JPH0359083B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a method for efficiently producing a conjugated diene polymer having a high trans bond content, high molecular weight, and narrow molecular weight distribution using a novel composite catalyst. [Prior Art] Techniques conventionally known as methods for producing conjugated diene polymers having a high trans bond content can be broadly classified into the following three types.
That is, (1) a so-called Ziegler catalyst system containing a transition metal compound as a main component, (2) an anionic polymerization catalyst system containing an alkaline earth metal as a main component, and (3) a system containing a rare earth metal as a main component. be. The first system containing transition metals such as nickel, cobalt, titanium, and vanadium as main components is known to undergo highly stereoregular polymerization. For example, as a method for polymerizing butadiene using titanium metal, Method using a carrier of tetravalent titanium metal compound and magnesium halide
67387). Furthermore, when the main component is a vanadium compound, a polymer having an extremely high trans bond content can be obtained. For example, a method of polymerizing isoprene using a composite catalyst of tetravalent vanadium halide and organoaluminum (Japanese Patent Application Laid-Open No. 1989-1998)
-36585), and a method for polymerizing isoprene using a composite catalyst consisting of a trivalent or tetravalent vanadium compound, an organoaluminium, and a tetravalent titanium compound (Japanese Patent Application Laid-open No. 49-29386, 50−
122586) etc. are known. However, these catalysts are generally insoluble in hydrocarbon solvents, and copolymerization of conjugated dienes and aromatic vinyl hydrocarbon compounds is also difficult. Furthermore, at an advanced stage of polymerization,
It has the disadvantage that it tends to become a highly branched polymer, and the resulting polymer has a significantly broad molecular weight distribution. When such a polymer is used as a rubber, it has a major drawback in that the strength and abrasion resistance of the vulcanizate are inferior. On the other hand, as for those belonging to the above type (2),
There are examples in which organometallic compounds of metal _A are used as polymerization catalysts, but in general, compounds other than beryllium and magnesium are used as polymerization catalysts.
Organometallic compounds of metal _A are difficult to synthesize, and the polymerization activity of their conjugated dienes is extremely low. In the case of the above two types of organometallic compounds, although the synthesis is relatively easy, their polymerization reactivity with conjugated dienes is not active except under certain special reaction conditions, and there are no examples of them being put to practical use. On the contrary,
A method using a composite catalyst combining an organic compound of metal _A with another organometallic compound includes barium di-tert-butoxide and organic lithium (Japanese Patent Application Laid-open No. 47-3728), or barium di-tert-butoxide and organic lithium tert−
Butoxide and organic magnesium
48910), etc., and there is also a method of polymerizing conjugated dienes using an organic compound of barium or strontium, an organolithium, and an organometallic compound of metal _B or _A (Japanese Patent Application Laid-open No. 48910). (Sho 52-30543) etc. are also known. In a system using a composite catalyst containing these _A metal compounds, a conjugated diene polymer having a somewhat high trans bond content is obtained, and the molecular weight distribution is also relatively narrow. Copolymerization with aromatic vinyl hydrocarbons is also possible. However, in order to obtain polymers with even higher trans linkage contents of diene moieties, for example as much as 90%, it is generally necessary to use lower polymerization temperatures, in which case the polymerization activity is significantly lower. As a result, it was not satisfactory for industrial use. Furthermore, as belonging to the third type, a composite catalyst using a rare earth metal compound as a main catalyst and an organomagnesium compound as a co-catalyst is also known.
For example, JP-A-59-1508 proposes a method using a versatile salt of Di, Nd, Pr, etc., or a special α, γ-diketone complex. However, this composite catalyst also has extremely low polymerization activity;
In addition, it has the disadvantage that the resulting polymer has a low molecular weight and a wide molecular weight distribution. As mentioned above, various catalyst systems have been known so far, but at an industrially usable level, conjugated diene polymers with high trans content, high molecular weight, and narrow molecular weight distribution, especially polybutadiene. No catalyst was known that could provide extremely high activity. [Problems to be Solved by the Invention] The present invention improves the drawbacks of the known catalysts (1) to (3) above, and provides a conjugated catalyst with extremely high activity, high trans content, high molecular weight, and narrow molecular weight distribution. This invention was made in order to provide a catalyst and a polymerization method that make it possible to obtain a diene polymer. [Means and effects for solving the problems] The present invention provides a method for producing a conjugated diene polymer, characterized by using a composite catalyst consisting of (a) an organic acid salt of lanthanum and (b) an organomagnesium compound. provide. Lanthanum, which is the main component of the composite catalyst of the present invention, is
It is an abundant metal among the lanthanide transition metals, and can be obtained industrially easily and at low cost. However, its performance as a conjugated diene polymerization catalyst was known to be capable of producing polymers with a high cis content, but its activity was extremely low [for example, J. Polym. Sci., Polym. Chem. .
Ed., 18, 3345 (1980)], and it was not known to obtain a butadiene polymer with a high trans content. However, we have conducted intensive research on composite catalysts containing lanthanum, and surprisingly, when conjugated dienes are polymerized using the composite catalyst of the present invention, conjugated diene polymers with a high trans content can be polymerized with extremely high activity. The present inventors have discovered that the resulting polymer has a high molecular weight and a narrow molecular weight distribution, and that the polymer thus obtained exhibits excellent physical properties, leading to the present invention. The organic acid salt of lanthanum, which is component (a) of the composite catalyst of the present invention, can be obtained by, for example, reacting the alkali metal salt of the organic acid shown below with chloride of lanthanum in water or an organic solvent such as alcohol or ketone. Therefore, it can be easily obtained. The lanthanum element used does not need to be particularly pure, and may contain a small amount of other rare earth metal elements or metal elements other than rare earth metals. Further, the organic acid salt of lanthanum may contain a small amount of lanthanum or an organic acid as an impurity. Further, the organic acid compounds used are represented by the following general formulas () to (). ^R1 −LH……() (Here, R ¹ , R ² and R ⁵ to R ⁸ represent an aliphatic hydrocarbon group or an aromatic hydrocarbon group, R ³ represents an aromatic hydrocarbon group, and R ⁴ represents an aliphatic hydrocarbon group. , R ⁹ to ^{R 12} represent an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an alkoxy group or a phenoxy group. L represents an oxygen atom or a sulfur atom. Furthermore, j, k, l and m are 1 or more and 6 represents the following integer.) The above general formula () represents alcohol, thioalcohol, phenol or thiophenol. Examples of these are methyl alcohol, ethyl alcohol, n-propyl alcohol, iso-
propyl alcohol, tert-butyl alcohol,
tert-amyl alcohol, n-hexyl alcohol, cyclohexyl alcohol, allyl alcohol, 2-butenyl alcohol, 3-hexenyl alcohol, 2,5-decadienyl alcohol, benzyl alcohol, phenol, catechol, 1
-naphthol, 2-naphthol, 2,6-di-
tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, 4-phenylphenol, ethanethiol, 1-butanethiol, 2
-pentanethiol, 2-iso-butanethiol,
Examples include thiophenol, 2-naphthalenethiol, cyclohexanethiol, 3-methylcyclohexanethiol, 2-naphthalenethiol, benzenemethanethiol, 2-naphthalenemethanethiol, and the like. The general formula () represents a carboxylic acid or a sulfur congener. Examples of these are isovaleric acid, caprylic acid, octanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid,
linoleic acid, cyclopentanecarboxylic acid, naphthenic acid, ethylhexanoic acid, pivalic acid, versatic acid (a synthetic acid composed of a mixture of isomers of C10 monocarboxylic acids sold by Siel Chemical),
Examples include phenylacetic acid, benzoic acid, 2-naphthoic acid, hexanethiolic acid, 2,2-dimethylbutanethionic acid, decanethionic acid, tetradecanethionic acid, and thiobenzoic acid. General formula () represents alkylarylsulfonic acid. Examples include dodecylbenzenesulfonic acid, tetradecylbenzenesulfonic acid, hexadecylbenzenesulfonic acid, octadecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, n
-hexylnaphthalene sulfonic acid, dibutylphenyl sulfonic acid, etc. General formula () represents a monoalcohol ester of sulfuric acid. Examples of these include sulfuric monoester of lauryl alcohol, sulfuric monoester of oleyl alcohol, sulfuric monoester of stearyl alcohol, and the like. The general formula () represents a phosphoric diester of an ethylene oxide adduct of alcohol or phenol. Examples of these are phosphoric diesters of ethylene oxide adducts of dodecyl alcohol, phosphoric diesters of ethylene oxide adducts of octyl alcohol, phosphoric diesters of ethylene oxide adducts of stearyl alcohol, and phosphoric diesters of ethylene oxide adducts of oleyl alcohol. Examples include acid diesters, phosphoric esters of ethylene oxide adducts of nonylphenol, and phosphoric esters of ethylene oxide adducts of dodecylphenol. The general formula () represents a phosphorous diester of an ethylene oxide adduct of alcohol or phenol. Examples of these are the phosphite diester of the ethylene oxide adduct of dodecyl alcohol, the phosphite diester of the ethylene oxide adduct of stearyl alcohol, the phosphite diester of the ethylene oxide adduct of stearyl alcohol, and the ethylene oxide of nonylphenol. Examples include phosphorous acid diester of an adduct, phosphorous acid diester of an ethylene oxide adduct of dodecylphenol, and the like. General formula () represents a pentavalent organic phosphoric acid compound. Examples of this include dibutyl phosphate, dipentyl phosphate, dihexyl phosphate, diheptyl phosphate,
Dioctyl phosphate, bis(1-methylheptyl) phosphate, bis(2-ethylhexyl) phosphate, dilauryl phosphate, dioleyl phosphate, diphenyl phosphate, bis(p-nonylphenyl) phosphate, butyl phosphate ( 2-ethylhexyl), phosphoric acid (1
-methylheptyl) (2-ethylhexyl), (2-ethylhexyl) phosphoric acid (p-nonylphenyl),
Monobutyl 2-ethylhexylphosphonate, 2-
Mono-2-ethylhexyl ethylhexylphosphonate, mono-2-ethylhexyl phenylphosphonate, mono-p-2-ethylhexylphosphonate
Nonylphenyl, dibutylphosphinic acid, bis(2-ethylhexyl)phosphinic acid, bis(1
-Methylheptyl)phosphinic acid, dilaurylphosphinic acid, dioleylphosphinic acid, diphenylphosphinic acid, bis(p-nonylphenyl)phosphinic acid, butyl (2-ethylhexyl)phosphinic acid, (2-ethylhexyl) (1 -methylheptyl)phosphinic acid, (2-ethylhexyl)
Examples include (p-nonylphenyl)phosphinic acid. General formula () represents a trivalent phosphoric acid compound.
Examples include bis(2-ethylhexyl) phosphate, bis(1-methylheptyl) phosphate, mono-2-ethylhexyl 2-ethylhexylphosphonate, and bis(2-ethylhexyl)phosphinic acid. Another catalyst component (b), an organomagnesium compound forming the present invention, is represented by the following general formula (). Mg・R ¹³・R ¹⁴ ...() (Here, R ¹³ and R ¹⁴ represent an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and even if they are the same group, they may be different groups. ) Furthermore, the organomagnesium may contain a small amount of organoaluminum or organozinc in order to improve its solubility in hydrocarbon solvents. Such examples include diethylmagnesium,
Di-n-propylmagnesium, di-isopropylmagnesium, di-n-butylmagnesium,
n-butyl-sec-butylmagnesium, di-sec
-butylmagnesium, di-tert-butylmagnesium, di-n-hexylmagnesium, di-n
-Propylmagnesium, diphenylmagnesium, MAGALA-6E, 7.5E (Texas Alkyl Corporation), etc. are preferred, and more preferred are di-isopropylmagnesium, di-n-butylmagnesium, di-sec-butylmagnesium, MAGALA-6E, 7.5E (Texas Alkyl Corporation), etc. Examples include -6E, -7, 5E, etc. The composite catalyst of the present invention has extremely high activity, and the amount of catalyst used is 100 g of the conjugated diene monomer to be polymerized.
Component (a) is preferably used in an amount of 0.01 to 1 mmol, more preferably 0.05 to 0.6 mmol.
Component (b) is preferably also a conjugated diene monomer
Expressed in concentration per 100g, 0.02 to 10 mmol,
More preferably, it is 0.1 to 6 mmol. in general,
If the amount of organomagnesium used is too small for a certain amount of lanthanum metal, not only will the polymerization activity decrease, but the trans bond content in the resulting conjugated diene polymer will also be low, and its molecular weight distribution will be affected. It will also be wider. On the other hand, when the amount of organomagnesium used is too large, the molecular weight distribution of the resulting conjugated diene polymer becomes narrow, while both the polymerization activity and the trans bond content decrease. Moreover, using an unnecessarily large amount of catalyst not only increases the amount of catalyst residue remaining in the conjugated diene polymer, but also is not preferable from an economic standpoint.
That is, the preferred amount of the composite catalyst used in the present invention is expressed as the ratio of the catalyst components (a) and (b), and is expressed as (a)/(b).
is in the range of 1/0.1 to 1/50, more preferably 1/0.5 to 1/10. The composite catalyst of the present invention further comprises one or more components of (c) an organic compound of lithium, (d) an organoaluminum compound, and (e) an electron-donating compound, preferably in a molar ratio of an organomagnesium compound. By allowing 1/10 or more of the coexistence, the polymerization activity can be further increased. The organic compounds of lithium used are represented by the following general formulas () to (). R ¹⁵ (Li) _w … () R ¹⁶ (OLi) _w … () R ¹⁷ (OCH ₂ CH ₂ ) _y OLi … () (where R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹
represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and w, x, y and z represent an integer of 1 or more and 6 or less. ) Examples of the general formula () are methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, isoamyllithium, sec-amyllithium-n-hexyllithium. , n-octyllithium, allyllithium, benzyllithium, phenyllithium, 1,
1-diphenyllithium, tetramethylene dilithium, pentamethylene dilithium, 1,2-dilithio-1,1,2,2-tetraphenylethane,
Examples include 1,3-bis(1-lithio-1,3-dimethylpentyl)benzene. Preferably n-butyllithium, sec-butyllithium,
Examples include organic lithium compounds such as tert-butyllithium and 1,3-bis(1-lithio-1,3-dimethylpentyl)benzene. Examples of the general formula () are ethyl alcohol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, 2-butyl alcohol, tert-butyl alcohol, n-amyl alcohol, and n-hexyl alcohol. , n-heptyl alcohol, n-
Octyl alcohol, cyclohexyl alcohol, allyl alcohol, cyclopentyl alcohol, benzyl alcohol, phenol, 1-naphthol, 2,6-di-tert-butylphenol,
Examples include lithium salts of alcohols and phenols such as 2,4,6-tri-tert-butylphenol, nonylphenol, and 4-phenylphenol. Examples of general formula () include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,
Examples include lithium salts such as diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, and diethylene glycol monophenyl ether. Examples of general formula () include dimethylaminoethanol, diethylaminoethanol, di-n
-Lithium salts such as propylaminoethanol are mentioned. Examples of general formula () are dimethylamine,
diethylamine, di-n-propylamine, di-
iso-propylamine, di-n-butylamine,
Examples include lithium salts of secondary amines such as di-n-hexylamine. Examples of general formula () are ethyleneimine,
triethyleneimine, pyrrolidine, piperidine,
Examples include lithium salts of cyclic imines such as hexamethyleneimine. Particularly preferred organic compounds of lithium are n-butyllithium, sec-butyllithium and iso-amyllithium. Depending on the amount of the lithium organic compound coexisting in the composite catalyst of the present invention, it is possible to change the trans bond content in the resulting conjugated diene polymer. Generally, as the amount of the organic lithium compound used increases, the polymerization activity increases, while the trans bond content in the resulting conjugated diene polymer decreases. However, when used in appropriate amounts, it is possible to obtain polymers with high trans bond content and even higher activity. Therefore, the amount of lithium organic compound to be used varies depending on the trans bond content in the target polymer, but generally when trying to obtain a trans bond content of 80% or more. is expressed as the ratio of lithium atoms in an organic compound of lithium to magnesium atoms in an organomagnesium compound,
It is desirable that the Li/Mg molar ratio is 1.5 or less. In particular, when trying to obtain a resin-like polymer with a trans bond content of 85% or more,
Similarly, it is desirable that the Li/Mg molar ratio is 0.7 or less. In addition, in order to increase the polymerization activity of the composite catalyst,
The organoaluminum compound (d), which is the second component that can coexist, can be represented by the following general formula (). AlR ²² R ²³ R ²⁴ ...() (Here, R ²² and R ²³ represent hydrogen or an aliphatic hydrocarbon group, and R ²⁴ represents an aliphatic hydrocarbon group.) Such examples include trimethyl Examples include aluminum, triethylaluminum, triisopropylaluminium, triisobutylaluminum, trihexylaluminum, tricyclohexylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, ethylaluminum dihydride, isobutylaluminum dihydride, and the like. Particularly preferred are triethylaluminum, triisobutylaluminum, diethylaluminum hydride, and diisobutylaluminum hydride. When an organoaluminum compound is used, especially if it is used in too large an amount, both the polymerization activity and the trans bond content are reduced. Therefore, the amount of the organoaluminum compound used should be kept at an appropriate level, in which case both the polymerization activity and the trans bond content can be increased. Generally, the amount of organoaluminum compound used, expressed as Al/Mg molar ratio, is
It is preferably 10 or less, more preferably 1 or less. Furthermore, as a third component capable of increasing the polymerization activity of the composite catalyst, (e) an electron-donating compound that can be made to coexist is a compound known as a so-called Lewis base, and in the present invention, , ethers, thioethers, and amines. Specifically, ethers such as dimethyl ether, diethyl ether, diphenyl ether, tetrahydrofuran, anisole, diglyme, dimethylamine, diethylamine, trimethylamine, triethylamine, di-n-butylamine,
Amines such as aniline, diphenylamine, N-ethylaniline, N,N,N',N'-tetramethylethylenediamine, dipiperidinoethane, as well as thiophene, tetrahydrothiophene, 2,
Examples include thioethers such as 5-dihydrothiophene. Preferably diethyl ether, tetrahydrofuran, triethylamine,
N,N,N',N'-tetramethylethylenediamine. The amount of the electron-donating compound used varies depending on the strength of the compound as a Lewis base, but generally speaking, a smaller amount of a strongly basic compound is required than a weakly basic compound. When the above-mentioned electron-donating compounds are used in large amounts,
On the contrary, it not only lowers the polymerization activity of the composite catalyst but also lowers the trans bond content in the polymer. The preferred amount used is 50 or less, more preferably 5 or less, expressed as the number of moles per mole of the organomagnesium compound. The above-mentioned (c) organolithium compounds, (d) organoaluminium compounds, and (d) electron-donating compounds may be used alone, or two or more of these compounds may be used simultaneously. I do not care.
When any of these compounds is used, by using an appropriate amount, a conjugated diene polymer having a high trans bond content can be obtained at a higher conversion rate. The composite catalyst of the present invention can further increase its polymerization activity by pre-reacting in the presence or absence of a conjugated diene monomer prior to polymerization, and the resulting conjugated diene polymer It is possible to narrow the molecular weight distribution of At that time, (c) an organic compound of lithium, (b) an organoaluminum compound,
(e) An electron donating compound may coexist in the preliminary reaction system. This preliminary reaction is preferably carried out at a reaction temperature of 0 to 100°C. At temperatures below this, the pre-reaction is insufficient, while at temperatures above 100℃,
This is not preferable because the molecular weight distribution expands. Particularly preferred temperatures are 20°C to 80°C. Also, the reaction time is
The time period is preferably 0.01 to 24 hours. If the reaction time is shorter than this, the preliminary reaction is insufficient, and a longer reaction time is unnecessary. Particularly preferred conditions are 0.05 to 5 hours. It is also possible to make a conjugated diene monomer exist when performing this preliminary reaction, in which case the resulting conjugated diene polymer will have an even narrower molecular weight distribution. The preferred amount of conjugated diene monomer to be used, expressed as a molar ratio to lanthanum metal atoms, is from 1 to 1000.
Whether it is below or above this level, the effect due to the presence of the conjugated diene monomer is small. Moreover, if the conjugated diene monomer is present in a molar ratio higher than that shown above, it becomes difficult to control the temperature in the preliminary reaction because rapid polymerization of the conjugated diene monomer occurs. A particularly preferred molar ratio is 5-200. The monomers used in the present invention are selected from the group consisting of conjugated diene monomers, mixtures of conjugated diene monomers and other conjugated dienes, or mixtures of conjugated dienes and aromatic vinyl hydrocarbons. Examples of preferably used conjugated diene include 1,3-butadiene, isoprene, 2,
Examples include 3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene, 2-phenyl-1,3-butadiene, and the like. Preferred examples of aromatic vinyl hydrocarbons include styrene, α-methylstyrene, vinyltoluene, methoxystyrene, divinylbenzene, and 1-vinylnaphthalene. The most preferred practical polymerization form of the present invention is butadiene homopolymerization, isoprene homopolymerization, butadiene-isoprene copolymerization, or butadiene-styrene copolymerization. The assembly in the present invention can be carried out without a solvent or in the presence of a solvent. In the latter case, the solvent used is preferably an aliphatic or alicyclic hydrocarbon such as n-pentane, n-hexane, n-heptane, or cyclohexane, or an aromatic hydrocarbon such as benzene or toluene. These may be a mixture of two or more types, or may contain a small amount of impurities. Further, the polymerization temperature is -30°C to 150°C, preferably 10 to 120°C. Furthermore, the polymerization reaction format may be either a batch method or a continuous method. After the polymerization reaction reaches a predetermined polymerization rate, a known polymerization terminator is added to the reaction system to terminate the reaction, and the usual steps of solvent removal and drying in the production of conjugated diene polymers can be carried out. That is, the present invention provides a method for obtaining extremely highly active conjugated diene polymers having a high trans content, a high molecular weight, and a narrow molecular weight distribution using the above-mentioned novel composite catalyst. Furthermore, the trans content and molecular weight of the conjugated diene polymer obtained as necessary in the method of the present invention are low,
Needless to say, it is easily possible to widen the molecular weight distribution. For example, in the case of butadiene polymers, the trans content can be freely controlled within the range of 98% to 60% by adjusting the catalyst composition or polymerization temperature, etc. Even rubber-like polymers can be produced. The molecular weight of the polymer can be controlled in the range of several thousand to several hundred thousand by adjusting the composition or concentration of the catalyst used. Furthermore, the molecular weight distribution of the polymer can be controlled within the w/n range of 1.1 to 3.0 by adjusting the composition of the catalyst used. In addition, known coupling reaction techniques may be used, such as coupling agents that utilize the reactive ends of living polymers such as ester compounds, halogenated hydrocarbon compounds, halogenated silicon compounds, and halogenated tin compounds, or polyfunctional monomers such as divinylbenzene during polymerization. Alternatively, if necessary, it is also possible to impart a branched structure to the polymer chain or expand the molecular weight distribution by adding it to the polymerization system after completion of the polymerization. The applications of the polymers obtained by the process of the invention are wide-ranging depending on their polymer structure and properties. For example, if the polymer has a high molecular weight and is amorphous, it can be used as a rubber-like polymer for tire treads, carcass, sidewalls, etc., and exhibits excellent properties such as abrasion resistance and heat generation properties. If the polymer has a high molecular weight and is crystalline, it can be used as a resin material for golf ball skins, hygiene materials, etc. If the polymer has a relatively low molecular weight and is crystalline, it can be used to improve the processability of NBR, chloroprene rubber, etc. agent,
Can be used as a hot melt adhesive. [Examples] Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples. Example 1 A sufficiently dried 700 ml pressure-resistant glass bottle was capped, and the inside was purged with dry nitrogen for 3 hours. 60
After sealing a 300 gn-hexane mixture containing 1,3-butadiene in a bottle, a rare earth metal organophosphate compound, Ln (P ₁ ) ₃ [Ln indicates a lanthanide metal, and P ₁ shows. ] 0.08 mmol and di-n-butylmagnesium, 0.32 mmol were added, and polymerization was carried out at 75° C. for 1.5 hours. After polymerization, methanol was added to stop the reaction, and the polymer was precipitated and separated with a large amount of methanol, followed by vacuum drying at 50°C. Table 1 shows the conversion rate and microstructure of the polymer thus obtained.

【table】

[Table] It can be seen from Table 1 that among the rare earth metals, lanthanum metal is the most superior in terms of high polymerization activity, high weight average molecular weight of the resulting polymer, and narrow molecular weight distribution. Examples 2 to 23 In the same manner as in Example 1, 0.08 mmol of the lanthanum metal salt of an organic acid shown in Table 2 was added to a mixed solution of 300 g of n-hexane containing 60 g of 1,3-butadiene. 0.32 mmol of the organic metal shown in 1 was added and polymerization was carried out at 75°C for 2 hours. The polymerization results are shown in Table 2.

【table】

【table】

Table 2 shows that lanthanum salts of various organic acids are effective as component (a) of the composite catalyst of the present invention. Furthermore, it is clear that the effect of the present invention is exhibited only when an organomagnesium compound is used as the organometallic compound as component (b). Examples 24-31 In a similar manner to Example 1, 300 g containing 60 g of 1,3-butadiene in a 700 ml pressure-resistant glass bottle
An organic phosphate of lanthanum metal [La(P ₁ ) ₃ ] (however, P ₁
is the same as described in Example 1. ) and di-n-butylmagnesium were added in a predetermined amount.75
Polymerization was carried out for 90 minutes at °C. The polymerization results are shown in Table 3.

【table】 ‖
* P ₁ :(C ₄ H ₉ CHCH ₂ O) ₂ P−O−
｜
C ₂ H ₅
Table 3 shows that the ratio of magnesium atoms to lanthanum metal atoms exhibits extremely high polymerization activity over a wide range of composition ratios. Moreover, it can be seen that under conditions where this composition ratio is preferable, the composite catalyst of the present invention exhibits extremely excellent activity, and the resulting polymer has a large weight average molecular weight and a narrow molecular weight distribution. Examples 32 to 52 Performed in the same manner as in Example 1, 0.2 organophosphate of lanthanum metal per 100 g of 1,3-butadiene.
mmol and 0.6 mmol of di-n-butylmagnesium were added as catalysts, and an organic compound of lithium, an organoaluminum compound and/or an electron-donating compound were added under the conditions shown in Table 4. Polymerization was carried out at 75°C for 90 minutes. The polymerization results are shown in Table 4.

[Table] ｜
C ₂ H ₅

[Table] From Table 4, the polymerization activity of the catalyst can be increased and the trans content of the resulting polymer can be increased by adding appropriate amounts of lithium organic compounds, organoaluminum compounds, and/or electron-donating compounds. It can be seen that the weight average molecular weight and molecular weight distribution can be controlled. Examples 53 to 64 100ml pressure-resistant bottles were sufficiently purged with dry nitrogen and then capped. Examples 53 to 57 were lanthanum metal organic phosphates [La (P ₁ ) ₃ or La (P ₂ ) ₃ : However, P ₁ and P ₂ are the same as those listed in Table 4. ]0.2 mmol, di-n-butylmagnesium
A preliminary reaction of the catalyst was carried out by adding 0.6 mmol and 10 ml of n-hexane under the conditions shown in Table 5. In Examples 58 to 61 and 63, 1.
In the coexistence of 2.3 g of a 20% n-hexane mixture of 3-butadiene, and in Example 62, 0.072 mmol of n-butyllithium and 0.216 mmol of tetrahydrofuran.
Preliminary reaction was carried out under the conditions shown in Table 5 with 1 mmol of the reaction mixture present. The composite catalyst pre-reacted in this way was mixed with 20% n-1,3-butadiene in a 700ml pressure-resistant glass bottle, which was subjected to the same operation as in Example 1.
It was added to 300 g of a hexane mixture and polymerized at 65°C for 3 hours. Example 64 is an organic phosphate of lanthanum
Polymerization was carried out in the same manner without pre-reaction using 0.2 mmol of di-n-butylmagnesium and 0.6 mmol of di-n-butylmagnesium as a composite catalyst. The above preliminary reaction conditions and polymerization results are summarized in Table 5.

【table】

〔Effect of the invention〕

According to the present invention, a conjugated diene polymer having a high trans bond content, high molecular weight, and narrow molecular weight distribution can be produced with extremely good yield. Furthermore,
In the method of the present invention, it goes without saying that it is easily possible to lower the trans bond content, lower the molecular weight, and widen the molecular weight distribution of the conjugated diene polymer obtained if necessary. The polymers thus obtained exhibit properties ranging from crystalline resin-like polymers to non-crystalline rubber-like polymers depending on the trans bond content, etc., and have a wide range of uses. For example, if the polymer has a high molecular weight and is amorphous, it can be used as a rubber-like polymer for tire treads, carcass, sidewalls, etc., and exhibits excellent properties such as wear resistance and heat generation properties. If the polymer has high molecular weight and crystallinity, golf ball skin,
It can be used as a resin material for sanitary materials, etc., and the polymer has a relatively low molecular weight and crystallinity.
It can be used as a processability improver for NBR, chloroprene rubber, etc., and as a hot melt adhesive. In addition to the above examples, the polymer obtained by the present invention can be used in a wide range of applications, and the present invention has great industrial significance.

Claims (1)

[Claims] 1 (a) An organic acid compound represented by the following general formulas () to () and R ¹ −LH ... () (Here, R ¹ , R ² and R ⁵ to ^{R 8} represent an aliphatic hydrocarbon group or an aromatic hydrocarbon group,
R ³ represents an aromatic hydrocarbon group, R ⁴ represents an aliphatic hydrocarbon group, and R ⁹ to ^{R 12} represent an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an alkoxy group, or a phenoxy group. L represents an oxygen atom or a sulfur atom. Furthermore, j, k, l
and m represents an integer of 1 or more and 6 or less. ) an organic acid salt with lanthanum, and (b) an organomagnesium compound represented by the following general formula () Mg・R ¹³・R ¹⁴ ...() (where R ¹³ and R ¹⁴ are aliphatic hydrocarbons or an aromatic hydrocarbon group, which may be the same group or different groups. 2. The method for producing a conjugated diene polymer according to claim 1, wherein some or all of the catalyst components are pre-reacted in the presence or absence of a conjugated diene monomer prior to polymerization. 3 (a) An organic acid compound represented by the following general formulas () to () and R ¹ −LH ... () (Here, R ¹ , R ² and R ⁵ to ^{R 8} represent an aliphatic hydrocarbon group or an aromatic hydrocarbon group,
R ³ represents an aromatic hydrocarbon group, R ⁴ represents an aliphatic hydrocarbon group, and R ⁹ to ^{R 12} represent an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an alkoxy group, or a phenoxy group. L represents an oxygen atom or a sulfur atom. Furthermore, j, k, l
and m represents an integer of 1 or more and 6 or less. ) an organic acid salt with lanthanum, and (b) an organomagnesium compound represented by the following general formula () Mg・R ¹³・R ¹⁴ ...() (where R ¹³ and R ¹⁴ are aliphatic hydrocarbons group or aromatic hydrocarbon group, and they may be the same group or different groups.) When using a composite catalyst consisting of (c) the following general formulas () to () The organic compound of lithium represented by R ¹⁵ (Li) _w ... () R ¹⁶ (OLi) _x ... () R ¹⁷ (OCH ₂ CH ₂ ) _y OLi ... () (Here, R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and
R ²¹ represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and w, x, y and z represent an integer of 1 or more and 6 or less. ) (d) An organoaluminum compound represented by the following general formula (), AlR ²² R ²³ R ²⁴ ... () (Here, R ²² and R ²³ represent hydrogen or an aliphatic hydrocarbon group, and R ²⁴ is (represents an aliphatic hydrocarbon group) (e) A method for producing a conjugated diene polymer, characterized by using in combination one or more of electron-donating compounds selected from ethers, thioethers, and amines. 4. The method for producing a conjugated diene polymer according to claim 3, wherein some or all of the catalyst components are pre-reacted in the presence or absence of a conjugated diene monomer prior to polymerization.