JPS5915926B2 - Method for producing polymers with reactive aromatic systems - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention enables multilateral chemical modification of the system.
- This invention relates to a synthetic polymer having a phenylenediamine skeleton in its side chain and a method for producing the same.

The production of modified polymers has undergone rapid development due to the interest in reactive functional group-containing polymers as raw materials for a large number of products of technical and application importance.

These polymers are prepared, on the one hand, by carrying out subsequent chemical reactions to modify the basic polymer backbone, or, on the other hand, by combining suitable monomers with possible reactants in further reactions. 0
It is prepared by copolymerizing with a reactive group. The preformed polymers undergo further chemical changes and are converted into substances useful for biochemical and industrial applications. ■5 These were developed as substances with an aliphatic or aromatic primary amino group in their side chains. It is useful for the purpose of coupling with suitable types of substrates.

However, many of these systems are used only for specific applications. In addition, the reaction for denaturation lacks quantitative
In some reactions, incomplete products may be produced due to unfavorable reactivity of the corresponding copolymerizable monomer.
It can only be 5. The object of the present invention is to solve the following general formula I (wherein, R1 is a hydrogen atom or a methyl group, R2
is an alkyl group having 1 to 6 carbon atoms, R3 is an acyl group, carpoxyl group or sulfo group, and Ar is a phenylene residue.

) and having a reactive aromatic system in its side chain. The polymer according to the present invention is produced by combining a monomer represented by the following general formula (however, the meaning of each symbol is the same as above) in the presence of a free radical polymerization initiator, at or below the decomposition temperature of the initiator. It is prepared by free radical polymerization at the above temperature.

Other comonomers include methacrylic or acrylic monomers, such as acrylamide, methacrylamide, acrylic acid, methacrylic acid, or esters thereof, and vinyl compounds such as butadiene, isoprene, and styrene. is preferably used. The polymerization is conveniently carried out in the presence or suspension of a polymer solvent and a precipitant so as to form porous polymer particles having a large internal surface area.

The present invention provides for the preparation of polymers which, due to their chemical reactivity due to their conjugated nitrogen-containing groups, allow several reactions aimed at producing products with special properties. Regarding the polymerization reactivity ratio, the above-described structural material having a high content of reactive groups can be adjusted by using acrylates and methacrylates.

Copolymers can also be prepared with other types of monomers, such as styrene, divinylbenzene and its derivatives, isoprene, butadiene, and the like. Preferred characteristics of the reaction system are hydrophilic monomers, such as esters having a hydroxyl group in the side chain such as glycol, polyglycol or glycerin esters, acrylamide, methacrylamide or N- This is a copolymerization reaction with amides such as substituted acrylamide and methacrylamide, as well as methacrylic acid and acrylic acid. The preparation of a copolymer with a three-dimensional network structure obtained by a copolymerization reaction with multi-bond monomers such as divinylbenzene, ethylene glycol dimethacrylate, or methylene bisacrylamide produces insoluble homogeneous or heterogeneous copolymers. A combined product is obtained.

When carried out in the presence of suitable solvents, polymers with large internal surface areas and porosity are formed, and these physical properties can dictate various uses of the product, e.g. in the form of small spherical particles. Once prepared, it can be used for chromatography, catalysis, and even ion exchange. These preformed polymers can also undergo further chemical modification to convert them into materials useful for biochemical and industrial applications. The monomer having a p-phenylenediamine skeleton of the general formula described above is a chloride of an unsaturated organic acid (for example, acryloyl chloride or methacryloyl chloride).
and the following types of hydroxy derivatives of p-phenylenediamine.

However, the free primary amino group must be blocked with an acyl group, carboxyl group or sulfo group by a known reaction such as acylation.

The above monomers can also be synthesized by the synthesis of N-alkylanilines or ethoxylated derivatives of anilines, followed by nitrosation, reduction and subsequent reaction with chlorides of unsaturated organic acids, such as acryloyl chloride or methacryloyl chloride. It is also prepared by

Many starting compounds can be employed for the preparation of this monomer.

First, it is a simple basic raw material, such as a common compound of the phenylenediamine type, which is often used in photographic chemistry. A feature of this type of monomer is that it has a suitable copolymerization reactivity ratio with conventional monomers.

These are simultaneously prepared as mono- or difunctional monomers and are used as a result for the production of solvent-soluble linear polymers and for the production of insoluble crosslinked polymers.
The polymer according to the present invention can be effectively used as an ion exchanger, a catalyst for chemical reactions, biochemical applications, and the like.

Methods for synthesizing monomers and polymers having a p-phenylenediamine skeleton are further explained in the following examples, but the present invention is not limited to these examples. Monomer synthesis example 1 N-ethyl-N-(2-hydroxyethino(c)-p-
Phenyl diamine (5609) was dissolved in 211 water at 45°C, 2309 acetic anhydride was added under stirring, and the mixture was neutralized with sodium hydroxide and made alkaline (PH=9).

After dilution with three volumes of water, a crystalline product (melting point 133° C.) was obtained, which was further reacted with methacryloyl chloride (10% excess) in anhydrous pyridine medium.

Methacryloyl chloride was added to the reaction mixture within 1 hour at 5°C, and the reaction was then stirred for 10 hours while maintaining the temperature at 25-30°C. After dilution with 5 times water, the oil was separated and recrystallized from a mixture of toluene and ethanol/water to obtain a crystalline product (melting point 93-94°C).

Monomer Synthesis Example 2 Synthesis except that acetate, sulfate or hydrochloride of N-ethyl-N-(2-hydroxyethyl)-p-phenylenediamine was used as a starting material and reacted with methacryloyl chloride. Monomers were prepared in the same manner as in Example 1.

Monomer synthesis example 3 N-ethylaniline (0.5 mol) was mixed with 0.6 mol of ethylene oxide in an autoclave, then
Seal, pressurize to 30 atm with nitrogen, and heat at 130℃ for 2 hours.
heated for an hour.

The ethoxyethylated product was obtained in 95% yield based on N-ethylaniline. This product was subjected to a nitrosation reaction with sodium nitrite at a temperature of 5°C, and then
It was reduced with tin in hydrochloric acid, and then methacrylated in the same manner as in Synthesis Example 1. Example 1 N-ethyl-N-(2-methacryloylethyl)-N'
-Acetyl-p-phenylenediamine 59 was dissolved in 109 of methyl cellosolve and 0.019 of azobisisobutyronitrile was added.

The mixture was flushed with nitrogen and polymerized at 60°C. The obtained polymerization reaction solution was diluted with ether and subjected to precipitation. The polymer was soluble in methyl cellosolve, acetone and dilute acid. Example 2 N-ethyl-N-(2-methacryloylethyl)-N1
-acetyl-P-3 phenylenediamine 2.69.
79 ethylene glycol monomethacrylate and 0
．． 19 of azobisisobutyronitrile.

The polymerization reaction at 50°C gave a hard, glossy material.

Example 3 1 g of N-ethyl-N-(2-methacryloylethino(c)-V-acetyl-P-phenylenediamine) was dissolved in 49 methyl methacrylate, and 1.3% by weight of azobisisobutyronitrile was dissolved. added.

The mixture was sealed in an ampoule under nitrogen and heated to 50°C.
After 10 hours of polymerization reaction, a glassy polymer plug was obtained. Example 4 N-hydroxyethyl-N-(2-methacryloylethyl)-N'-acetyl-p-phenylenediamine 1.5
9 was dissolved in 4.59 parts of ethylene glycol monomethacrylate and 0.0069 parts (i.e., 0.1% by weight) of azobisisobutyronitrile was added.

The mixture was transferred to a polymerization mold formed by two parallel plates. After a polymerization reaction at 60°C for 8 hours,
The polymer was obtained as a uniform plate.

Example 5 31.99 ethylene glycol dimethacrylate, 2
9.49 ethylene glycol monomethacrylate, 2
Polymerization reaction consisting of 0.49 N-ethyl-N-(2-methacryloylethyl)-N'-acetyl-p-phenylenediamine and 0.829 (1% by weight per monomer) azobisisobutyronitrile The mixture was stirred with 98.5 g of cyclohexanol and 9.79 g of dodecanol in a reaction medium of 6009 water and 69 polyvinylpyrrolidone in a reactor, first at a temperature of 50° C. for 2 hours and then at 65° C. for 8 hours. The polymerization reaction was carried out at ℃.

Claims (1)

[Claims] 1 General formula II ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (II) (However, in the formula, R' is a hydrogen atom or a methyl group, and R^2 is a carbon number of 1
-6 alkyl group, R^3 is an acyl group, carboxyl group or sulfo group, and Ar is a phenylene residue. ), or copolymerized with an acrylic or methacrylic monomer, a vinyl monomer, a difunctional monomer, or an OH group-containing monomer. The following general formula I ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (However, in the formula, R^1, R^
2, R^3, and Ar are as described above).