JPS60108407A - Manufacture of conjugated diene polymer - Google Patents

Abstract

PURPOSE:To obtain the titled polymer in high efficiency with outstanding rubber elasticity having sharp molecular weight distribution, by performing polymerization of conjugated diene monomer in the presence of a catalyst made up of specific rare earth metal rosin acid salt, organoaluminum compound and halogen-contg. Lewis acid compound. CONSTITUTION:The objective polymer can be obtained by polymerization of conjugated diene monomer in the presence of a catalyst made up of (A) rare earth metal rosin acid salt of formula I (Ln is a metal whose atomic number falls between 57 and 71 in the periodic table; formula: -OCOR<1> is organic acid group of rosin acid or modified one) (e.g. rosin acid neodymium salt), (B) organoaluminum compound of formula II (R<2>, R<3>, and R<4> are each H, or 1-10C hydrocarbon, not all of them being H) (e.g. triisobutylaluminum) and (C) halogen- contg. Lewis acid compound (e.g. ethylaluminum sesquichloride).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for efficiently producing a conjugated diene polymer having a sharp molecular weight distribution and excellent rubber elasticity.

A large number of methods for producing conjugated diene polymers have been known in the past.
In particular, conjugated diene polymers obtained using composite catalysts containing transition metal compounds such as nickel, cobalt, and titanium as main components have a cis content of over 90%, and are known as high-cis polyzotadiene, high-cis isoprene, etc. , along with low-sis type JM using lithium-based catalysts, are produced industrially in large quantities and are widely used in various applications.

As one of the methods for producing this high-cis type conjugated diene polymer, a composite catalyst containing a rare earth metal compound, especially a cerium compound as a main component, is known. It is said to have superior adhesiveness compared to diene polymers. (Kautsc
huk und Gummi Kunststoffe
.

(Vol. 22, p. 293, published in 1969) However, the activity of this type of catalyst may be uneven because the rare earth metal compound, which is the main component of the catalyst, or the entire polymerization catalyst is not completely dissolved in the polymerization solvent. However, it was insufficient. Furthermore, the molecular weight distribution of the obtained conjugated diene polymer was extremely broad, and the rubber elasticity was not particularly superior to that of other high-cis conjugated diene polymers.

Various attempts have been made to improve the drawbacks of these composite catalysts mainly composed of rare earth metals. For example, a polymerization catalyst is preformed in the presence of a conjugated diene monomer prior to polymerization, and
and ripening method to improve activity (Special Publication No. 47-14
No. 729), a method of using a rare earth metal Alcolade compound, especially neodymium Alcolade, as the rare earth metal compound that is the main component of the catalyst, and a method of making the catalyst homogeneous by using a specified tertiary organic calzenate of neodymium. Method (JP-A-54-40890, 55-66903),
A composite catalyst based on a specified organophosphate of neodymium (Pyoc, China-US B11ate)
ral 8ymp, Polym.

Ohem, Phys, 1979, p. 382 (19
(published in 1981), etc. are known. However, the improvement was still insufficient, and the development of a new catalyst was desired for industrialization.

In order to solve the above-mentioned problems in the production of conjugated diene polymers, the present inventors have conducted studies focusing on the type of rare earth metal compound that constitutes this composite catalyst, and have developed a rare earth metal rosin acid salt. This makes it possible to prepare a complex catalyst that is easy to prepare, has excellent solubility, and has extremely high activity, allowing polymerization to be carried out using a small amount of catalyst, and the molecular weight distribution of the resulting conjugated diene polymer is also extremely high. It was discovered that the image can be sharpened, leading to the present invention.

That is, the present invention provides the following as shown in the claims: (A) general formula Lr++, 0OORsu3 (in the formula, Ln
is a metal with atomic number 57 to 71 in the periodic table, -00
0FLI represents an organic acid group of rosin acid or capped rosin acid. ), a rare earth metal rosin acid salt represented by (Bl general formula AtR2.R3.R4c), B2.
H, a and HL4 are each the same or different,
Hydrogen or a hydrocarbon group having 1=-10 carbon atoms, not all hydrogen. ) and (0) a conjugated diene monomer in the presence of a catalyst comprising a halogen element-containing Lewis acid compound.

The main component constituting the composite catalyst of the present invention is a rare earth metal rosin acid salt compound. The rare earth metals used are:
Preferred metals include cerium, lanthanum, praseodymium, neodymium, and gadolinium. Among these metals, neodymium is industrially easily and inexpensively available, and moreover, it can be used as a catalyst with high polymerization activity. This is the most preferred option.

The rare earth metal of the present invention may be a mixture of two or more of these metals, or may contain a small amount of other rare earth metals or metals other than rare earth metals. Furthermore, the composite catalyst of the present invention may contain catalyst components other than the above-mentioned rare earth metal rosin acid salt compounds, such as rare earth metal carginate compounds, phosphate compounds, alcoholade compounds, phenolate compounds, etc. It's okay.

The rosin acid compound, which is another component forming the rare earth metal rosin acid salt compound of the present invention, is represented by the following general formula.

Oh.

6- (The carbon-carbon bond in the formula 2 indicates a saturated single bond or an unsaturated = double bond.) Examples of this include abietic acid, dehydrogenated abietic acid,
Examples include ShihyP-roabinitic acid, Tetrahy-P-roabinitic acid, and the like. These are rophosphoric acid compounds obtained by hydrogenation reaction or disproportionation reaction of rophosphoric acid or rosin acid.

The second component constituting the composite catalyst of the present invention is an organoaluminum compound and is represented by the following general formula.

AtR,”・R3・R4 (in the formula, B!, R3 and R4 are hydrogen or have 1 to 1 carbon atoms
0 hydrocarbon groups, not all hydrogen. ) Preferred organoaluminum compounds include trimethylaluminum, triethylaluminum, triisozorobylaluminum, triisobutylaluminum, trihexylaluminum, tricyclohexylaluminum, diethylaluminum hydride, diisobutylaluminum rhamno-hydride, ethylaluminum cybide dry P5 isobutylaluminum hydride. Examples include Dry P, and particularly preferred are triethylaluminum, triisobutylaluminum, diethylaluminum hydride, and diisobutylaluminum Hytryr. These may be a mixture of two or more types.

The third component constituting the composite catalyst of the present invention is a Lewis acid compound containing a nitrogen element. Preferred examples of these include organic metal halides and organic metal halides of elements belonging to the main groups ms, Ya, or Va of the periodic table, and the halides are preferably chlorine or bromine. Examples of these compounds include methylaluminum dibromide, methylaluminum dichloride P1 ethylaluminum dizolomyr1 ethylaluminum dichloride, butylaluminum dibromide, dimethylaluminum dichloride P1 dimethylaluminum bromide,
Dimethylaluminum chloride, diethylaluminum bromide, diethylaluminum chloride, dibutylaluminum bromide, dibutylaluminum chloride, methylaluminum sesquibromide, methylaluminum sesquichloride P, ethylaluminum sesquibromide, ethylaluminum sesquichloride, dibutyltin dichloride P1 aluminum tribromide, There are silicon tetrachloride, antimony trichloride, antimony pentachloride, phosphorus trichloride, phosphorus pentachloride and tin tetrachloride.
Particularly preferred are diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminium bromide, ethylaluminum sesquibromide, and hyethylaluminum dibromy P.

The composite catalyst of the present invention has extremely high activity, and the amount of catalyst used is preferably 0.5 x 10" mol or less per 10 (1) conjugated diene monomer to be polymerized, expressed as rare earth metal, and a particularly preferable range is 0. 0.015 to 0.3 x 10" mole. Use of more than this is unnecessary for the present invention, and the use of an unnecessary catalyst can greatly increase catalyst residues such as rare earth metals remaining in the conjugated diene polymer. Moreover, it is not preferable from an economical point of view.In the production method of the present invention, the amount of catalyst used is extremely small as mentioned above, and in some cases, a so-called deashing step is required to remove catalyst residue from the υ conjugated diene polymer. In addition, the preferred composition ratio of the three catalyst components of the present invention is preferably 1/2 to 100/2 to 6, particularly preferably 1/2 to 100/2 to 6, expressed as rare earth metal/aluminum/halogen element. is in the range of 115-50/2.5-5. Outside this range, it is difficult to obtain a highly active conjugated diene polymer with a sharp molecular weight distribution.

In the present invention, it is preferable that the composite catalyst undergoes a preliminary reaction between a rare earth metal rosin acid salt and an organoaluminum compound in the presence or absence of a conjugated diene monomer prior to addition of the halogen-containing Lewis acid compound. This preliminary reaction is carried out at 0 to 100°C for a reaction time of 1 minute to 10 hours. The preliminary reaction conditions are preferably carried out at a conjugated diene/rare earth metal ratio (molar ratio) of θ to 1000.

The polymerization in the present invention is carried out in the absence of a solvent or in the presence of a solvent. In the latter case, the solvents used include aliphatic or alicyclic hydrocarbons such as n-pentane, n-hexane, n-hebutane, and cyclohexane, aromatic hydrocarbons such as benzene and toluene, or methylene chloride and chloride. Halogenated hydrocarbons such as benzene are preferred.

These may be a mixture of two or more types, or may contain a small amount of impurities. Also, the polymerization temperature is -3
It is carried out at 0°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 are performed.

Conjugated diene monomers polymerized by the method of the present invention include, for example, 1,3-butadiene, isoprene, 1,3-pentadiene, and the like. Moreover, a mixture of these conjugated dienes may be used.

The conjugated diene polymer that can be obtained extremely efficiently by the method of the present invention has a uniform molecular weight distribution and is a raw material rubber that exhibits extremely excellent rubber elasticity. Taking advantage of this property, it can be used alone or blended with other diene rubbers or synthetic rubbers to produce tires such as treads, carcass, sidewalls, and beer tires, or industrial products such as hoses, window frames, belts, and anti-vibration rubber.
Used as raw material rubber for automobile parts. It is also used as a toughening agent for impact-resistant polystyrene, AB8 resin, etc.

Examples will be described below, and the rare earth metals used in the examples have a purity of 99.9% unless otherwise specified. In addition, when ethylaluminum sesquichloride is used as the halogen element-containing Lewis acid, structural formula A
IEt1. ,01. ．． ．． represents 1 mole.

Examples 1 to 4 and Comparative Examples 1 to 3 Sufficiently dried 700 xi pressure-resistant glass bottles were capped, and the inside was purged with dry nitrogen for 3 hours. 60f 1
・After sealing 400 t of n-hexane mixed solution containing 3-butadiene in a bottle, 0.12 mmol of neodymium rosinate or various organic acid salts and 3.6 mmol of tri-1-sozothylaluminium were added. Preliminary reaction was carried out for 15 minutes while maintaining the temperature at 23°C in a water bath.

Furthermore, 0.28 mmol of ethylaluminum sesquichloride F' was added, and polymerization was carried out at 65° C. for 1 hour. After polymerization, the reaction was stopped with a 10% methanol solution of BHT (2,6-bis(2-butyl)-4-methylphenol) at 10 mA', and the polymer was further precipitated and separated with a large amount of methanol. It was dried under vacuum at ℃.The conversion rate, Mooney viscosity, molecular weight distribution,
and the microstructure are shown in Table 1.

Table 1 shows examples using a composite catalyst mainly composed of a neodymium rosin acid salt of the present invention and comparative examples using a conventionally known composite catalyst containing a neodymium alcohol salt or an organic carboxylate salt. It can be seen that the resulting polybutadiene has a high catalytic activity and a sharp molecular distribution.

131 Examples 5 to 10 The method was carried out in the same manner as in Examples 1 to 4, and 0.12 mmol of the rare earth metal rosinate shown in Table 2 was used as a composite catalyst.
3.6 mmol of triisobutylaluminum and 0.28 mljmol of ethylaluminum sesquichloride were used. Table 2 shows the conversion rate, Mooney viscosity, molecular weight distribution and microstructure of the obtained polymer.

Examples 11 to 17 Performed in the same manner as Examples 1 to 4, using 0.12 mmol of neodymium rosinate as a composite catalyst, 3.6 mmol of the organoaluminum compound shown in Table 3, and 28 mmol of ethylaluminum sesquichloride ro. was used. Table 3 shows the conversion rate, Mooney viscosity, molecular weight distribution and microstructure of the obtained polymer.

Examples 18 to 28 A method similar to Examples 1 to 4 was carried out, and a halogen element-containing Lewis acid compound containing 0.12 mmol of neodymium rosinate and 3.6 mmol of triisodityl aluminum was used as a composite catalyst. The amount of halogen atoms used was 0.36 mmol. Table 4 shows the conversion rate, Mooney viscosity, molecular weight distribution and microstructure of the obtained polymer.

Examples 29 to 32 Examples 1 to 4 were carried out in the same manner as in Examples 1 to 4, using 0.12 mmol of neodymium rosinate, 3.6 mmol of triisobutylaluminum, and 0.28 mmol of ethylaluminum sesquichloride as the composite catalyst. As the solvent during polymerization, the solvents shown in Table 5 were used instead of n-hexane. Table 5 shows the conversion rate, Mooney viscosity, molecular weight distribution, and microstructure of the obtained polymer.

Example 33 Thoroughly dried 700 m/l' pressure glass, N)
The bottle was capped and the inside was purged with dry nitrogen for 3 hours. 60
After sealing 300 t of n-hexane mixture containing 1,3-butadiene in the zetle, 0.1 ml of neodymium rosinate was added.
2 mmol of triisobutylaluminum, 3.6 mmol of triisobutylaluminum, and 0.28 mmol of ethylaluminum sesquichloride were sequentially added, and polymerization was carried out at 65° C. for 1 hour.

After polymerization, the polymer solution was treated in the same manner as in Examples 1-4. Table 6 shows the conversion rate, Mooney viscosity, molecular weight distribution and microstructure of the obtained polymer.

Example 34 A sufficiently dried 100 ml pressure-resistant glass bottle was capped, and the inside was purged with dry nitrogen for 3 hours. 203i lid% n-hexane solution of l-3-butadiene 2.27 f
was collected in a bottle, and additionally 0.12 mmol of neodymium rosinate and 1.2 mmol of diisobutylaluminum hydride.
mmol and ethylaluminum sesquichloride)4o
, 2 mmol of a were sequentially added, and a preliminary reaction was carried out at 23° C. for 15 minutes. The aged catalyst obtained in this way was
Add to 300 t of 1-hexane mixture containing 601F 1,3-citadiene in a pressure-resistant bottle of OO-, and heat at 65°C.
Polymerization was carried out for 1 hour. Table 6 shows the conversion rate, Mooney viscosity, molecular weight distribution and microstructure of the obtained polymer.

Example 35 It was carried out in the same manner as in Examples 1 to 4, and 400 f (Dn-
The hexane mixture was used as a composite catalyst with 0 neodymium rosin acid.
．． 12 mmol, triisobutylaluminum 3°6 mmol and ethylaluminum sesquichloride ro, 2
s mmol was used. Table 7 shows the conversion rate, Mooney viscosity, molecular weight distribution and microstructure of the obtained polymer.

Margin below 17- -19- JP-A-108407 (6) Self-procedural amendment (self-motivated) December 20, 1980 Director-General of the Patent Office Kazuo Wakasugi 1, Indication of the case 1988 Patent Application No. 214127 No. 2 Name of the invention Process for producing a conjugated diene polymer a Relationship to the case by the person making the amendment Patent applicant 1-2-6-4 Dojimahama, Kita-ku, Osaka-shi, Osaka Prefecture, subject of the amendment

Claims (1)

[Claims] 1. General formula L n -4-000R1)B (wherein Ln is a metal with an atomic number of 57 to 71 in the periodic table,
-000R,l represents an organic acid group of rosin acid or modified rosin acid. ) Rare earth metal rosin acid salt represented by (B) general formula AtR1・R8・R4 (in the formula Bl,
R, 3 and R4 are each the same or different,
It can be hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, but not all hydrogen. ) A method for producing a conjugated diene polymer characterized by polymerizing a military diene monomer in the presence of a catalyst consisting of an organoaluminum compound represented by (0) and a halogen element-containing Lewis acid compound z Conjugated diene monomer Production of a conjugated diene polymer according to claim 1, characterized in that the catalyst component and the catalyst component (B) are pre-reacted in the presence or absence of a catalytic compound prior to the addition of the catalyst component (0). Method λ A method for producing a conjugated diene polymer according to claim 1 or 2, characterized in that the catalyst components are aged in the presence of some conjugated diene monomers prior to polymerization, The method for producing a conjugated diene polymer according to claim 1.2 or 3, wherein the conjugated diene monomer is 1.3-butadiene.