JPS6264810A - Production of hydroxyl group-containing liquid copolymer - Google Patents

Abstract

PURPOSE:To make it possible to decrease the viscosity and peroxide content of the obtained hydroxyl group-containing liquid copolymer, by treating a product obtained by copolymerizing a diene monomer with a vinyl monomer in the presence of hydrogen peroxide with water containing a phenolic hydroxyl group-containing compound. CONSTITUTION:A hydroxyl group-containing liquid copolymer is obtained by copolymerizing a diene monomer with a vinyl monomer in the presence of hydrogen peroxide. At this time, the product obtained by this copolymerization is treated with water containing a phenolic hydroxyl group-containing compound. The case where said diene monomer is butadiene and said vinyl monomer is acrylonitrile or styrene is particularly preferable. As said phenolic hydroxyl group-containing compounds, 2,2'-methylenebis(4-ethyl-6-t-butylphenol) or p-t- butylcatechol is preferable. The treatment with the phenolic hydroxyl group- containing compound preferably consists in treating with water containing 10-10,000ppm of this compound at 10-200 deg.C for 1-1,000min.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing a hydroxyl group-containing liquid copolymer, and more specifically, a hydroxyl group-containing liquid copolymer having a low viscosity and a reduced peroxide content. Relating to a manufacturing method.

[Prior art and problems to be solved by the invention] A hydroxyl group-containing liquid copolymer obtained by copolymerizing a diene monomer, a vinyl monomer, and a vinyl monomer in the presence of hydrogen peroxide is a liquid copolymer containing only the diene monomer. They have various advantages compared to polymers. For example, butadiene-acrylonitrile copolymers have superior oil resistance compared to butadiene polymers, and 1-butadiene-styrene copolymers have similarly superior adhesive properties. However, such a diene monomer-vinyl monomer copolymer has a higher viscosity than a polymer of the diene monomer alone, which poses a problem in that it is extremely difficult to handle.

In order to solve this problem, it has been proposed to increase the amount of hydrogen peroxide used in the copolymerization reaction, reduce the molecular weight of the resulting copolymer, and thereby lower the viscosity of the copolymer. .

However, this method has the following drawbacks.

(1) When hydrogen peroxide is removed by adding water after the copolymerization reaction, if the concentration of hydrogen peroxide is high, an emulsion will be formed due to the presence of polar groups in the residual vinyl monomer, making oil-water separation difficult.

(2) Since the hydrogen peroxide concentration in the oil phase obtained by oil-water separation increases, the peroxide content (active oxygen amount) in the resulting copolymer increases.

(3) If the temperature or time during solvent distillation is increased in order to reduce the amount of peroxide in the copolymer, the peroxide and the remaining monomers will react and co-exist. The viscosity of the polymer increases.

[Failure to solve the problem]

The present inventors have completed the present invention as a result of intensive research to solve the above problems.

That is, the first aspect of the present invention is to copolymerize a diene monomer and a vinyl monomer in the presence of hydrogen peroxide to produce a hydroxyl group-containing liquid copolymer. A method for producing a hydroxyl group-containing liquid copolymer is characterized in that it is treated with water containing a compound having a phenolic hydroxyl group. In producing a hydroxyl group-containing liquid copolymer through a polymerization reaction, the product obtained by the copolymerization reaction is treated with water containing a compound having a phenolic hydroxyl group, and then a thin film is evaporated. This is a method for producing a liquid copolymer.

The first method of the present invention is described in detail: (1) a step of copolymerizing a diene monomer and a vinyl monomer in a suitable solvent in the presence of hydrogen peroxide; (2) converting the product of the copolymerization reaction into a phenolic It consists of a process of treating with water containing a compound having a hydroxyl group, and after the treatment, the solvent, residual monomer, etc. are removed from the resulting oil phase by a conventional method such as distillation to produce the desired hydroxyl group-containing liquid copolymer. This is the way to do it.

Hydroxyl group-containing liquid copolymers to which the method of the present invention can be applied include diene monomers such as butadiene, isoprene, and chloroprene, and acrylonitrile, styrene, p-methylstyrene, and α-methylstyrene.

It is a copolymer obtained by reaction with a vinyl monomer such as acrylic acid ester. Here, the diene monomer and vinyl monomer used are not limited to those exemplified above, and various types can be used. The method of the present invention is particularly suitable as a method for producing butadiene-acrylonitrile copolymers and butadiene-styrene copolymers. The ratio of diene monomer and vinyl monomer used in the reaction (
The molar ratio (molar ratio) may be determined as appropriate depending on the monomers used and the purpose of use of the resulting copolymer, but usually the former is -99°1 to 50°50, preferably 90:10 to 70.
It is 30.

Next, the amount of hydrogen peroxide used in the reaction is not particularly limited, but the concentration is usually 5 to 90% by weight, preferably 30 to 7% by weight.
1 to 100 parts by weight of 0% by weight based on 100 parts by weight of the total amount of the diene monomer and vinyl monomer,
It is preferably used in a proportion of 5 to 50 parts by weight.

Further, the solvent used in the copolymerization reaction is not particularly limited as long as it is inert to the diene monomer and vinyl monomer. An example of such is isopropyl alcohol.

Suitable examples include alcohols such as ethyl alcohol and t-butyl alcohol. The amount of the solvent used is not particularly limited, but is usually 10 to 1 part by weight per 100 parts by weight of the diene monomer and vinyl monomer.
000 parts by weight, preferably 30 to 300 parts by weight.

The reaction conditions for the copolymerization reaction using the above materials may be determined as appropriate depending on the raw materials used and the amount used, but usually the temperature is 50 to 200°C, preferably 100 to 150°C,
Pressure 1-50 kq/crAG, preferably 1-30
kg/crAG for 0.5-5 hours, preferably 1-3
A time copolymerization reaction may be performed.

The copolymerization reaction product obtained by the above copolymerization reaction is treated with water containing a compound having a phenolic hydroxyl group as described below.

Various compounds can be used as the compound having a phenolic hydroxyl group. Specifically, catechol.

pt-butylcatechol, 2,2'-methylenebis(
4-ethyl-6-t-7'f ruphenol), in particular pt-butylcatechol.

2.2'-methylenebis(4-ethyl-6-tert-butylphenol) is preferred.

The amount of the compound added to water is usually 10 to 110,000.
ppm, preferably 50 to 5000 ppm. If the amount added is less than 10 ppm, the addition effect cannot be expected, and 1
If it exceeds 10,000 pp, it is not preferable because the copolymer may be colored or its properties may change, such as a change in the hydroxyl group content of the copolymer. Water containing such a compound having a phenolic hydroxyl group is added or press-injected into the copolymerization reaction product, and the mixture is heated at a temperature of 10 to 200°C, preferably 20 to 80°C, for 1 to 1,000 minutes, preferably 2 to 80°C. 2
After treatment for 00 minutes (for example, shaking treatment), the solvent and residual monomers are removed from the oil phase obtained by standing still, by a method such as distillation, to obtain the desired hydroxyl group-containing liquid copolymer.

Next, the second aspect of the present invention is a method for producing a hydroxyl group-containing liquid copolymer by subjecting the copolymer obtained by the method of the first aspect to a thin film evaporation treatment to remove the solvent and residual monomer. .

There are no particular restrictions on the conditions of the thin film evaporation treatment, such as temperature, degree of vacuum, treatment time, etc., but usually the temperature is 20 to 200°C, preferably 30 to 150°C, and the degree of vacuum is 0, 1 to 100.
HY, preferably 0.5-50 mmHf.

The convection time is 0.1 to 100 minutes, preferably 0.3 to 30 minutes.

As a device for the thin film evaporation treatment, a thin film evaporator such as a film evaporator can usually be used.

Next, one example of the above-mentioned thin film evaporator will be explained with reference to the drawings, but the present invention is not limited by the drawings. FIG. 1 is a sectional view of a thin film evaporator used in an embodiment of the present invention.

Inside the horizontal tapered body, there are rotor blades (flat blades) that rotate with a small gap between them, and the rotor with these rotor blades is supported by left and right bearings. Additionally, the left and right bearings have double mechanical seals, allowing high vacuum operation.

The copolymer obtained by the first method of the present invention is supplied into the thin film evaporator from the raw solution inlet by a pump, and a liquid film is formed in the gap between the wing tip and the fuselage by the centrifugal force of the rotating shaft.

This liquid film moves on the heat transfer surface in such a way that it is pushed out by the injected liquid while being stirred by the rotary blade, and during this time the solvent, residual monomer, etc. are evaporated by the heat medium in the jacket.

The steam generated by evaporation passes between the blades and is guided to the steam outlet. On the other hand, the hydroxyl group-containing liquid copolymer is led downward to the concentrate outlet.

〔Effect of the invention〕

Since the hydroxyl group-containing liquid copolymer obtained by the method of the present invention has a low viscosity, it is convenient to handle.

Furthermore, since the method of the present invention realizes the production of a low-viscosity hydroxyl group-containing liquid polymer without increasing the amount of hydrogen peroxide used in the copolymerization reaction, the peroxide content in the copolymer is also reduced. There is an advantage.

Moreover, according to the second aspect of the present invention, a hydroxyl group-containing liquid copolymer with a further reduced peroxide content can be obtained.

Therefore, the method of the present invention is excellent as a method for producing a hydroxyl group-containing liquid copolymer, and the hydroxyl group-containing liquid copolymer obtained by the method of the present invention is useful as an adhesive 1 elastic material 2 reaction injection molding material, etc. be.

〔Example〕

Next, the present invention will be explained by examples.

Example 1 A first container was placed in a stainless steel pressure-resistant container with a capacity of 1 and equipped with a stirrer.
Predetermined amounts of a diene monomer, a vinyl monomer, a hydrogen peroxide solution, and a solvent shown in the table were charged, and a copolymerization reaction was carried out under the reaction conditions shown in Table 1. After the reaction was completed, the temperature of the container was returned to room temperature, the container was opened to remove residual butadiene, and the reaction product was transferred to a 3-volume separating funnel. Next, water containing a predetermined amount of a compound having a phenolic hydroxyl group shown in Table 1 was added to the separating funnel, and the mixture was subjected to a shaking treatment under the treatment conditions shown in Table 1. Thereafter, the mixture was allowed to stand for 3 hours to separate the oil phase and the water phase. Next, the solvent and remaining monomers were distilled off from the kernel oil phase to obtain a hydroxyl group-containing liquid copolymer. Table 1 shows the viscosity and peroxide content of the obtained copolymer at 30°C.

Example 2 Instead of the shaking treatment using a separating funnel in Example 1,
The same procedure as in Example 1 was carried out except that water containing a compound having a phenolic hydroxyl group was directly poured into a pressure container and treated by stirring. Table 1 shows the viscosity and peroxide content of the obtained hydroxyl group-containing liquid copolymer.

Examples 3 and 4 The copolymer obtained after distilling off the solvent and residual monomer from the oil phase in Example 1 was further subjected to thin film evaporation treatment under the conditions shown in Table 1 to remove the solvent and residual monomer. The other operations were the same as in Example 1. Table 1 shows the viscosity and peroxide content of the obtained hydroxyl group-containing liquid copolymer. Note that in Example 4, styrene was used as the vinyl monomer.

Comparative Examples 1 to 3 Instead of the treatment with water containing a compound having a phenolic hydroxyl group in Example 1, the copolymerization reaction product was treated with the first
The same procedure as in Example 1 was carried out except that the amount of water indicated in the table was added. Table 1 shows the viscosity and peroxide content of the obtained hydroxyl group-containing liquid copolymer. :,

[Brief explanation of drawings]

FIG. 1 is a sectional view of a thin film evaporator used in an embodiment of the present invention. 1...... Raw solution inlet, 2... Main shaft, 3... Curved/Rotor blade, 4... Jacket, 5 Curved/ Gap , 6... steam outlet, 7...
・・・・・・Heat medium outlet, 8・・・・ Concentrate outlet. Patent applicant Idemitsu Petrochemical Co., Ltd. Figure 1/a Procedural amendment (voluntary) October 3, 1985

Claims (10)

[Claims] (1) In producing a hydroxyl group-containing liquid copolymer by copolymerizing a diene monomer and a vinyl monomer in the presence of hydrogen peroxide, the product obtained by the copolymerization reaction has a phenolic hydroxyl group. 1. A method for producing a hydroxyl group-containing liquid copolymer, which comprises treating with water containing a compound. (2) The method according to claim 1, wherein the diene monomer is butane diene and the vinyl monomer is acrylonitrile or styrene. (3) The method according to claim 1, wherein the compound having a phenolic hydroxyl group is pt-butylcatechol or 2,2'-methylenebis(4-ethyl-6-t-butylphenol). (4) The method according to claim 1, wherein the treatment with water containing a compound containing a phenolic hydroxyl group is carried out at a temperature of 10 to 200°C for 1 to 1000 minutes. (5) Water containing a compound having a phenolic hydroxyl group contains a compound having a phenolic hydroxyl group of 10 to 1000
The method according to claim 1, wherein the water contains 0 ppm. (6) In producing a hydroxyl group-containing liquid copolymer by copolymerizing a diene monomer and a vinyl monomer in the presence of hydrogen peroxide, the product obtained by the copolymerization reaction has a phenolic hydroxyl group. 1. A method for producing a hydroxyl group-containing liquid copolymer, which comprises treating with water containing a compound, followed by thin film evaporation. (7) The method according to claim 6, wherein the diene monomer is butadiene and the vinyl monomer is acrylonitrile or styrene. (8) The method according to claim 6, wherein the compound having a phenolic hydroxyl group is pt-butylcatechol or 2,2'-methylenebis(4-ethyl-6-t-butylphenol). (9) The method according to claim 6, wherein the treatment with water containing a compound having a phenolic hydroxyl group is carried out at a temperature of 10 to 200°C for 1 to 1000 minutes. (10) Water containing a compound having a phenolic hydroxyl group contains a compound having a phenolic hydroxyl group of 10 to 100%.
The method according to claim 2, wherein the water contains 00 ppm.