JPS6138203B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for polymerizing 1,3-butadiene in a hydrocarbon solvent using a catalyst obtained from a halogen-containing organoaluminum compound, a soluble cobalt compound, and an organophosphorus compound. The viscosity (measured at 30℃) is 100 to 10,000 centipoise (C.
After contacting and mixing a polymerization reaction mixture containing liquid polybutadiene (abbreviated as P.) with an aqueous solution of sodium hydroxide or potassium hydroxide, the aqueous phase is separated and removed, and the resulting oil phase polymer is After contacting and mixing the mixed solution with an aqueous solution of subzincate or hydrogen peroxide, the aqueous phase was separated and removed, and then the hydrocarbon solvent was removed from the polymer mixture in the oil phase by distillation. The present invention relates to a method for purifying liquid polybutadiene, which comprises contacting and mixing liquid polybutadiene and methanol, and then separating and obtaining liquid polybutadiene.

The polymerization reaction mixture containing liquid polybutadiene obtained by polymerizing 1,3-butadiene in the presence of the catalyst is washed with water and flashing volatile matter of the polymerization reaction mixture, which is usually applied as a method for purifying liquid polybutadiene. The liquid polybutadiene obtained by purifying the liquid polybutadiene is colored blue or yellow, and the maleated polybutadiene obtained by maleating this liquid polybutadiene is colored blackish brown and opaque, making it suitable for use in photosensitive resins. It cannot be used as a polymer, limiting the applications of liquid polybutadiene.

The inventors of this application completed this invention as a result of intensive research into a method for purifying liquid polybutadiene that does not have the above-mentioned drawbacks.

According to this invention, the viscosity obtained by polymerizing 1,3-butadiene in a hydrocarbon solvent (measured at 30°C ) is 100 to 10000 C.P. can be purified.

Examples of the halogen-containing organoaluminum compounds include dimethylaluminum monochloride, diethylaluminium monochloride, dipropylaluminum monochloride, dibutylaluminum monochloride, diisobutylaluminum monochloride, dipentylaluminum monochloride, di-n-hexylaluminum monochloride, Diethylaluminum monobromide, methylaluminum sesquichloride, ethylaluminum sesquichloride, propylaluminum sesquichloride, butylaluminum sesquichloride, isobutylaluminum sesquichloride, n-pentylaluminum sesquichloride, n-hexylaluminum sesquichloride, ethylaluminum sesquibromide, etc. can be mentioned.

As the soluble cobalt compound, any cobalt compound can be used as long as it is soluble in the hydrocarbon solvent used, but cobalt compounds such as cobalt chloride, cobalt bromide, cobalt iodide, and cobalt nitrate are preferably used. Complexes of inorganic acid salts with pyridine or ethyl alcohol, organic acid salts of cobalt such as cobalt octenoate, cobalt naphthenate, cobalt stearate, and cobalt acetylacetonate, cobalt bisacetylacetonate, cobalt acetoacetic acid ethyl ester, etc. Examples include cobalt chelate complexes such as:

As the organic phosphorus compound, an organic phosphine compound and an ester compound of phosphorous acid can be used.

Specific examples of organic phosphine compounds include triphenylphosphine, triallylphosphine, triethylphosphine, tri-n-propylphosphine, tri-n-butylphosphine, tri-n-hexylphosphine, tri-n-octylphosphine. , tricyclohexylphosphine, diethylphenylphosphine, di-n-butylphenylphosphine,
Examples include ethyldiphenylphosphine and n-butyldiphenylphosphine.

Specific examples of phosphite compounds include triisopropyl phosphite, tri n-propyl phosphite, tri n-butyl phosphite, tri n-amyl phosphite, tri n-hexyl phosphite, and tri n-octyl phosphite. , tri-n-dodecyl phosphite, tri-n-octadecyl phosphite, triphenyl phosphite,
Tri(4-methylphenyl) phosphite, tribenzyl phosphite, tri(phenylethyl)
Phosphite, triallylphosphite, triolylphosphite, tricyclohexylphosphite, trinaphthylphosphite, diisopropylphosphite, di-n-butylphosphite,
Diphenyl phosphite, diisodecyl phosphite, didodecyl phosphite, dioleyl phosphite, di(2-ethylhexyl) phosphite, ethyl diphenyl phosphite, n-propyl diphenyl phosphite, isopropyl diphenyl phosphite, n-butyl Diphenyl phosphite and the like can be mentioned.

In the method of this invention, the amount of the soluble cobalt compound that is one component of the catalyst used is preferably 0.005 to 1 mol, particularly 0.01 to 0.5 mol, per 1 mol of the organoaluminum compound.

The amount of organic phosphorus compound used, which is one component of the catalyst, varies depending on the type of organic phosphorus compound, but depending on the amount of organic phosphorus compound used, the viscosity of liquid polybutadiene (measured temperature 30°C) can be adjusted from 100 to 100.
It can be changed within the range of 10000C.P.
Generally, as the amount of the organic phosphorus compound used increases, the viscosity of the obtained liquid polybutadiene decreases.

In addition, the amount of catalyst used relative to 1,3-butadiene is generally
1,3- using a soluble cobalt compound catalyst
The amounts used when polymerizing butadiene can be applied, but it is preferred to use a catalyst containing from 2 to 0.002 mmol of organoaluminum compound per gram of 1,3-butadiene.

In the method of this invention, the polymerization solvent is
Use hydrocarbon solvents. For example, benzene, toluene, xylene, n-hexane, n-pentane, cyclohexane, etc. can be used as the polymerization solvent.

In the method of this invention, the microstructure, viscosity and molecular weight of the polybutadiene produced are not significantly affected by trace amounts of water present in the polymerization system. Furthermore, the microstructure, viscosity, and molecular weight of the polybutadiene produced are not significantly affected by the order of addition of the catalyst components.

In the method of this invention, the polymerization conditions, e.g.
Polymerization temperature, polymerization pressure, polymerization time, 1/3 in solvent
-The concentration of butadiene, etc. may be the same polymerization conditions as in conventionally known methods, but the polymerization temperature is -80 to 80℃.
Particularly preferred is 0 to 50°C, and the polymerization pressure is particularly preferably normal pressure, polymerization is possible even under pressure, and 1.3
- The concentration of butadiene is between 1 and 30% relative to the solvent used.
Weight percent is preferred.

In addition, in the method of the present invention, the polymerization of 1,3-butadiene is carried out by introducing gaseous 1,3-butadiene into a solvent containing a catalyst.
Polymerization can be carried out while blowing 3-butadiene,
Alternatively, polymerization can also be carried out by dissolving the entire amount of 1,3-butadiene in a polymerization solvent and adding a catalyst to the system.

The polybutadiene obtained by polymerizing 1,3-butadiene under the above polymerization conditions has a cis-1,4 structure content of 30 to 65%, a vinyl structure content of 30 to 65%, and a trans-1,4 structure content of 15%. It is a viscous liquid polybutadiene with a microstructure of less than

In the method of this invention, a polymerization reaction mixture obtained by polymerizing 1,3-butadiene and an aqueous solution of sodium hydroxide or potassium hydroxide are
Under normal pressure or increased pressure, preferably at 50-100°C,
Contact mix for 10-60 minutes.

When the polymerization reaction mixture and an alkaline aqueous solution of sodium hydroxide or potassium hydroxide are brought into contact and mixed, 2,6-di-tert-butyl-para-cresol, β-naphthol, phenyl-β-naphthylamine is added to the polymerization reaction mixture. It is preferable to add an antioxidant such as , tetramethyldiaminodiphenylmethane in advance. The amount of antioxidant added is per 100g of 1,3-butadiene used for polymerization.
Amounts within the range 0.01-2g are preferred.

The amount of the alkali is preferably such that the pH of the aqueous alkali solution after contacting and mixing the polymerization reaction mixture and the aqueous alkali solution is 7 or more.

After contacting and mixing the polymerization reaction mixture and the alkaline aqueous solution, the aqueous phase is separated and removed by static separation, centrifugation, etc. either as is or by adding a small amount of water.
The oil phase is then washed with water.

In the method of this invention, the polymer mixture of the oil phase obtained by the alkali treatment as described above and an aqueous solution of hypochlorite or hydrogen peroxide are preferably heated at 10 to 50°C. , contact and mix for 5 minutes to 3 hours.

Examples of the hypochlorite include alkali metal salts or alkaline earth metal salts of hypochlorous acid, such as sodium salts, potassium salts, calcium salts, and the like. Moreover, those containing these salts as main components can also be used. The amount of hypochlorite or hydrogen peroxide is 1 mol or more, especially 1.2 to 20
Amounts within the molar range are preferred. If the amount of hypochlorite or hydrogen peroxide is less than the above lower limit, the polybutadiene obtained will not be sufficiently purified, and if the amount of hypochlorite or hydrogen peroxide is greater than the above upper limit, the polybutadiene obtained will not be sufficiently purified. This is not preferable because it increases the amount of gel inside.

After contacting and mixing the polymer mixture with an aqueous solution of hypochlorite or hydrogen peroxide, the aqueous phase is separated and removed by static separation or centrifugation, either as is or by adding a small amount of water, and then the oil Wash the phase with water.

In the method of the present invention, the hydrocarbon solvent is removed by distillation from the polymer mixture of the oil phase in which the aqueous phase has been separated and removed as described above, and the obtained liquid polybutadiene and methanol are mixed, preferably at 20 to 50%
After contact mixing for 5 to 60 minutes at ℃, liquid polybutadiene is separated and obtained.

The amount of methanol brought into contact is preferably in the range of 200 to 1000 ml per 100 g of liquid polybutadiene.

According to the method of the present invention, it is possible to obtain a liquid polybutadiene having a Hazen color number of 70 or less and a Gardner color number of maleated polybutadiene obtained by maleating liquid polybutadiene by the method described below being 5 or less. .

Next, Examples and Comparative Examples will be shown.

In the Examples and Comparative Examples, the microstructure of liquid polybutadiene was determined by infrared absorption spectroscopy [D.Morero, A.Santambrogio, L.Porri, F.
Ciampelli, Chem. eInd., 41 , 758 (1959)]. Viscosity is measured using a rotational viscometer.
Measured at 30°C and calculated as absolute viscosity (CP). The Hazen color number of liquid polybutadiene was measured according to JIS-K6901.
In addition, the Gardner color number of the maleic anhydride adduct of liquid polybutadiene obtained by maleating liquid polybutadiene by the method shown below is
Measured according to JIS-K6901. The method for producing a maleic anhydride adduct of liquid polybutadiene is to add 30 g of liquid polybutadiene, 21.8 g of maleic anhydride, and 60 ml of pseudocumene to a 200 ml flask, and react under reflux at 167°C for 5 hours. In this method, maleic anhydride and pseudocumenoic acid are removed by vacuum distillation to obtain a maleic anhydride adduct of liquid polybutadiene.

Example 1 The air in a one-glass flask equipped with a reflux condenser and a stirrer was replaced with nitrogen, and a solution of 60 g of butadiene dissolved in 400 ml of benzene was added.Then, the solution was stirred and truffled under a nitrogen atmosphere. 3.4 mmol of enylphosphine, 16.0 mmol of diethylaluminum monochloride and 1.3 mmol of cobalt octenoate were added in this order, and the mixture was stirred at 20° C. for 1 hour to carry out polymerization. Add 0.09 g of 2,6-di-tert-butyl-para-cresol to the polymerization system and heat at 50°C.
After raising the temperature to , 40 ml of an aqueous solution in which 2 g of sodium hydroxide was dissolved was added, and the mixture was boiled under reflux at 73° C. for 30 minutes. The mixed solution was allowed to cool and stand to separate and remove the aqueous phase, and then the oil phase was washed with 100 ml of water. Add 0.5 ml of 30% by weight hydrogen peroxide solution to the water-washed oil phase polymer mixture, stir and mix at 20°C for 30 minutes,
After adding ml of water and stirring for 10 minutes, the mixture was allowed to stand and the aqueous phase was separated and removed. After washing the oil phase with 100 ml of water, the polymer mixture in the oil phase was distilled under reduced pressure to remove benzene, yielding 51.0 g of liquid polybutadiene.
Add 100ml of methanol to this liquid polybutadiene, stir and mix at 20°C for 1 hour, leave to stand still to separate the liquid polybutadiene, and then distill under reduced pressure to remove residual methanol to create the liquid polybutadiene.
48.0g was obtained. This liquid polybutadiene has a viscosity of
260C.P., cis-1/4 structure 30%, vinyl structure 61
%, trans-1/4 structure 9%, Hazen color number 30
The maleic anhydride adduct of this liquid polybutadiene had an acid value of 180 and a Gardner color number of 3.

Comparative Example 1 2,6-di-tert-butyl-para-cresol was added to the polymerization reaction mixture obtained by polymerizing in the same manner as in Example 1.
0.09g and 500ml of water were added and boiled under reflux at 73°C for 30 minutes. The mixed solution was allowed to cool and stand to separate and remove the aqueous phase, and then the oil phase was washed with 100 ml of water. The water-washed oil phase polymer mixture was directly distilled under reduced pressure to remove benzene, yielding 52.4 g of liquid polybutadiene. This liquid polybutadiene has a viscosity of 230 C.P., a cis-1/4 structure of 30%, and a vinyl structure.
61%, trans-1/4 structure 9%, Hazen color number
140, the acid value of this liquid polybutadiene with maleic anhydride is 180, and the Gardner color number is 18.
It was hot.

Example 2 Liquid polybutadiene was produced in the same manner as in Example 1 except that the amount of triphenylphosphine used in the polymerization of 1,3-butadiene was changed to 0.4 mmol.
50.0g was obtained. This liquid polybutadiene has a viscosity of
2520C.P., cis-1/4 structure 58%, vinyl structure 30
%, trans-1/4 structure 12%, Hazen color number 30
The maleic anhydride adduct of this liquid polybutadiene had an acid value of 185 and a Gardner color number of 3.

Example 3 Triphenylphosphine 3.4 was used as an organic phosphorus compound component used in the polymerization of 1,3-butadiene.
The same procedure as in Example 1 was carried out except that 1.4 mmol of tri-n-butyl phosphite was used instead of 1.4 mmol of tri-n-butyl phosphite to obtain 48.0 g of liquid polybutadiene. This liquid polybutadiene has a viscosity of 1800 C.P. and a cis-1/4 structure of 59
%, vinyl structure 32%, trans-1/4 structure 9
% and a Hazen color number of 50, and the maleic anhydride adduct of this liquid polybutadiene had an acid value of 188 and a Gardner color number of 2.

Example 4 Triphenylphosphine 3.4 was used as an organic phosphorus compound component used in the polymerization of 1,3-butadiene.
The same procedure as in Example 1 was carried out except that 1.7 mmol of tri-n-butylphosphine was used instead of 1.7 mmol of tri-n-butylphosphine, to obtain 45.0 g of liquid polybutadiene. This liquid polybutadiene has a viscosity of 1200 C.P. and a cis-1/4 structure of 56
%, vinyl structure 34%, trans-1/4 structure 9
% and a Hazen color number of 30, and the maleic anhydride adduct of this liquid polybutadiene had an acid value of 190 and a Gardner color number of 3.

Example 5 47.0 g of liquid polybutadiene was obtained by carrying out the same procedure as in Example 1 except that 5 ml of a 10% by weight sodium hypochlorite aqueous solution was added to the alkali-treated polymer solution instead of the hydrogen peroxide aqueous solution. Ta. This liquid polybutadiene has a viscosity of 270C.P., cis-1.4
The structure was 31%, the vinyl structure was 60%, the trans-1.4 structure was 9%, and the Hazen color number was 70. The maleic anhydride adduct of this liquid polybutadiene had an acid value of 175 and a Gardner color number of 5.

Example 6 Liquid polybutadiene was prepared in the same manner as in Example 1 except that 4 ml of 30% by weight aqueous hydrogen peroxide solution was used.
47.0g was obtained. This liquid polybutadiene has a viscosity of
260C.P., cis-1/4 structure 30%, vinyl structure 60
%, trans-1/4 structure 10%, Hazen color number 30
The maleic anhydride adduct of this liquid polybutadiene had an acid value of 182 and a Gardner color number of 2.

Claims (1)

[Claims] 1.3 in a hydrocarbon solvent using a catalyst obtained from a halogen-containing organoaluminum compound, a soluble cobalt compound, and an organophosphorus compound.
- Viscosity obtained by polymerizing butadiene (measurement temperature
After contacting and mixing a polymerization reaction mixture containing liquid polybutadiene with a temperature of 100 to 10,000 centipoise (30℃) and an aqueous solution of sodium hydroxide or potassium hydroxide, the aqueous phase is separated and removed, and the resulting oil phase is After contacting and mixing the polymer mixture with an aqueous solution of hypochlorite or hydrogen peroxide, the aqueous phase is separated and removed, and then the hydrocarbon solvent is removed from the oil phase of the polymer mixture by distillation. A method for purifying liquid polybutadiene, which comprises contacting and mixing the obtained liquid polybutadiene and methanol, and then separating and obtaining the liquid polybutadiene.