JPS59117512A - Preparation of high cis 1,4-polybutadiene - Google Patents

Abstract

PURPOSE:To obtain the titled polymer with reduced energy having improved Mooney viscosity and suppressed gel content, by polymerizing 1,3-butadiene in a hydrocarbon solvent having high solubility parameter at high temperature using an Ni catalyst. CONSTITUTION:1,3-Butadiene is polymerized in a hydrocarbon solvent (e.g., mixed solvent containing n-hexane, etc.) having 7.35-7.85 solubility parameter (25 deg.C) in the presence of a catalyst consisting of three components selected from each group of (A) an organic acid salt of Ni and an organic complex compound, (B) boron trifluoride, boron trifluoride complex, hydrogen fluoride, and a hydrogen fluoride complex compound, and (C) an organometallic compound of a metal of I -III group of periodic table usually at 90-150 deg.C high temperature, to give the desired polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention 8A relates to a method for producing high cis 1,4-polybutadiene.

More particularly, the present invention relates to a method for producing high-cis 1,4-polybutadiene, which is characterized by combining in a solvent having a specific solubility parameter at a high temperature IK.

In recent years, polymerization at high temperatures has been strongly desired due to energy saving requirements. If polymerization can be carried out at high temperatures, it will be easier to remove the heat of one polymerization reaction, and the amount of cooling medium required for heat removal will be reduced! ! Since the viscosity of the polymerization system decreases, polymerization can be performed under conditions where a small amount of solvent is used, resulting in 9M coalescence, solvent separation, and solvent recovery n! It takes less energy to produce and is more compact. Therefore, polymerization under high temperature is a suitable polymerization method from the viewpoint of energy saving.

Conventionally, high-cis 1.4-
As for the manufacturing method of Polyptadier/, 'rt, co.

A typical method is to use a N1 catalyst.

However, when these catalysts are used, high-temperature polymerization may generate gels or reduce Mooney viscosity. It has been difficult to obtain a practical high-cis 1.4 polybutadiene with a content of 0.5 polybutadiene or less (filtration method using a No. 3 glass filter).

The present inventors have conducted intensive studies on a method for obtaining high-cis 1.4 polybutadiene with high Mooney viscosity and low gel content even at high temperatures of 90°C or higher. It was discovered that the object of the invention could be achieved by carrying out the reaction using a solvent, leading to the present invention.

In other words, 1. The present invention is directed to the preparation of (A) an organic acid salt of nickel and an organic complex compound, (B) boron trisulfide, a complex compound of boron trisulfide, hydrogen fluoride, and fluoride in a hydrocarbon solvent. Hydrogen compounds and (C) organometallic compounds of metals belonging to groups r, n, and m of the periodic table.

When carrying out the polymerization of 1,3-butadiene using a catalyst (() consisting of at least one component of 3et selected from each group of (A), (B) and (C), 90 to 1
Under high temperature of 50 °C, and solubility parameters (25 °C)
The present invention provides a method for producing high-cis 1,4-polybutadiene characterized by using a hydrocarbon solvent in the range of 7.35 to 7.85.

Due to the invention, the gel content is 0.5% or less and the Mooney viscosity (
It is possible to produce a high cis 1.4 polybutadiene having a MLs +4100°C) of 35 or more and a cis 1.4 content of 90% or more.

The present invention will be explained in detail below.

What is used as a catalyst for non-invention?

Preferred four-component substances include nickel naphthenate, nickel acetate, nickel octoate, nickel benzoate,
Examples include nickel oxalate, nickel carbonyl, nickel acetoacetate, and nickel acetylacetone.

(A preferred substance for the Bl component is boron trifluoride.

Examples include a complex compound of boron trifluoride and a compound selected from ether, phenol, and alcohol, and a complex compound of hydrogen fluoride, hydrogen fluoride, and a compound 1a selected from ether, phenol, and alcohol.

A preferred material for the tel component is butyllithium.

Examples include diethyl saliva lead, diethyl cadmium, trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum monochloride, diisobutylaluminum rhamnohydride, and the like.

The amount of catalyst used is usually 0.05 to 2.6 mW per 1002 of 1.3-butadiene based on component (A).
The amount is about the same as that of the secondary nickel phase.

The ratio of each component of the catalyst is 0.02 to 2 moles of the four components to 1 mole of component (C) and 0.2 to 10 moles of component (B). , benzene, toluene, xylene, mesitylene, ethylbenzene.

Aromatic hydrocarbons such as cumene at n-butane, n-pentane, isopentane, n-hexane, n-hebutane,
n-octane, isooctane, butene.

With aliphatic hydrocarbons such as octene, or aliphatic hydrocarbons such as cyclohexane and cyclohexene.

25 with a mixture of 11 types or 2 or more of these hydrocarbons
Solvents having a bath solubility parameter of 7.35 to 7.85 at °C can be used.

In 5-7, the acetic acid solubility parameter of the volatile liquid is determined experimentally and is calculated by the following formula.

The solubility parameters described in this invention are Hydroca
rbon Processing 46 +21 (1
967) 1'1 MU 48263 (1969
) was calculated using the above formula.

The msolubility parameter of a mixture of miscible liquids is generally the arithmetic mean of each 114W4 solidity parameter by volume fraction of each component.

Specific examples of solvents that can be used in the present invention include n
- An n-hexane/toluene mixed active agent containing 60 to 95% hekinane, and an n-hexane/benzene mixed solvent containing 60 to 95% n-hexane.

N-hexane/cyclohexane mixed solvent containing 30-92% n-hexane, n-hexane/cyclopentane mixed bath agent containing 30-6-92% n-hexane, 45-75% n-pentane Examples include n-pentane/toluene mixed bath agents. Most preferred is a reconstituted water swamp medium containing at least 50% n-hexane.

The common IW parameter of the present invention at 25°C is 7.35.
If the polymerization is carried out at a temperature of 90 to 150°C using a solvent in the range of ~7.85°C, the polymerization system will not undergo phase separation.
A high-cis 1.4 polybutadiene with high compound activity and high Mooney viscosity is obtained.

Solvents such as hexane, pentane, butane, propane, and isooctane alone having a solubility parameter (at 25°C) of less than 7.35 are undesirable because phase separation occurs under 1 degree of coherence conditions of 90 to 150°C, resulting in a decrease in II polymerization activity. In addition, gel is formed, and workability is also poor.

Cyclohexane, toluene, xyleno. 90 for solvents with solubility parameters exceeding 7.85, such as benzene alone.
It is difficult to produce high cis 1.4 polybutadiene with a Mooney viscosity of 35 or higher under polymerization temperature conditions of ~150°C.

- If the polymerization temperature is less than 90°C, the viscosity of the polymerization system will increase significantly, and the temperature of the polymerization system will be low, making it difficult to remove heat.
X Nowadays, a lot of solvent is required.

Therefore, the amount of recovered solvent increases and a lot of energy is required.

If the temperature exceeds 150°C, 1,3-butadiene reaches a critical temperature, resulting in a significant decrease in polymerization activity. 100-130℃
is more preferable. The amount of solvent used is 1,3-butadiene I
0.5 to 41 parts per 1 part is used.

By carrying out polymerization at 90 to 150°C using the nickel-based catalyst of the present invention in a hydrocarbon solvent with a solubility parameter in the range of 7.35 to 7.85 at 25°C, excellent polymerization of the sheet skin with rollability can be achieved. A union is obtained.

Next, the invention will be specifically illustrated by examples, but the invention is not limited by the examples.

Example side Oμ (1) N-hexane 70 in a stainless steel reactor
0f, cyclohexa/300t, 1,3-butadiene 5
After adjusting the temperature to 110° C., 0.341 mmol of nickel octoate and 1.87 fiunol of boron trifluoride ethyl etherate were added.

1.53 mmol of triethylaluminum (Y) was added to the reactor, and an isothermal reaction was carried out at 110'C.

In addition, n-hexane/cyclohexane = 70/30<
yxa ratio) of this mixed solvent (25°C
) is 7.51. 60 minutes after the start of the first match.

After adding 3F 2,6-ditertiary-butyl-P-cresol to the 1-coalescence solution, the solvent was removed by steam stripping and dried with a heated roll at 100°C to obtain a polymer.

Next, the mixtures were blended in a Brabender blast mill and roll according to the formulation shown in Table 1-2, and vulcanization was performed at 145°C for 35 minutes.

Results are shown in Table 7-1.

91 Example 2 In Example 1, n-hexane y700f, cyclohexane 3
The same procedure as in Example 1 was conducted except that n-hexane 13002 and cyclohexane 7002 were charged instead of 00F.

r, (o, n-hexane/cyclohexane = 65/3
The solubility parameter (25
°C) is 7.55.

The results are shown in Table 1.6 Example 3 The same procedure as in Example 1 was carried out except that the polymerization temperature was changed to 90°C.

The results are shown in Table-1.

Example 4 The same procedure as in Example 1 was carried out except that the polymerization temperature was changed to 150°C.

The results are shown in Table-1.

Example 5 In place of n-hexane 700 r and cyclohexane 300 f in Example 1, n-hexane 9209°=
10- 80t of microhexane, '4r-Example 1 except for charging
I did the same thing. The solubility parameter (25° C.) of this mixed solvent of n-hexane/cyclohexane-92/8 (Xit ratio) is 7.35.

The results are shown in Table-1.

Example 6 Example 1rc'''Cn-hexane 70 (iF, cyclohexane 300 S', 11-pentane 520
f.

The same procedure as in Example 1 was carried out except that benzene 480 F was charged. In addition, n-pentane/benzene = 40760
Solubility parameter (25℃) of the sintering solvent (total ratio)
is 7.85.

The results are shown in Table-1.

Comparative Example 1 In Example 1, 700 f of n-hexane, 300 f of cyclohexane, and 1000 f of n-hexane were used instead of 1.
The same procedure as in Example 1 was conducted except that t was charged. In addition, n
-The solubility parameter (25°C) of hexane alone is 7.
It is 30.

The results are shown in Table-1.

Comparative Example 2 In Kosao side 1, instead of charging n-hexane 700 f, cyclohexane 3 oor, v cyclohexane 100
The same procedure as in Example 1 was carried out except that 0 f was charged. In addition, the solubility parameter of cyclohexane alone (25°C)
is 8.10.

The results are shown in Table-1.

Comparative example 3 Except for Comparative Example 2 where the polymerization temperature was 80°C.

The same procedure as in Comparative Example 2 was carried out.

Comparative Example 4 The same procedure as in Example 1 was conducted except that 1 rationality was set to 80°C.

The results are shown in Table-1.

Comparative Example 5 Example 1 except that 1 rationality is set to 160°C in Example 1
I did the same thing.

The results are shown in Table-1.

When a solvent of the present invention having a solubility parameter in the range of 7.35 to 7.85 was used (Examples 1 to 6), high cis 1. It is clear that 4-polybutadiene is obtained without forming a gel.

If a solvent with a solubility parameter of less than 7.35 was used in Comparative Example 1, phase separation would occur at high temperatures.

1 activity decreases markedly and processability deteriorates.

When a solvent with a solubility parameter exceeding 7.85 in Comparative Example 2 is used, the Mooney viscosity of the product 1 coalescence is significantly reduced.

When the polymerization temperature in Comparative Example 3.4 is less than 90°C, the energy saving effect cannot be improved.

Comparative Example 501 If the temperature exceeds 150° C., gel formation and a decrease in the amount of cis 1.4 occur, and the polymerization activity also decreases, which may change the effect of the present invention.

13- Table-2 Combination prescription 14-

Claims (1)

[Claims] (1) In hydrocarbon solvent A, (A) nickel organic acid salts and tangential complex compounds, (B) boron trifluoride, boron trisulfide complex compounds, fluoride water and hydrogen fluoride complex compounds, and ( C) No. 1 of the periodic table. The production of 1,3-butadiene using a catalyst consisting of at least one component selected from each of groups (A), (B), and (C) of organometallic compounds of metals belonging to Groups M and I. 1. High cis 1,4-polybutadiene is characterized by using a hydrocarbon solvent having a solubility parameter (at 25°C) of 7.35 to 7.85 at a high temperature of 90 to 150°C. manufacturing method.