JPH0128052B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel basic copolymer and a method for producing the same. Polymers having basicity are used for various purposes by taking advantage of their basicity. For example, three-dimensional crosslinked polymers having basicity are widely used as cation exchange resins, and three-dimensional polymers such as dimethylaminostyrene, aminostyrene, and vinylpyridine are representative examples. Furthermore, linear polymers having basicity are also widely used as extraction agents. The present inventors conducted various studies on basic polymer compounds, and as a result, discovered the novel basic copolymer shown below. The novel copolymer according to the present invention has the structural formula ()
It is a copolymer consisting of repeating structural units represented by the structural formula ().

【formula】

[Formula] (wherein A and B represent hydrogen, an alkyl group having 1 to 17 carbon atoms, an aryl group, an aralkyl group, a pyridyl group, or a nitro group, and X and Y represent hydrogen,
Alkyl group or haloalkyl group having 1 to 10 carbon atoms, halogen, cyano group, aryl group, halogenophenyl group, alkylphenyl group having 1 to 5 carbon atoms or haloalkylphenyl group, COOR ₁ (R ₁ is hydrogen or to 10 hydrocarbon groups), COR ₂
(R ₂ is a hydrocarbon group having 1 to 10 carbon atoms), OCOR ₃
(R ₃ is a hydrocarbon group having 1 to 10 carbon atoms), CONHR ₄
(R ₄ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms),
Represents an imidazole group, pyridyl group or carbazole group. ) The copolymer of the present invention can be obtained by copolymerizing a monomer represented by the structural formula () and a monomer represented by the structural formula ().

【formula】

[Formula] (A, B, X and Y are the same as above.) The monomer represented by the structural formula () can be obtained from, for example, halogenomethylstyrene and imidazole or a derivative thereof. (A and B are the same as above.) A specific example is 1-(metastyryl)
Methyl-2-ethyl-4(5)-methylimidazole, 1-(para-styryl)methyl-2-ethyl-4(5)-methylimidazole, 1-(meth-styryl)methyl-2-benzyl-4( 5)-Methylimidazole, 1-(para-styryl)methyl-2-
Benzyl-4(5)-methylimidazole, 1-(meth-styryl)methyl-2-pyridyl-4(5)-methylimidazole, 1-(para-styryl)methyl-2-pyridyl-4(5)-methyl imidazole,
1-(meth-styryl)methylimidazole, 1
-(para-styryl)methylimidazole, 1-
(Meta-styryl)methyl-2-methylimidazole, 1-(para-styryl)methyl-2-methylimidazole, 1-(para-styryl)methyl-2-undecylimidazole, 1-(meth-styryl)methyl- Examples include 2-heptadecylimidazole, 1-(para-styryl)methyl-2-phenylimidazole, and 1-(para-styryl)methyl-5-nitroimidazole. The positions of the two substituents with respect to the benzene nucleus in the structural formula () of the copolymer may be any of the ortho, meta, and para positions, but the meta and/or para positions are preferred. Further, copolymers in which A and B are hydrogen, methyl group, ethyl group, benzyl group, pyridyl group, or nitro group, and copolymers in which either A or B is at the 2-position of the imidazole ring are preferred. Examples of monomers represented by structural formula () are:
Hydrocarbon compounds such as styrene, methylstyrene, diphenylethylene, ethylstyrene, dimethylstyrene, vinylnaphthalene, vinylphenanthrene, vinylmesitylene, 3,4,6-trimethylstyrene; chlorstyrene, methoxystyrene, bromustyrene, cyano Styrene derivatives such as styrene, fluorostyrene, dichlorostyrene, chloromethylstyrene, trifluorostyrene, trifluoromethylstyrene; acrylonitrile derivatives such as acrylonitrile, methacrylonitrile, α-acetoxyacrylonitrile; acrylic acid, methacrylic acid; acrylic acid Acrylic acid esters such as methyl, lauryl acrylate, chloromethyl acrylate, and ethyl acetoxyacrylate;
Methacrylic acid esters such as cyclohexyl methacrylate; diethyl maleate, diethyl fumarate; vinyl ketones such as methyl vinyl ketone and ethyl isopropenyl ketone; vinylidene compounds such as vinylidene chloride, vinylidene bromide, and vinylidene cyanide; acrylamide, methacrylamide, N
- Acrylamide derivatives such as phenylacrylamide; fatty acid vinyl derivatives such as vinyl acetate, vinyl butyrate, and vinyl caprate; and heterocyclic vinyl derivatives such as N-vinylcarbazole, vinylimidazole, methylvinylimidazole, vinylpyridine, and methylvinylpyridine. Compounds, etc. Among these, X and Y are hydrogen, cyano group, chloro group, methyl group, phenyl group, and COOH,
More preferred are COOMe, COMe, OCOMe, CONH ₂ . The copolymer of the present invention has the structural formulas () and ()
There are no particular restrictions on the polymerization method used for production using the monomers represented by the formula, and polymerization by heating is sufficient, but it is often preferable to use a polymerization initiator. The polymerization initiators used include acyl peroxides such as benzoyl peroxide and lauroyl peroxide, azobisisobutyronitrile,
Azonitriles such as 2,2'-azobis(2,4-dimethylmaleronitrile), peroxides such as ditertiary butyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, tertiary hydroperoxide, etc. Hydroperoxides. The polymer in the present invention can also be produced by polymerizing in the presence of an inert liquid. Inert liquids include aliphatic hydrocarbons such as normal pentane, normal hexane, normal heptane, and normal octane, alcohols such as methanol, ethanol, and isopropyl alcohol, acetone, methyl ethyl ketone,
Ketones such as diethyl ketone, diethyl ether, methyl ethyl ether, dibutyl ether,
Ethers such as dioxane and tetrahydrofuran, aromatic hydrocarbons such as benzene, toluene and xylene, esters such as ethyl formate, ethyl acetate and butyl acetate, amides such as dimethylformamide and dimethylacetamide, chloroform and methylene chloride. , aliphatic halides such as dichloroethane, aromatic halides such as chlorobenzene, and polar liquids such as dimethyl sulfoxide can also be used. These liquids can be used alone or as a mixture of two or more liquids. There is no limit to the reaction temperature, but it is preferably about 20°C to 120°C, more preferably 60°C to 100°C.
That's about it. Since the copolymer of the present invention has an imidazole group in its side chain, it has been found that it can be used as a metal extraction agent and as a paint material. Also, surprisingly, this anionic polymer had a suitable affinity for organic anions such as alkyl sulfonic acids compared to other known anionic polymers. Examples of the present invention are shown below, but these are not intended to limit the present invention. Example 1 6.39 g of imidazomethylstyrene (mixture with m/p ratio of 60/40), 3.61 g of styrene, and 0.1 g of azobisisobutyronitrile were mixed in a 30 ml ampoule tube, and the inside of the ampoule tube was purged with nitrogen. After that, the tube was sealed. After immersing this in a 90°C water bath for 24 hours, the sealed tube was broken and the solidified contents were taken out. The main peaks in the elemental analysis and infrared absorption spectrum of this product are as follows. Elemental analysis values: The values in parentheses represent theoretical values. C; 83.15 (83.30), H; 7.00 (6.99), N; 9.85
(9.71) Infrared absorption spectrum; unit cm ^-1 712, 815, 905, 1030, 1078, 1106, 1275,
1438, 1501, 1601, 2950, etc. Total amount of solid obtained is 10.0g (yield 100%)
It was hot. When 0.5 g of the obtained solid was mixed with 100 ml of 2N hydrochloric acid, all of the solid dissolved.
There was no oily liquid floating on the surface of the hydrochloric acid. In the infrared absorption spectrum, the peak due to the carbon-carbon double bond completely disappeared, and it was concluded that the solid obtained from the above hydrochloric acid dissolution test was a copolymer of imidazomethylstyrene and styrene. It was done. When the viscosity of a hydrochloric acid solution was measured at 25℃,
[η]=0.58. 1 g of this copolymer and ferric chloride (molecular formula:
0.270 g of FeCl ₃ .6H ₂ O) was dissolved in 2N hydrochloric acid to make a total volume of 50 c.c. After extracting this solution five times with 50 c.c. of chloroform, the iron concentration in the hydrochloric acid was measured and found to be 1 mmol/. On the other hand, when chloroform extraction was performed on a similar hydrochloric acid solution of ferric chloride that did not contain this copolymer, the iron concentration was 19 mmol/min, and the concentration hardly changed before and after the extraction. These results indicate that this polymer can be used as an extractant for metals. Examples 2 to 24 Copolymerization of the monomer represented by the structural formula () and the monomer represented by the structural formula () was carried out by a method substantially similar to that in Example 1. Some of these are listed in Table 1.

【table】

【table】

【table】

【table】

【table】

Claims (1)

[Scope of Claims] 1. A copolymer consisting of a repeating structural unit represented by the following structural formula () and a repeating structural unit represented by the structural formula (). [Formula] [Formula] (wherein A and B represent hydrogen, an alkyl group having 1 to 17 carbon atoms, an aryl group, an aralkyl group, a pyridyl group, or a nitro group, and X and Y represent hydrogen,
Alkyl group or haloalkyl group having 1 to 10 carbon atoms, halogen, cyano group, aryl group, halogenophenyl group, alkylphenyl group having 1 to 5 carbon atoms or haloalkylphenyl group, COOR ₁ (R ₁ is hydrogen or to 10 hydrocarbon groups), COR ₂
(R ₂ is a hydrocarbon group having 1 to 10 carbon atoms), OCOR ₃
(R ₃ is a hydrocarbon group having 1 to 10 carbon atoms), CONHR ₄
(R ₄ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms),
Represents an imidazole group, pyridyl group or carbazole group. ) 2 The copolymer according to claim 1, wherein in the structural formula (), the positions of the two substituents relative to the benzene nucleus are meta, para, or a mixture thereof. 3. The copolymer according to claim 1 or 2, wherein A and B are hydrogen, methyl group, ethyl group, benzyl group, pyridyl group, or nitro group. 4 Either A or B is an imidazole ring 2
A copolymer according to any one of claims 1 to 3, located in the following positions. 5 X and Y are hydrogen, cyano group, chloro group, methyl group, phenyl group, and COOH, COOMe,
Copolymers according to claims 1 to 4, which are COMe, OCOMe, CONH ₂ . 6 A repeating structural unit and structural formula represented by the following structural formula () characterized by copolymerizing a basic monomer represented by the following structural formula () and a monomer represented by the structural formula (). A method for producing a copolymer consisting of repeating structural units shown in parentheses. [Formula] [Formula] [Formula] [Formula] (wherein A and B represent hydrogen, an alkyl group having 1 to 17 carbon atoms, an aryl group, an aralkyl group, a pyridyl group, or a nitro group, and X and Y are hydrogen ,
Alkyl group or haloalkyl group having 1 to 10 carbon atoms, halogen, cyano group, aryl group, halogenophenyl group, alkylphenyl group having 1 to 5 carbon atoms or haloalkylphenyl group, COOR ₁ (R ₁ is hydrogen or to 10 hydrocarbon groups), COR ₂
(R ₂ is a hydrocarbon group having 1 to 10 carbon atoms), OCOR ₃
(R ₃ is a hydrocarbon group having 1 to 10 carbon atoms), CONHR ₄
(R ₄ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms),
Represents an imidazole group, pyridyl group or carbazole group. ) 7. The method for producing a copolymer according to claim 6, wherein the copolymerization is carried out in the presence of a polymerization initiator. 8. A method for producing a copolymer according to claims 6 and 7, wherein the copolymerization is carried out in the presence of an inert liquid.