JPS63122709A - Production of amino group-containing 1,2-polybutadiene - Google Patents

Abstract

PURPOSE:To readily obtain, using a simple system, the titled polybutadiene having anion exchange capability, high in ion exchange capacity, good in heat resistance and durability, by addition of a halogen (compound) to a specific polybutadiene followed by reaction with an amino compound. CONSTITUTION:An addition reaction is carried out pref. at -20-150 deg.C between (A) a polybutadiene having >=70wt% (pref. >=80wt%) of vinyl bond and (B) a halogen (compound) (pref., chlorine, in such an amount as to be >=30mol% based on the double bond in said polybutadiene) followed by reaction with an amino compound (pref., trimethyl-amino) pref. at -20-150 deg.C, thus obtaining the objective polybutadiene suitable for the production of demineralized water, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing 1,2-polybutadiene containing amino groups capable of exchanging anions.

[Conventional technology]

Currently, ion exchange resins are used in many ways, including removing dissolved cations or anions, producing highly pure water, and removing and recovering harmful metals from industrial wastewater.

However, as an anion exchange resin, a spherical styrene resin made by copolymerizing styrene with divinylbenzene as a crosslinking agent is reacted with chloromethyl ether using tin chloride as a catalyst, and then chloromethylated with a methylamine aqueous solution. Polystyrene resins that have been subjected to quaternary amination are mainly used.

However, the heat resistance and durability and ion exchange rate were not necessarily sufficient.

On the other hand, as a reaction for aminating 1,2-polybutadiene, A. Ban5leben et al. (American Chemical Society Abstracts, p. 106, 1985 Spring Meeting) carried out the Lefpe reaction to add amino groups to side chains. There is no mention of the ion exchange ability of aminated 1,2-polybutadiene, so its ability as an ion exchange resin is unknown.

The reaction of D, A, Ban51eben et al. is a method in which carbon oxide and dimethylamine are reacted at high temperature and high pressure, and there are many difficulties in industrial production. Moreover, when produced on an industrial scale, it has the disadvantage that a large amount of cost is required for reaction equipment.

On the other hand, the present inventors proposed a method for producing sulfonated 1,2-polybutadiene having a rapid ion exchange rate by sulfonating 1,2-polybutadiene, and filed a patent application.

He also proposed a method for producing an ion exchange membrane with heat resistance and durability by sulfonating a mixture of 1,2-polybutadiene and polyolefin, and filed a patent application.

Ion-exchange resins are generally used to exchange both anions and cations, and it is industrially meaningful to use the anion-exchange resin of the present invention and the cation-exchange resin of the previously filed application together.

[Problem that the invention seeks to solve]

An object of the present invention is to provide a method for easily producing amino group-containing 1,2-polybutadiene having a high ion exchange capacity and anion exchange ability using simpler reaction equipment than known methods.

[Means for solving problems]

According to the invention, the vinyl bond is 70% or more, preferably 8
A method for producing amino group-containing 1,2-polybutadiene is provided, which comprises adding a halogen or a halogen compound to polybutadiene containing 0% or more, and then reacting with an amino compound.

1.2 The crystallinity of polybutadiene is not particularly limited when reacting in a solution state, but when reacting in a powder state, the crystallinity should be 15 to avoid problems such as powder sticking. % or more, more preferably 17 to 50%.

1.2 When polybutadiene is used in the reaction as a powder, the average particle diameter is preferably 500 μm or less, particularly several tens of μm or less. If the average particle size is large, the reaction will be non-uniform;
This results in an unreacted portion inside.

There are no particular restrictions on the method for producing powdered 1,2-polybutadiene, but there are methods such as pulverization using mechanical impact force, or dissolving 1,2-polybutadiene in a solvent in advance and then dissolving it in the presence of water and a dispersant. A method such as stirring is used. In this case, it is also possible to add peroxide during dispersion to effect crosslinking. Powdered 1,2-polybutadiene can also be obtained by suspension polymerization as disclosed in Japanese Patent Application No. 59-2575 or by emulsion polymerization as disclosed in Japanese Patent Application No. 59-142221.

Further, mixtures with polyolefins such as high-density polyethylene, low-density polyethylene, linear low-density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polyvinyl chloride, and polyvinylidene chloride can also be used.

Further, polyolefin mixtures such as high density polyethylene, low density polyethylene, linear low density polyethylene, polypropylene, ethylene vinyl acetate copolymer, polyvinyl chloride, and polyvinylidene chloride can also be used.

The method for adding a halogen or a halogen compound to the halogen of the 1,2-polybutadiene is not particularly limited, and any known method for halogenating olefin double bonds can be used.

In the case of the present invention, for example, a solid of 1,2-polybutadiene (
A halogen or a halogen compound can be added by reacting a halogen or a halogen-containing compound with a halogen or a halogen-containing compound (lump, granule, powder), a solution dissolved in a solvent, or a solution dissolved in a solvent.

The amount of halogen or halogen compound added is preferably as large as possible when used as an ion exchanger, but usually 1
．． The amount is 20 mol% or more, more preferably 30 mol% or more, based on the double bonds of 2-polybutadiene.

Furthermore, when reacting 1,2-polybutadiene in a solution state, there are no particular restrictions on the solvent as long as it does not react with halogen compounds or amino compounds, but halogenated solvents such as 1,2-diglolethane, tetrachlorethylene, carbon tetrachloride, etc. Hydrocarbons are preferred.

1.2 The concentration of polybutadiene is 1 to 50% by weight
is preferable, and more preferably 3 to 30% by weight.

1.2 Compounds that halogenate polybutadiene include 1. Single halogens such as chlorine, bromine, and iodine; halogens such as bromine chloride, iodine chloride, and iodine fluoride; halogen acids such as hydrochloric acid, hydrochloric acid, and hydrogen iodide; halogens such as potassium iodide, sodium iodide, and potassium bromide; salt, N-
Examples include halogenating agents such as bromoacetamide and N-bromosuccinimide, halogenated ether compounds such as chloromethyl methyl ether, chloromethyl ethyl ether, and chloromethyl propyl ether, and halogenated alkyl compounds such as chloroform and carbon tetrachloride. I can do it. Among these, chlorine, bromine and chloromethyl methyl ether are preferred.

Next, 1, 2 with added halogen or halogen compound
- Polybutadiene is aminated by reacting with amines.

Amine compounds for amination reactions include methylamine, ethylamine, propylamine, butylamine,
Primary amines such as 5ec-butylamine, secondary amines such as dimethylamino, diethylamine, dipropylamine, methylethylamine, ethylpropylamine,
Examples include tertiary amines such as trimethylamine, triethylamine, tripropylamine, and tributylamine. Among these amino compounds, tertiary amino compounds are preferred.

Furthermore, diamino compounds to which two or more tertiary amino compounds are added, such as tetramethyldiaminomethane, bis(dimethylamino)methane, tetramethyl, ethylenediamine, tetramethylbutanediamine, and diaminopropane, are also preferred.

The temperature during the halogen addition reaction and amination reaction is from -50°C to 200°C, preferably from -20°C to 150°C.
It is.

Since the amino group-containing 1゜2-polybutadiene obtained by the method of the present invention usually has a high anion exchange capacity of 1.5 milliequivalent M/g or more, it can be used as an ion exchange resin for the production of pure water. It is used for the softening of hard water, separation, recovery and analysis of anions, and treatment of plating wastewater, etc. It can also be used as an ion exchange membrane by blending with other resins or rubbers, or to improve the conductivity of resins and rubbers. can.

〔Example〕

Examples of the present invention will be described below, but the present invention is not limited thereto. In addition, "part" and "%"
indicates weight parts and weight %.

Example [Production of amino group-containing 1.2 polybutadiene]: 1.
2-Polybutadiene (manufactured by Japan Synthetic Rubber Co., Ltd., trade name RB8)
30; 1,2 bond content: 93%, crystallinity: 29%) was crushed by applying mechanical impact to obtain a powder with an average particle diameter of 25 mμ.

Put 800 mf of methylene chloride and 100 g of bromine into a 2000-ml flask and cool to 10°C.
After slowly adding 17 g of polybutadiene with stirring, the temperature was raised to room temperature and the reaction was continued for an additional 24 hours. After 24 hours, leave to stand and remove the supernatant, add 2Il of methyl alcohol.
was added and stirred to remove unreacted bromine. The washing operation was repeated four more times, and vacuum drying was performed at 60°C. Bromination 1
, 2 polybutadiene (48.7 g) was obtained. The results of elemental analysis were 3.1% hydrogen, 27.3% carbon, and 69.3% bromine.

After contacting 1,3-diaminopropane 5- with 0.1523 g of the above-mentioned brominated 1,2-polybutadiene at room temperature for 90 hours, 100 ml of methyl alcohol was added to unreacted 1.
3-diaminopropane was removed. After repeating the washing operation four times, the product was vacuum dried and the anion exchange capacity was determined to be 3.4 milliliter It/g.

(Measurement is from "Original Experimental Method" Kitami Shobo, Masayuki Nakagaki (1)
984) See page 194) Example 2 When the crystallinity of the 1.2 polybutadiene in Example 1 was changed to 15% JSRRB 810 and the reaction was carried out in the same manner as in Example 1, the ion exchange capacity was 3.1 meq/g. An anion exchange resin was obtained.

Example 3 1,2-polybutadiene was chloromethylated using chloromethyl methyl ether and tin chloride as halogenating agents, and then aminated using 1,3-diaminopropane.

40 ml of chloromethyl ether and 4 ml of tin tetrachloride were added to a 100-bar flask, and 1 g of the 1,2-polybutadiene powder of Example 1 was added thereto. After reacting at room temperature for 24 hours, washing with methanol was repeated. After vacuum drying, 1.
It was fused with 10 g of 3-diaminopropane and left to stand for 90 hours. After washing with methanol, the ion exchange capacity was determined to be 2.8 milliequivalents/g.

Effects of the invention 1. By adding a halogen or a halogen compound to 2-polybutadiene and then reacting it with an amino compound, high ion exchange can be achieved with simple equipment because known reaction conditions of high pressure and high temperature are not required. It is possible to produce polybutadiene with the following properties.

In addition, the amino group-containing 1,2-polybutadiene obtained by the present invention has a high ion exchange rate and good heat resistance and durability, so it can be subjected to ion exchange treatment at relatively high temperatures, and the treatment rate is therefore extremely high. Highly efficient processing is possible.

The amino group-containing 1,2-polybutadiene obtained by the present invention is expected to form a pair when used in combination with the sulfonated 1,2-polybutadiene of the previous application and be used as an industrially excellent ion exchange resin. .

Claims (1)

[Claims] 1 having an amino group, which is characterized by adding a halogen or a halogen compound to polybutadiene containing 70% or more of vinyl bonds, and then reacting it with an amino compound.
, 2-polybutadiene manufacturing method