide metal (Ln) is 2: 1 to 100: 1. 8. The molar ratio of the carboxylic acid (B) and the lanthanide metal (Ln) is 3: 1 to 10: 1.
The manufacturing method described in.