JPS60112808A - Preparation of hydroxyl group-containing diene polymer - Google Patents

Abstract

PURPOSE:To obtain the titled polymer useful for improving urethane foam, etc. in a short in high yield, by reacting a conjugated diene monomer with hydrogen peroxide (time catalyst) by the use of sulfobenzimide or naphthylacetic acid as a cocatalyst. CONSTITUTION:(B) A conjugated diene monomer (e.g., chloroprene, etc.) is reacted with (C) a catalyst of hydrogen peroxide by the use of (A) sulfobenzimide and/or naphthylacetic acid as a cocatalyst in a reaction medium (preferably methanol, etc.) to give the desired polymer. The compound A used is preferably 0.05-10wt% based on the component C. The polymerization is preferably carried out at 100-150 deg.C at 10-50 atmospheric pressure for 30min-5hr.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an efficient method for producing a hydroxyl group-containing diene polymer.

BACKGROUND ART Conventionally, a method for producing a diene polymer having a hydroxyl group at the terminal by polymerizing a conjugated diene monomer using hydrogen peroxide as a catalyst has been known. However, in the conventional method, in order to obtain the polymer, it was necessary to conduct the reaction at a reaction temperature of about 130° C. for a relatively long time. Moreover, the yield was not sufficient.

Therefore, as a result of intensive research into a method for producing diene polymers in a short time and with high yield, the present inventor found that when a polymerization reaction is carried out using hydrogen peroxide and a specific co-catalyst, hydroxyl groups can be produced in a short time and with high yield. The present invention was completed by discovering that it is possible to produce a diene-containing polymer.

That is, the present invention is characterized in that a method for producing a hydroxyl group-containing diene polymer by reacting a conjugated diene monomer with hydrogen peroxide in a reaction medium uses sulfobenzimide and/or 7-tyl acetic acid as a cocatalyst. The present invention provides a method for producing a hydroxyl group-containing diene polymer.

The conjugated diene monomer used for Kinoe 11 is not particularly limited, but is usually a diolefinically unsaturated unsubstituted-12-substituted or 2,3-substituted-carbon atom having 4 to 12 carbon atoms.
1,3-diene is used.

Here, the substituent is an alkyl group or an aryl group.

Examples include halogen, cyano group, and nitro group. A specific example of a monomer is 1,3-butadiene.

Examples include isoprene, chloroprene, 2-cyano-1,3-butadiene, and 2,3-dimethyl-1,3-butadiene.

In the production of the above polymer, the above conjugated diene monomers are basically used alone or in combination of two or more, but
If necessary, a part of the conjugated diene monomer can be replaced with an ethylenically unsaturated monomer, and the conjugated diene monomer has 2 to 22 carbon atoms.
α-olefinic addition polymerizable monomers are used. Specifically, styrene, α-methylstyrene, and vinyltoluene.

Methyl methacrylate, acrylic acid, vinyl chloride.

vinylidene chloride, acrylonitrile, acrylamide,
Examples include 2-ethylhexyl acrylate, n-octadecyl acrylate, maleic anhydride, butene, and 2-hydroxyethyl methacrylate. This monoolefinically unsaturated monomer can be used in combination with the conjugated diene monomer, preferably in a range of 0 to 75% by weight.

The polymerization reaction of the conjugated diene monomer is carried out in a reaction medium, and the reaction medium is preferably a solvent having good compatibility with both the diene monomer and hydrogen peroxide. Such solvents include methanol, ethanol, n-propanol, isopropanol.

butanol, propyl ether, tetrahydrofuraf,
hNIk ethyl, cellosolve, cellosolve acetate,
Examples include ethyl cellosolve, N,N-dimethylformamide, acetone, and mixtures thereof. The amount of solvent used is 5 to 90% by weight of the total amount charged (monomer, hydrogen peroxide, cocatalyst and solvent), preferably 30 to 7% by weight.
It is 0% by weight.

In addition, hydrogen peroxide, which acts as a catalyst, is usually 30 to 8
It is used as a 0% aqueous solution, and in any case, 0.5% by weight or more, preferably 1 to 12% by weight of the conjugated diene monomer is added as hydrogen peroxide.

Furthermore, in the present invention, either sulfobenzimide or naphthyl acetic acid is used as a cocatalyst. This promoter serves to further promote the catalytic effect of hydrogen peroxide. By using sulfobenzimide and/or naphthyl acetic acid as a cocatalyst in the present invention, it is possible to improve the yield of the diene polymer and shorten the reaction time.

In the present invention, the amount of co-catalyst used is not particularly limited, but
The amount is usually 0.01 to 15% by weight, preferably 0.05 to 10% by weight based on the conjugated diene monomer. 0.0
If it is less than 1% by weight, the effect as a cocatalyst will be small;
Even if it is added in excess of 0% by weight, the corresponding effect cannot be expected.
On the contrary, decomposition of hydrogen peroxide may occur, which is undesirable.

The polymerization reaction conditions of the conjugated diene monomer according to the present invention vary depending on the type of diene monomer used, the amount used, etc., and are not uniquely determined, but usually the reaction temperature is 50°C while stirring.
-200° C1, preferably 100-150° C1, reaction pressure 5-100 atm, preferably 10-50 atm, reaction time 10 minutes-24 hours, preferably 30 minutes-5 hours.

In this way, the desired hydroxyl group-containing diene polymer is obtained, and this polymer has a high content of functional groups including hydroxyl groups, and is almost constant regardless of the reaction conditions, with an average of 1
The number is 1.5 or more per molecule, usually 1.7 to 2.5.

Further, the number average molecular weight of this polymer varies depending on the reaction conditions, but is usually 300 to 30,000.

The diene polymer obtained by the present invention is used to produce polyurethane by reacting with polyisocyanate. The cured polyurethane product obtained at this time is characterized by high strength and high elongation. Therefore, this polymer is used in urethane foams, adhesives, paints, molded products, and resins.

Extremely useful for modifying asphalts, etc.

Furthermore, from the viewpoint of the production method, the present invention has the characteristics that the desired hydroxyl group-containing diene polymer can be obtained in a higher yield than conventional methods, and the reaction time can be shortened.

Next, the present invention will be explained by examples.

Example 1 100 parts by weight of inpropanol and 10 parts of hydrogen peroxide (concentration 50%) were placed in a stainless steel 30° shaking autoclave.
parts by weight and 0.52 parts by weight of 0-sulfobenzimide were charged, and the air inside the autoclave was vacuum degassed while cooling. Next, 100 parts by weight of 1,3-butadiene was supplied, and then the temperature was raised to 130°C. Thereafter, the mixture was shaken and stirred at 55 strokes/min for 60 minutes to cause a reaction.

After the reaction is complete, add 3 Qm of isopropyl alcohol to the reaction solution.
1, Tolxun 60me and 15111 g of water were added and the oil layer was separated. Furthermore, the oil layer was preliminarily degassed using an evaporator, and then degassed at lmmHg and 80°C for 30 minutes to remove evaporated components. Table 1 shows the yield of the obtained polymer.

Example 2 100 parts by weight of Impropatool and hydrogen peroxide solution (concentration 50%) in a stainless steel 3 (1me shaking autoclave)
and 0.50 parts by weight of α-naphthyl acetic acid were charged, and the air inside the autoclave was vacuum degassed while cooling. Then, after supplying 100 parts by weight of 1,3-butadiene,
The temperature was raised to 130°C.

Thereafter, the mixture was shaken and stirred at 55 strokes/min for 60 minutes to react.

After the reaction was completed, the polymer was separated and purified in the same manner as in Example 1 to obtain a polymer. The yield of the polymer is shown in Table 1.

Comparative Example 1 A polymer was obtained in the same manner as in Example 1 except that sulfobenzimide was not used in Example 1.

The results are shown in Table 1.

Table 1 Patent applicant: Idemitsu Petrochemical Co., Ltd.

Claims (1)

[Claims] (11) In a method for producing a hydroxyl group-containing diene polymer by reacting a conjugated diene monomer with hydrogen peroxide in a reaction medium, sulfobenzimide and/or naphthyl acetic acid are used as cocatalysts. A method for producing a hydroxyl group-containing diene polymer characterized by: (2) The method according to claim 1, wherein the cocatalyst is added in an amount of 0.01 to 10% by weight based on the conjugated diene monomer.