JPS5936108A - Polybutadiene manufacturing method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polybutadiene using a novel catalyst.

Copolymers obtained by adding polybutadiene to styrene monomer and performing radical polymerization have improved impact resistance in addition to the excellent properties of polystyrene, and are therefore widely commercially available as impact-resistant polystyrene resins.

The polybutadiene used to produce this impact-resistant polystyrene thread resin is generally obtained by polymerizing 1,3-butadiene using an alkyl lithium as a catalyst and has a cis-1,4 structure content of 30 to 35%. Lance 1,
4-Structure content is 50-60%, 1,2 structure content is 1
1, with 0 to 20% poly7-tadiene (low cis polybutadiene) and a hycobalt or nickel catalyst.
The cis-1,4 structure content obtained by polymerizing 3-butadiene is 96 to 98%, and the trans-1,4 structure content is 1
~2%, and polybutadiene (high cis polybutadiene) with a 1,2 structure content of 1-2%.

The above-mentioned low cis polybutadiene has a high glass transition point "i'
(usually at 0.degree. C.), therefore, the impact-resistant polystyrene resin obtained using this low-cis polybutadiene is not fully satisfactory in terms of impact resistance.

On the other hand, the above-mentioned high-cis polybutadiene has a low l,2 structure content of 1 to 2%, so it has low reactivity [graft reactivity] with styrene monomers, and it cannot be obtained using high-cis polybutadiene. Impact resistant polystyrene resins also have the disadvantage of not being fully satisfactory in terms of impact resistance.

In addition, as a property of polybutadiene, in addition to the above-mentioned 1,2 structure or (or cis-1,4 structure content), it is important that the molecular weight is high. The resin is not fully satisfactory in terms of impact resistance because it is difficult to exhibit the rubber properties of polybutadiene.Cobalt compounds and halogen-containing organoaluminum compounds for the production of high-cis polybutadiene.

and an organic phosphorus compound as a fourth component in the water catalyst system,
Alternatively, when an organic sulfur compound is added and polymerized, polybutadiene having a relatively high 1,2 structure content is generally obtained. However, as the l,2 structure content increases, the molecular weight decreases, resulting in a nearly liquid form that cannot be practically used as a rubber (for example, JP-A-50-91689).

The catalyst system of the present invention comprises (a) a cobalt compound, (b)...
It consists of a logen-containing organoaluminum compound, (C) water or a polyhydric alcohol, and (d) dithiocarbamic acids as a fourth component.

When 1,3-butadiene is polymerized using this catalyst system,
Polybutadiene having a relatively high content of both cis-1,4 structure and 1,2 structure and high molecular weight can be obtained. This polybutadiene is suitably used as the polybutadiene for producing the above-mentioned impact-resistant polystyrene resin. If the method of the present invention is used, the content of each structure in polybutadiene will vary depending on the dipolymerization conditions, with the proportion of 1,2 structures ranging from 4 to 50%, preferably from 5 to 20%, and cis-1,4
The structural content is 48 to 96%, preferably 80% or more,
The trans-1,4 structure content can be varied within a range of 2% or more. In addition, polybutadiene has an intrinsic viscosity [η
] (Toluene, 30″C) can be varied in the range of 1 to 10, preferably 1.5 to 7.

Examples of the cobalt compound as a catalyst component used in the polymerization reaction of the present invention include β-diketone complexes of cobalt such as cobal) (J acetylacetonate, cobal) (Ill) acetylacetonate, and cobalt β-diketone complexes such as cobalt acetoacetic acid ethyl ester. β-keto acid ester, cobalt octoate, cobalt naphthene-1-, cobalt octoate and other organic carboxylic acid salts with 6 or more carbon atoms, conochloride (lutohyridine a, cobalt chloride ethyl alcohol complex, etc.), Examples include rogeno(ruto) complexes.

The halogen-containing organoaluminum compound has the general formula Aε
Rn
．． (a number from 5 to 2). Examples of organoaluminum compounds containing nitrogen include dialkylaluminum monochloride, diethylaluminum monobromide, diimbutylaluminum monochloride, etc., ethylaluminum sesquichloride, sesquinopolyhydric alcohol, etc. ethylene glycol.

Propylene glycol, trimethylene glycol.

Dihydric alcohols such as α-butylene glycol, β-butylene glycol, and tetramethylene glycol,
Examples include trihydric alcohols such as glycerin.

Dithiocarbamic acids have the general formula 2NCSH (R is hydrogen or an alkyl group having 1 to 10 carbon atoms.

phenyl group, cycloalkyl group, or pentamethylene group) and their salts, such as dimethyldithiocarbamic acid, diethyldithiocarbamic acid, dibutyldithiocarbamic acid, pentamethylenedithiocarbamic acid, and their respective ammonium salts and amine salts. can be mentioned.

When 1,3-butadiene is polymerized using a catalyst obtained from a cobalt compound, a halogen-containing organoaluminum compound, water (or polyhydric alcohol), and dithiocarbamic acids, 1,3-butadiene alone is used as the monomer. Alternatively, not less than 50% by weight (preferably not more than 20% by weight) of the 1,3-butadiene can be substituted with isoprene, L3-pentadiene, 2,3-dimethyl-
1,3-butadiene or the like may be used instead.

1. The amount of the 3-butadiene polymerization catalyst used is such that the cobalt compound is o, o
1 mmol or more of O, especially 0. O05 mi'J mole or more is preferred.

The molar ratio of cobalt compound to halogen-containing organoaluminum (co/AQ) is:

1:5~1:1000. Especially 1:15-1:5
A ratio of 00 is preferred.

The molar ratio of cobalt compound to dithiocarbamate compound is 1:0.01-1:20. Especially 1:o, 1
A ratio of ˜1:10 is preferred.

The molar ratio of water (or polyhydric alcohol) to halogen-containing organoaluminium 1d is preferably from 0.01:1 to 1:1, particularly from 0.1:1 to 0.5:1.

1. When polymerizing 3-butadiene, the combination solvent and shite,
Aromatic hydrocarbons such as benzene, toluene, xylene,
Aliphatic hydrocarbons such as butane, butene, n-hebutane, n-hexane, n-octane.

The Φ-combination may be carried out in a polymerization solvent such as an alicyclic hydrocarbon such as cyclohexane or methylcyclohexane.

(2) The polymerization temperature of 3-butadiene is 5 to 100°C.

Particularly preferred is 20 to 80°C, and the double polymerization pressure may be normal pressure or higher.

1.3 - When polymerizing butadiene, known molecular weight regulators 1, such as non-conjugated dienes such as cyclooctadiene and allene, or ethylene and propylene.

Alpha-olefins such as styrene and butene-1 can be used.

After the polymerization reaction is completed, the polyphtadiene can be removed by adding an antiaging agent and treating with alcohol, hot water or water in a known manner.

The polybutadiene of the present invention is 2, for example, polybutadiene 2
~25 parts by weight, preferably 2 to 20 parts by weight and styrene 7
Impact-resistant polystyrene is produced by radical polymerizing a mixture of 5 to 98 parts by weight, preferably 80 to 98 parts by weight, by a bulk method or a bulk/suspension method, preferably a bulk/suspension method. It can be made of resin. Alternatively, the polybutadiene of the present invention exhibits excellent properties even when blended as is with styrene-butadiene rubber (SBR) and used for trend tires.

Example 1 1,3-Butadiene 622 was added to 200 ml of benzene, then 0.44 mmol of water was added, and the mixture was stirred at 30° C. for 30 minutes to dissolve the water.

Next, 1.56 mmol of diethylaluminium monochloride, 0.015 mmol of diethyldithiocarbamic acid diethylamine salt (hereinafter referred to as (1)), and 0.02 mmol of cobal octenoate! After sequentially adding J moles, 30℃
The mixture was stirred for 30 minutes to polymerize 1,3-butadiene.

After the polymerization reaction is complete, add 2,6-di-tert-butyl-4 to the polymerization solution.
- A large amount of methanol containing 0.1% of methylphenol was added, and the precipitate was dried under reduced pressure at room temperature for 24 hours to obtain polybutadiene 19.052. This polybutadiene has a 1,2 structure content of 5.0% and a 7-1,4 structure content of 93%. .

The trans-1,4 structure content was 2.0%.

The intrinsic viscosity [η] (toluene, 30"C, hereinafter the same) was 5.28.

Example 2. ．． 5.4-, Comparative Example 1 A polymerization reaction was carried out in the same manner as in Example 1 except that the amount of compound (1) was changed.

The results obtained are shown in Table 1.

Table 1 Example 5 A song using 1 mmol of cobalt octenoate was made in the same manner as in Example 2, with 11.55 g of polybutadiene.
I got it. This polybutadiene has a cis-1,4 structure content of 89.7% and a trans-1,4 structure content of 1.0%.
, l, 2 structure content is 9.3%.

The intrinsic viscosity [η] was 6.54.

Examples 6 and 7 A polymerization reaction was carried out in the same manner as in Example 5 except that the polymerization temperature was changed. The results obtained are shown in Table 2.

Table 2 Examples Example 8.952 of polybutadiene was obtained in the same manner as in Example 6 using 0.66 mmol of water. This polybutadiene has a cis-1,4 structure content of 88.5%.

The trans-1,4 structure content was 1.4%, the 1,2 structure modification content was 1000%, and the intrinsic viscosity [η] was 4.17. Example 9 Compound (1) as a dithiocarbamic acid compound The song using o and ol millimole of dibutyl dithiocarbamate dibutylammonium salt (abbreviated as (■)) is Example 6.
Polybutadiene 15.281 was obtained in the same manner as above. This polybutadiene has a cis-1,4 structure: content rate of 92.8
%, the trans-1,4 structure content is 1.1%, the 1,2 structure content is 6.1%, and the intrinsic viscosity [η] is 5.28
Met.

Example 10 10.24 g of polybutadiene was obtained in the same manner as in Example 9 using 0.02 mmol of compound (1).

This polybutadiene has a cis-1,4 structure content of 89
．． 8%, and the trans-1,4 structure content is 1.0%.

1.2 The crushing content is 9.2% and the intrinsic viscosity (η) is 5
．． It was 06.

Example 11 A pond in which 0.44 mmol of ethylene glycol was used instead of water was prepared in the same way as in Example 6, and polybutadiene lo, 5
I got 6y. This polybutadiene has a cis-1,4 structure content of 91.5% and a trans-1,4 structure content of 0.5%.
9%, 1,2 structure content 7.6%, and intrinsic viscosity [η]
was 5.21.

Patent applicant: Ube Industries Co., Ltd.

Claims (1)

[Claims] A method for producing polybutadiene by polymerizing 1,3-butadiene in the presence of a catalyst, in which (a) a cobalt compound, (b) a halogen-containing organoaluminum compound, (C) water or Polyhydric alcohol. and (d) a method for producing polybutadiene, which comprises polymerizing l,3-butadiene using a catalyst obtained from dithiocarbamic acids.