CA1225798A - Basic polymer, a process for the preparation thereof and a use as ion exchange resin - Google Patents

Abstract

ABSTRACT

This invention relates to a novel basic polymer, a process for the preparation thereof and a use as an ion ex-change resin. More particularly, this invention relates to a linear homopolymer, linear copolymer and cross-linked co-polymer having pendant imidazolylmethylphenyl groups, a process for the preparation thereof and the use of the cross-linked copolymer as an ion exchange resin.

Description

~:2~7~

This invention relates to a novel basic polymer, a process for the preparation thereof and a use as an ion ex-change resin. r~ore particularly, this invention relates to a linear homopolymer, linear copolymer and cross-linked co-polymer having pendant imidazolylmethylphenyl groups, a process for the preparation thereof and the use of the cross-linked copolymer as an ion exchange resin.
Polymers having functional groups are employed for various purposes industrially by making use of their functions, for example, as medical materials, functional mem~ranes, various plastics, extracting materials and adsorbents. Many polymers having basic functional groups which act a role of the polymers in these fields are known and include, for example, polydimethylaminomethylstyrene, polystyrylmethyltrimethyl-ammonium chloride, polyimine, polyvinylpyridine, polyvinyl-carbozole, polyvinylimidazole and polyaminomethylacrylamide.
The chemical resistance and the thermal resistance of polymers, however, are not necessarily satisfactory.
In accordance with a first aspect of the present invention, there is provided a linear homopolymer of Formula (I):
H2--CH ~

(I) R2 ~ N~ R~ t ~2~5~

wherein Rl and R2 each independently represents a hydrogen atom~ a straight chain or branched alkyl group having 1 to 17 carbon atoms, a phenyl group unsubstituted or substituted with one or more sub-stituents selected from Cl-C8 straight chain or branched alkyl groups, halogen atoms and an amino group, a naphthyl group, an aralkyl group having as an alkyl moiety a Cl-C4 straight chain or branch-ed alkylene yroup and as an aryl moiety a phenyl group unsubstituted or substituted with one or more substituents selected from halogen atoms and an amino group, a pyridyl group unsubstituted or sub-stituted with one or more substituents selected from Cl-C4 straight chain or branched alkyl groups, halogen atoms and an amino group, or a nitro group;
and n is an integer of 5 to 20,000.
Preferred examples of Rl and R2 include a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a phenyl group, a benzyl group, a pyridyl group and a nitro group. Rl and R2 may be the same or dif-ferent.
The position of the imidazol-l-ylmethyl group rela-tive to the vinyl group in the linear homopolymer of Formula (I) may be the ortho-, meta- or para-position, and is prefer-ably the meta- or para position. It is preferred that Rl be located at the 2-position of the imidazole ring.

~L2~

In accordance with a second aspect of the present invention, there is provided a process for the preparation of the linear homopolymer of Formula (I) which comprises polymer-izing a basic compound of Formula (II):

CH2 -N ~
CH2 = CH ~ ~ (II) wherein R~ and R2 are the same as defined above.
In preparing the linear homopolymers of Formula (I), any of the conventionally employed polymerization procedures can be employed. The basic compound of Formula (II) can be heat-polymerized but it may be preferred that a polymerization initiator be added.
Exemplary polymerization initiators which can be employed in the present invention include acyl peroxides such as benzoyl peroxide and lauroyl peroxide; azonitriles such as azobisisobutyronitrile and 2,2'-azobis(2,4-dimethylmalero-nitrile); peroxides such as di-tert-butyl peroxide, dicumyl peroxide and methyl ethyl ketone peroxide; and hydroperoxides such as cumenyl hydroperoxide and tertiary hydroperoxide.
The amount of the polymerization initiator which can be em-ployed in this invention is ~enerally 0.01 to 5% by weight based on the weight of the basic compound of Formula (II).
A preferred amount is 0.1 to 2% by weight.
The linear homopolymer according to the present invention may be produced by conducting polymerization reac-~22~

tion either in the presence or absence OI an inert solvent.Exemplary inert solvents which can be employed include aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane and n-octane; alcohols such as methanol, ethanol and isopropyl alcohol; ketones such as acetone, methy] ethyl ketone and diethyl ketone; ethers such as diethyl ether, methyl ethyl ether, dibutyl ethers, dioxane and tetrahydrofuran; aromatic hydrocarbons such as benzene, toluene and xylenes; esters such as ethyl formate, ethyl acetate and butyl acetates;
amides such as dimethyl formamide and dimethyl acetamide;
halogenated aliphatic nydrocarbons such as chloroform, methylene chloride and dichloroethanes; halogenated aromatic hydrocarbons such as chlorobenzene; and sulfoxides such as dimethyl sulfoxide~
These solvents may be used either alone or in mixture. Pre-ferred inert solvents are water, acetone, methanol, ethanol, diethyl ether, ethyl acetate, chloroform, dimethylformamide and mixtures thereof.
The reaction temperature is not critical but the reaction may usually be carried out at a temperature of 20C
to 120C, preferably 60C to 100C.
The linear homopolymer according to the present invention is useful as an extractant of metals and coating material. Surprisingly, the linear homopolymer according to the present invention has more adequate affinity to organic anions such as alkylsulfonic acid than generally known basic polymers. Further, the linear homopolymer according to the i~.22~9~

present invention surprisingly has greater resistance to oxida-tion than known amino group-containing po:Lymers such as polyvinyl-imidazole.
In accordance with a third aspect of the present invention, there is provided a linear copolymer comprising 95 to 5% by weight of recurring units of Formula (I'), (I') ~ N Rl wherein Rl and R2 are the same as defined above, and 5 to 95~ by weight of recurring units of Formula (III), Rl3 - CH2- C - (III) ~herein R3 and R4 each independently represents a hydrogen atom, a halogen atom, a cyano group, an aryl group, a halogenophenyl group, a phenyl group sub-stituted with one or more substituents selected from C,-Cs straight chain or branched alkyl or haloalkyl groups, alkoxy groups and a cyano group, -COOAl in which Al represents a hydrogen atom or a C~-C~0 hydrocarbon or halogenated hydrocarbon residue, -COA2 in which A2 represents a C~-Cl0 hydrocarbon residue, -OCOA3 in which A3 represents a Cl-C~0 25~

hydrocarbon residue, -CONHA4 in which A4 represents a hydrogen atom or a Cl-C~ D hydrocarbon residue, an imidazolyl, pyridyl and carbazolyl groups which are unsubstituted or substituted with a C~-C4 alkyl group, based on the total weight of the recurring units of Formula (I') and Formula (III).
In accordance with a fourth aspect of the present invention, there is provided a process for the preparation of the linear copolymer comprising 95 to 5% by weight of the re-curring units of Formula (I') and 5 to 95% by weight of the recurring units of Formula (III) based on the total weight of the recurring units of Formula (I') and Formula (III), which comprises copolymerizing 95 to 5% by weight of the basic com-pound of Formula (II), and 5 to 95% by weight of a monomer of Formula (IV), CH2= (IV) wherein R3 and R4 are the same as defined above, based on the total weight of the basic compound of Formula (II) and the monomer of Formula (IV).
In accordance with a fifth aspect of the present invention, there is provided a cross-linked copolymer comprising 99 to 40% by weight of the recurring units of Formula (I'), and 1 to 60% by weight of either or both of the recurring units of Formula (V) and Formula (VI), ~L225~7~8 Rs Rs --CH2--C --C~2--C-- CH2 16 R8 -C - Rg (V) (VI) wherein Rs~ R7 and Rg each independently represents a hydrogen atom or a methyl group; and R6 represents wherein Zl and Z2 each lndependently Z2 represents a hydrogen atom.oraC~-CS hydro-carbon residue; ~

- Dl ~ wherein Dl represents -O-, -S-, -NH- or a Cl-Cs alkylene group;
O O
-SO-; -CO-; ~ ~ ; -CH2-NH-CH2-; -CH20C--COCH2-, -CH20CBlCoCH2- wherein Bl represents a divalent C~-C8 hydrocarbon residue; 1l wherein B2 represents a divalent Cl-Cs hydrocarbon residue; or O O
-CNH-B3-NHC- wherein B3 represents a divalent C1-C3 hydrocarbon residue; and R8 represents B4 Bs wherein s., and Bs each independently represents a hydrogen atom or a. Cl-Cs hydrocarbon residue;

7~

-CH2 - N - CH2- or I -H2CO ~ OCH2-based on the total weight of the recurring units of Formula (I'), Formula (V) and Formula (VI).
In accordance with a sixth aspect of the present in-vention, there is provided a process for the preparation of the cross-linked copolymer comprising 99 to 40% by weight of the recurring units of Formula ~I') and 1 to 60% by weight of either or both of the recurring units of Formula (V) and Formula (IV) based on the total weight of the recurring units of Formula (I'), Formula (V) and Formula (IV) which comprises 99 ~o 60~ by weight of the basic compound of Formula (II) with 1 to 40~ of at least one of a monomer of Formula (VII) and a monomer of Formula (VIII), " Rs Rs CH2 =C CH2= C Rg ~6 Ra - C =CH2 CH2 =C CH2= C
`I I

(VII) (VIII) based on the total weight of the basic compound of Formula (II), the monomer of Formula (VII) and the monomer of Formula (VIII).
In the recurring units of Formula (I') in the above described linear copoIymer and the above described cross-linked copolymer, the imidazol-l-ylmethyl group may be located at the g ~L~Z5~98 ortho-, meta- or para-position relative to the vinyl moiety, but it is preferred that the group be located at the meta-or para-position. To obtain a preferred copolymer, Rl and R2 are expected to each independently represents a hydrogen atom, a methyl group, an ethyl group, a benzyl group, a pyridyl group or a nitro group, and either Rl or R2 is expected to be located at the 2-position of the imidazole ring.
Exemplary monomers of Formula (IV) which can be employed in the process according to the present invention include hydrocarbons such as styrene, methylstyrene, diphenylethylene, ethylstyrene, dimethylstyrene, vinyl-naphthalene, vinylphenanthrene, vinylmesitylene and 2,4,6-trimethylstyrene, chlorostyrene, methoxystyrene, bromostyrene, cyanostyrene, fluorostyrene, dichlorostyrene, chloromethyl-styrene, trifluorostyrene and trifluoromethylstyrene;
acrylonitriles such as acrylonitrile, methacrylonitrile, and ~-acetoxyacrylonitrile; acrylic acid, methacrylic acid;
acrylates such as methyl acrylate, lauryl acrylate, chloro-methyl acrylate and ethyl acetoxylacrylate; methacrylates 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;
acrylamides such as acrylamide, butyl acrylamide, octyl acrylamide, methacrylamide and N-phenylacrylamide; esters of vinyl alcohol and aliphatic acid such as vinyl acetate, ~L22S~
vinyl butyrate and vinyl caproate; heterocyclic vinyl com-pounds such as N-vinylcarbazole, vinylimidazole, methylvinyl-imidazole, vinylpyridine and methylvinylpyridine; and allyl halide such as allyl bromide.
Preferred examples of R3 and R4 in the recurring units of Formula (III) and Formula (IV) include a hydrogen atom, a cyano group, a chlorine atom, a methyl group, a phenyl group, a COOH group, a COOC~3 group, a COC~3 group, a OCOCH3 group and a CONH 2 group.
In the linear copolymer, the amount of the recurring units of Formula (I') may be optionally varied and typically ranges from 99 to ~0% by weight based on the total weight of the recurring units of Formula (I') and Formula (III).
Exemplary monomers of Formula (VII) an~ Formula (VIII) which can be employed in the process according to the present invention include divinylbenzene, divinyltoluene, divinylxylene, divinylethylbenzene, trivinylbenzene, divinyldiphenyl, divinyl-diphenylmethane, divinyldibenzyl, divinylphenyl ether, divinyl-diphenyl sulfide, divinyldiphenylamine, divinyl sulfone, divinyl ketone, divinylpyridine, diallyl phthalate, diallyl maleate, diallyl fumarate, diallyl succinate, diallyl oxalate, diallyl adipate, diallyl sebacate, diallylamine, triallylamine, N,N'-ethylenediacrylamide, N,N'-methylenediacrylamide, N,~'-methylene-dimethacrylamide, ethylene glycol dimethacrylate, ethylene glycol diacrylate, l,3-butylene glycol diacrylate and triallyl iso-cyanurate. These compounds may be used either alone or in mixture.

I' ~;2;25i7~3 In the cross-linked copolymer, the amount of either or both of the recurring units of Formula ~V) and Formula (VI) may be optionally varied and typically ranges l to 60% by weight based on the total weight of the recurring units of Formula ~I'), Formula (V) and Formula (VI). When the cross-linked copolymer is employed as an ion exchanger, the amount of either or both of the recurring units of Formula (V) and Formula (VI) preferably ranges from 3 to 40% by weight based on the total weight of the recurring units of Formula (I'~, Formula (V) and Formula (VI).
Furthermore, the cross-linked copolymer comprising the recurring units of Formula (I') and either or both Formula (V) and Formula (VI) according to this invention may contain another type of recurring units in such an amount that will not adversely affect the properties of the cross-lin]ced co-polymer. Usually, such additional recurring units may be added in an amount not exceeding 55% based on the total weight of the copolymer. Such additional recurring units may be afforded by adding another monomer having an unsaturated group in the copolymerization reaction. The kind of the additional monomer is not critical. Exemplary monomers which can be additionally incorporated in the copolymerization ac-cording to the present invention include hydrocarbons such as s-tyrene, methylstyrene, diphenylethylene, ethylstyrene, dirllethylstyrene, vinylnaphthalene, vinylphenanthrene, vinyl-mesitylene, 2,4,6-trimethylstyrene, l-vinyl-2-ethylacetylene, ;25~
butadiene, isoprene and piperylene; styrene derivatives such as chlorostyrene, rnethoxystyrene, bromostyrene, cyanostyrene, fluorostyrene, dichlorostyrene, chloromethylstyrene, tri-fluorostyrene, trifluoromethylstyrene, N,N-dimethylaminostyrene, nitrostyrene and aminostyrene; vinyl sulfides such as methyl vinyl sulfide and phenyl vinyl sulfide; acrylonitriles such as acrylonitrile, methacrylonitrile and ~-acetoxyacrylonitrile;
acrylic acid, methacrylic acid; acrylates such as methyl acrylate, lauryl acrylate, chloromethyl acrylate and ethyl acetoxylacrylate; methacrylates such as cyclohexyl methacrylate, dimethylaminoethyl methacrylate, glusidyl methacrylate, tetra-hydrofurfuryl methacrylate and hydroxyethyl methacrylatei diethyl maleate, diethyl fumarate; vinyl ketones such as methyl vinyl ketone and ethyl isopropenyl ketone; vinylidene compounds such as vinylidene chloride, vinylidene bromide and vinyliden.e cyanide; acrylamides such as acrylamide, methacrylamide, N-phenylacrylamide, N-butoxymethylacrylamide, diacetonacrylamide and N,N-dimethylaminoethylacrylamide;
esters of vinyl alcohol and aliphatic acid such as vinyl acetate, vinyl butyrate and vinyl caprylate; thioesters such as phenyl thiomethacrylate, methyl thioacrylate and vinyl thioacetate; and heterocyclic vinyl compounds such as N-vinylsucc.inimide, N-vinylpyrrolidone, N-vinylphthalimide, N-vinylcarbazole, vinylfuran, 2-vinylbenzofuran, vinyl-thiophene, vinylimidazole, methylvinylimidazole, vinyl pyrazole, vinyl oxazolidone, vinylthiazole, vinyltetrazole, ~2~5~

vinylpyridine, methylvinylpyridine, 2,4-dimethyl-6-vinyl-triazine and vinylquinoline.
In copolymerizing the basic compound of Formula (II) with the monomer of Formula (IV) or the basic compound of Formula (II) with at least one of the monomer of Formula (VII) and the monomer of Formula (VIII), and if desired, the above described monomer of another type, any of the conventionally employed polymerization procedures can be employed. A mixture of the monomers can be heat polymerized, but it may be pre-ferred that a polymerization initiator be added. Exemplary polymerization initiators employed according to the present invention include acyl peroxides such as benzoyl peroxide and lauroyl peroxide; azonitrlles such as azobisisobutyro-nitrile and 2,2'-azobis(2,4-dimethylmaleronitrile); peroxides such as ditert-butyl peroxide, dicumyl peroxide and methyl ethyl ketone peroxide; and hydroperoxides such as cumenyl hydroperoxide and tertiary hydroperoxide. The amount of the polymerization initiator which can be employed in this inven-tion is generally 0.01 to 5% by weight, preferably 0.1 to 2%
by weight:on the totaI weight of the monomers employed.
The copolymers according to the present invention may be produced by performing copolymerization reaction either in the absence of or in the presence of an inert solvent.
As the inert solvent, there can be mentioned, for example, aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane and n-octane; alcohols such as methanol, ethanol and isopropyl -- 1~ --9~3 alcohol; ketones such as acetone, methyl ethyl ketone and diethyl ke~one, ethers such as diethyl ether, methyl ethyl ether, dibutyl ethers, dioxane and tetrahydrofuran; aromatic hydrocarbons such as benzene, toluene and xylenes; esters such as ethyl formate, ethyl acetate and butyl acetates;
amides such as dimethyl forrnamide and dimethyl acetamide;
halogenated aliphatic hydrocarbons such as chloroform, methylene chloride and dichloroethanes; halogenated aromatic hydrocarbons such as chlorobenzene; and sulfoxides such as dimethyl sulfoxide. These solvents may be used either alone or in mixture. The reaction temperature is not critical but the reaction may usually be carried out at a temperature of 20C to 120C, preferably 60C to 100C.
In accordance with a seventh aspect of the present invention, there is proviaed a method of ion exchange which comprises contacting the cross-linked copolymer comprising 99 to 40% by weight of the recurring units of Formula (I') and 1 to 6n% by weight of either or both of the recurring units of Formula (V) and Formula (~I) with an aqueous ferric chloride solution.
Of the above described copolymers in the present invention, the three dimensional cross-linked copolymer may be employed as an ion exchange resin by taking advantage of a basic property of the imidazole ring attached to the main chain as a side chain. Moreover, according to the present invention, it has been found that the linear copolymer in ~L22S79~
the present invention can be used as an extractant of metals, a sizing agent, an antistatic agent and the like. Furthermore, it has been surprisingly found that the copolymers in the present invention has an excellent resistance to oxidation as compared with the homologues. The copolymers in the present invention have showed a particularly excellent oxidation resistance to Fe~III) ion. The copolymers in the present invention have showed only a small degree of deterioration of performance, for example, when the cross-linked copolymer was used as an ion exchange resin in contact with Fe(III) ion and when the linear copolymer was used as an extractant of Fe(II~) ion. In addition, the copolymers in the present lnvention also have showed an excellent oxidation resistance to ions such as Cu2+, MnO42+, CQO3-, Sn4+, UO22+, PtCQ62-, Hg2+, AUCQ4 , Mn3+, Ce4+ and Pr4+.

2~

The present invention will now be illustrated in more detail with reference to the following Examples, but they are given for illustrative purposes only and are not to be construed as limiting the scope of the invention.
Example 1 A 50 ml ampule was charged with a solution of 10 g of imidazolylmethylstyrene(a mixture of 60% of the meta-isomer and 40% of the para-isomer) dissolved in 20 ml of methanol, and 0.1 g of azobisisobutyronitrile(AIBN) was added to the solution.
After sufficiently shaking the ampule, the ampule was purged with nitrogen and sealed. Then the ampule was kept ln a water bath maintained at ~0C for 20 hours. Then the ampule was broken off and the contents were taken out into n-hexane, followed by fi]tration to obtain a precipitate. The precipitate was washed with n-hexane and dried to obtain 10.0 g of a white product.
The elemental analysis of the product thus obtained gave the following results.
C: 77.72(78.23), H: 6.68(6.57), N: 15.60(15.20) Each parenthesized figure shows a theoretical value.
Main absorption peaks in an infrared absorption spectrum of the product were as follows:
712, 815, 905, 1030, 1078, 1106, 1275, 1438, 1501, 1601, 2950 etc. (unit: cm~l) As is apparent from the main adsorption peaks, the absence of carbon-carbon double bond implied by the lacks of ~2~sq~
peaks near the frequency 1630 cm~l showed the formation of a polymer.
The limiting viscosity number [n] of the obtained polymer was 0.60 at 25C in 2N hydrochloric acid.
1 g of the polymer thus obtained and 0.676 g (2.5 mmoles) of ferric chloride (FeCQ3 6H2O) were dissolved in 2N
hydrochloric acid to prepare a solution having a total volume of 50 ml. After the solution was extracted with five 50 ml portions of chloroform, the iron concentration of the aqueous phase was measured. As a result, the iron concentration was found to be 2 mmole/liter. Substantially the same procedures as mentioned above were repeated to prepare a sol~1tion of ferric chloride in hydrochloric acid except that the polymer was not added. Thus prepared solution was extracted with five 50 ml portions of cnloroform. After extraction, the concentra-tion of iron in the aqueous phase was measured. As a result, the iron concentration was found to be 50 mmoles/liter. The iron concentration was equal to the concentration before extraction. From the above described results, it was found that the polymer can be used as an extractant of metals.
Examples 2 to 10 Substantially in the same manner as in Example 1, various kinds of linear homopolymers of formula (I) were synthesized. The materials, experimental conditions and the analysis results are summarized in Table 1.

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X r-l h 7~8 Example 11 6.39 g of imidazolylmethyls-tyrene(a mixture of 60%
of the meta-isomer and 40% of the para-isomer), 3.61 g of styrene and 0.1 g of azobisisobutyronitrile were placed in a 30 ml ampule having a capacity of 30 ml. After sufficiently shaking the ampule, the ampule was purged with nitrogen and sealed. The ampule was then kept in a water bath maintained at 90C for 24 hours. Then the ampule was broken off and the solidified contents were taken out. With respect to the product thus obtained, elemental analysis and infrared analysis were carried out. The results are as follows:
Elemental analysis:
C, 83.15(83.30); H, 7.00(6.99); N, 9.85(9.71) Each parenthesized figure shows a theoretical value.
Infrared absorption spec rum (cm~l):
712, 815, 905, 1030, 1078, 1106, 1275, 1438, 1501, 1601, 2950, etc.
The solid product obtained amounted to 10.0 g (yield:
100%). When 0.5 g of the solid product obtained was mixed with 100 ml of 2N hydrochloric acid, the product was completely dis-solved in the hydrochloric acid solution and oily liquid did not appear on the surface of the hydrochloric acid solution at all.
Judging from both the infrared absorption spectrum of the product which indicated the lack of peaks due to the carbon-carbon double bond and the result of the above-described _ 21 -57~8 dissolving test using a hydrochloric acid solution, the product was concluded to be an imidazolylmethylstyrene-styrene copolymer.
The limiting viscosity number [n~ of the polymer ob-tained was 0.5~ at 25C in 2N hydrochloric acid.
1 g of the copolymer obtained and 0.270 g of ferric chloride(FeCQ3-6~l20) were dissolved in 2N hydrochloric acid to prepare a solution having a total volume of 50 ml. After the solution was extracted with five 50 ml portions of chloroform, the concentration of iron contained in the hydrochloric acid solution was measured. As a result, the iron concentration was found to be 1 mmole/liter. Substantially the same proce-dures as described above were repeated to prepare a solution of ferric chloride in hydrochloric acid except that the polymer was not added. The solution thus prepared was extracted with five 50 ml portions of chloroform. After extraction, the concentration of iron in the aqueous phase was measured. As a result, the iron concentration was found to be 19 mmoles/
liter. The iron concentration was nearly equal to the con-centration before extraction. From the above described results, it was found that the polymer can be used as an ex-tractant of metals.
Examples 12 to 33 Substantially in the same manner as in Example 11, using a basic compound of Formula (II) and a monomer of Formula (IV), copolymerization was carried out. The materials, experi-mental conditions and the analysis results are summarized in Table 2.

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Example 34 A 50 ml ampule was charged with 7 g of imidazolyl-methylstyrene(a mixture of 60% of the meta-isomer and 40% of the para-isomer), 3 g of m-divinylbenzene and 0.1 g of azobisisobutyronitrile. 10 g of toluene was added in the mixture as obtained above and the resulting mixture was suf-ficiently shaken. After the ampule was sufficiently purged with nitrogen, the ampule was sealed and kept in a water bath maintained at 90C for 6 hours. The contents of the ampule completely solidified. The ampule was then broken off and the contents were ta]cen out. Then the product was crushed and pulverized in a mortar. The product pulveri~ed was washed with acetone and dried to give 10.0 g of the intended product.
With respect to the product thus obtained, elemental analysis and infrared analysis were carried out. The results are as follows:
Elemental analysis:
C, 82.6(82.5); H, 6.5(6.9); N, 10.9(10.6) Each parenthesized figure shows a theoretical value.
Infrared absorption spectrum (cm~l):
712, 815, 905; 10~0, 1078, 1106, 1275, 1438, 1501,1601, 2950, etc.
The solid product obtained was insoluble in acetone.
The yield was 100%. In the infrared absorption spectrum, the peaks due to the carbon-carbon double bond of the monomer material disappeared. Frorn the above mentioned analysis, ;i79~3 this product was concluded to be a m-divinylbenzene-~imidazolylmethylstyrene cross-linked copolymer.
Examples 35 to 57 Substantially in the same manner as in Example 34, copolymerization was carried out using a basic compound of Formula (II) and a monomer of ~ormula (VII) or a monomer of Formula (VIII). The materials, experimental conditions and the analysis results are summarized in Table 3.

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Example 58 A column was packed with 1 g of the copolymer obtained in Example 3~ and then 100 ml of lN hydrochloric acid and 100 ml of acetone were passed through the column in sequence. Then 100 ml of lN potassium nitrate was passed through the column, where-upon chlorine ion was no more detected in the effluent flowing from the column. In this case, an AgNO3 solution was used to detect chlorine ion. All the effluent that has flowed from the column after the potassium nitrate solution was supplied was collected and the total amount of chlorine ion was measuxed.
As a result, the total amount of chlorine ion was 3.80 mmoles.
~hen 100 ml of lN hydrochloric acid and 100 rnl of acetone were again supplied lnto the column in sequence. ~he copolymer was dried at 60C overnight and then its weight was measured. As a result, the copolymer weighed 1.13 g. From this result, this copolymer was found to have 3.36 meq of an exchange group per gram of its dried hydrochloric acid type.
0.360 g of ferric chloride (FeCQ 3 6H2O) was dissolved in 2N hydrochloric acid to prepare a solution having a total volume of 13.3 ml. 1 g of the above obtained dry resin was added in the solution. Ultraviolet absorbances (350 nm) of the solution were measured before and after the addition of the dry resin to evaluate the change in concentration of iron contained in the solution. As a result, the D-value (a ratio of the iron concentration of the resin phase to the iron con-centration of the liquid phase) was found to be 80.

~2;~ 9~

Example 59 1 g of an imidazolylmethylstyrene polymer as obtained in Example 1, 1 g of an iMidazolylmethylstyrene-styrene copolymer as obtained in Example 11, 1 g of polyvinylimidazole and 1 g of polyvinylpyridine were weighed out. To each sample weighed was added 40 ml of a ferric chloride solution having a concentration of 1 mole/liter. Then each sample was charged in each ampule and the ampules were sealed. These ampules were kept in an oil bath maintained at 180C for three days. Then the ampules were cooled to room temperature and the contents were taken out.
In order to evaluate the amount of Fe 3~ consumed in the oxidation reaction, the concentration of Fe 3~ contained in each solution after the oxidation reaction was measured by means of potenti-ometry using an a~ueous titanium trichloride solution. The results are given in Table 4.
Table 4 , ~
Amount of Amount of Amount of Fe ion Fe ion Fe ion before after consumed*
reaction reaction (mmole) (mmole~

Polyimidazolylmethyl-styrene 40 28 2.2 Imidazolylmethylstyrene-styrene copolymer 40 33 2.0 Polyvinylimidazole 40 5 3.3 Polyvinylpyridine 401 or less 4.2 Note: * Number of moles of Fe ion consumed by one mole of each monomer having an exchange group.

- 3~ -~L22~j79~

Example 60 In a 20 ml ampule were charged 8 g of 4-vinylpyridine, 2 g of a commercially available divinylbenzene having a purity of 56~ and 0.1 g of azobisisobutyronitrile(AI~N). In another 20 ml ampule were charged 8 g of l-vinylimidazole, 2 g of di-vinylbenzene and 0.1 g of azobisisobutyronitrile(AIBl~l). In still another 20 ml ampule were charged 8 g of (l-imidazolyl-methyl)styrene (m/p = 6/4), 2 g of divinylbenzene and 0.1 g of azobisisobutyronitrile(AIBN). These three ampules were then heat-sealed and shaken sufficiently. The ampules were kept in a water bath maintained at 80C to react for 16 hours. After completion of the reaction, the ampules were broken off to take out the reaction products. The reaction products were crushed and pulverized.
In order to evaluate oxidation resistance of the tnree copolymers obtained, in three 20 ml ampules was separate-ly charged 1 g of each copolymer and added 20 ml of a lM ferric chloride solution. The ampules were sealed and allowed to stand at 18QC for 3 days. After 3 days, the total exchange capacity of eacn copolymer was uetermined and compared with that deter-mined before treating with a ferric chloride solution. The results are shown in Table 5.

~j ~;~257~

Table 5 Total Total exchangeexchange capacitycapacity *
before after ~EC
treatment: treatrnent:
ECO(meq.)EC~(meq.) 4-Vinylpyridine-divinylbenzene copolymer 5.95 2.74 54 l-Vinylimidazole-divinylbenzene copolymer 6.49 4.02 38 _ _ Imidazolylmethylstyrene-divinylbenzene copolymer 3.74 3.18 15 Note: * QEC is given by ECoEc ECl x 100

Claims (39)

WHAT IS CLAIMED IS:

1 . A linear homopolymer of Formula (I):

(I) wherein R1 and R2 each independently represents a hydrogen atom, a straight chain or branched alkyl group having 1 to 17 carbon atoms, a phenyl group unsubstituted or substituted with one or more substituents selected from C1-C8 straight chain or branched alkyl groups, halogen atoms and an amino group, a naphthyl group, an aralkyl group having as an alkyl moiety a C1-C4 straight chain or branched alkylene group and as an aryl moiety a phenyl group unsubstituted or substituted with one or more substituents selected from halogen atoms and an amino group, pyridyl group unsubstituted or substituted with one or more substituents selected from C1-C4 straight chain or branched alkyl groups, halogen atoms and an amino group, or a nitro group;
and n is an integer of 5 to 20,000.

2. The linear homopolymer according to claim 1, wherein R1 and R2 each independently represents a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a phenyl group, a benzyl group, a pyridyl group or a nitro group.

3. The linear homopolymer according to claim 1, wherein the position of the imidazol-1-ylmethyl group relative to the vinyl group is the meta- or para-position.

4. The linear homopolymer according to claim 1, wherein R1 is located at the 2-position of the imidazole ring.

5. A process for the preparation of the linear homo-polymer of Formula (I) according to claim 1 which comprises polymerizing a basic compound of Formula (II), (II) wherein R1 and R2 each independently represents a hydrogen atom, a straight chain or branched alkyl group having 1 to 17 carbon atoms, a phenyl group unsubstituted or sub-stituted with one or more substituents selected from C1-C8 straight chain or branched alkyl groups, halogen atoms and an amino group, a naphthyl group, an aralkyl group having as an alkyl moiety a C1-C4 straight chain or branched alkylene group and as an aryl moiety a phenyl group unsubstituted or substituted with one or more substituents selected from halogen atoms and an amino group, a pyridyl group unsubstituted or substituted with one or more substituents selected from C1-C4 straight chain or branched alkyl groups, halogen atoms and an amino group, or a nitro group.

6. The process according to claim 5, wherein the poly-merization is performed in the presence of a polymerization initiator.

7. The process according to claim 5, wherein the poly-merization is performed in the presence of an inert solvent.

8. A linear copolymer comprising 95 to 5% by weight of recurring units of Formula (I'), (I') wherein R1 and R2 each independently represents a hydrogen atom, a straight chain or branched alkyl group having 1 to 17 carbon atoms, a phenyl group unsubstituted or substituted with one or more substituents selected from C1-C8 straight chain or branched alkyl groups, halogen atoms and an amino group, a naphthyl group, an aralkyl group having as an alkyl moiety a C1-C4 straight chain or branched alkylene group and as an aryl moiety a phenyl group unsubstituted or substituted with one or more substituents selected from halogen atoms and an amino group, a pyridyl group unsub-stituted or substituted with one or more substituents selected from C1-C4 straight chain or branched alkyl groups, halogen atoms and an amino group, or a nitro group, and 5 to 95% by weight of recurring units of Formula (III), (III) wherein R3 and R4 each independently represents a hydrogen atom a halogen atom, a cyano group, an aryl group, a halogenophenyl group, a phenyl group sub-stituted with one or more substituents selected from C1-C5 straight chain or branched alkyl or haloalkyl groups, alkoxy groups and a cyano group, -COOA, in which A1 represents a hydrogen atom or a C1-C10 hydrocarbon or halogenated hydrocarbon residue, -COA2 in which A2 represents a C1-C10 hydrocarbon residue, -OCOA3 in which A3 represents a C1-C10 hydrocarbon residue, -CONHA4 in which A4 represents a hydrogen atom or a C1-C10 hydrocarbon residue, an imidazolyl, pyridyl and carbazolyl groups which are unsubstituted or substituted with a C1-C4 alkyl group, based on the total weight of the recurring units of Formula (I') and Formula (III).

9. The linear copolymer according to claim 8, wherein the position of the imidazol-1-ylmethyl group relative to the vinyl moiety in the recurring units of Formula (I') is the meta- or para-position.

10. The linear copolymer according to claim 8, wherein R1 and R2 each independently represents a hydrogen atom, a methyl group, an ethyl group, a benzyl group, a pyridyl group or a nitro group.

11. The linear copolymer according to claim 8, wherein either R1 or R2 is located at the 2-position of the imidazole ring.

12. The linear copolymer according to claim 8, wherein R3 and R4 each independently represents a hydrogen atom, a cyano group, a chlorine atom, a methyl group, a phenyl group, -COOH, -COOCH3, -COCH3, -OCOCH3 or -CONH2.

13. A process for the preparation of the linear copolymer according to claim 8 which comprises copolymerizing 95 to 5%
by weight of a basic compound of Formula (II), (II) wherein R1 and R2 each independently represents a hydrogen atom, a straight chain or branched alkyl group having 1 to 17 carbon atoms, a phenyl group unsubstituted or substituted with one or more substituents selected from C1-C8 straight chain or branched alkyl groups, halogen atoms and an amino group, a naphthyl group, an aralkyl group having as an alkyl moiety a C1-C4 straight chain or branched alkylene group and as an aryl moiety a phenyl group unsubstituted or substituted with one or more substituents selected from halogen atoms and an amino group, a pyridyl group unsubstituted or substituted with one or more substituents selected from C1-C4 straight chain ox branched alkyl groups, halogen atoms and an amino group, or a nitro group, with 5 to 95% by weight of a monomer of Formula (IV), (IV) wherein R3 and R4 each independently represents a hydrogen atom, a halogen atom, a cyano group, an aryl group, a halogenophenyl group, a phenyl group sub-stituted with one or more substituents selected from C1-C5 straight chain or branched alkyl or haloalkyl groups, alkoxy groups and a cyano group, -COOA1 in which A1 represents a hydrogen atom or a C1-C10 hydro-carbon or halogenated hydrocarbon residue, -COA2 in which A2 represents a C1-C10 hydrocarbon residue, -OCOA3 in which A3 represents a C1-C10 hydrocarbon residue, -CONHA4 in which A4 represents a hydrogen atom or a C1-C10 hydrocarbon residue, an imidazolyl, pyridyl and carbazoyl groups which are unsubstituted or sub-stituted with a C1-C4 alkyl group, based on the total weight of the basic compound of Formula (II) and the monomer of Formula (IV).

14. The process according to claim 13, wherein the copoly-merization is performed in the presence of a polymerization initiator.

15. The process according to claim 13, wherein the co-polymerization is performed in the presence of an inert solvent.

16. A cross-linked copolymer comprising 99 to 40% by weight of recurring units of Formula (I') (I') wherein R1 and R2 each independently represents a hydrogen atom, a straight chain or branched alkyl group having 1 to 17 carbon atoms, a phenyl group unsubstituted or substituted with one or more substituents selected from C1-C8 straight chain or branched alkyl groups, halogen atoms and an amino group, a naphthyl group, an aralkyl group having as an alkyl moiety a C1-C4 straight chain or branched alkylene group and as an aryl moiety a phenyl group unsubstituted or substituted with one or more substituents selected from halogen atoms and an amino group, a pyridyl group unsubstituted or substituted with one or more substituents select-ed from C1-C4 straight chain or branched alkyl groups, halogen atoms and an amino group, or a nitro group, and 1 to 6090 by weight of either or both of the recurring units of Formula (V) and Formula (VI), (V) (VI) wherein R5, R7 and R9 each independently represents a hydrogen atom or a methyl group; and R6 represents wherein Z1 and Z2 each independently repre-sents a hydrogen atom or a C1-C5 hydrocarbon residue;
; wherein D1 represents -O- , -S- , -NH- or a C1-C5 alkylene group; -SO- ; -CO- ; ; -CH2-NH-CH2- ;
; wherein B1 repre-sents a divalent C1-C8 hydrocarbon residue;

wherein B2 represents a divalent C1-C5 hydrocarbon residue; or wherein B3 represents a divalent C1-C3 hydrocarbon residue;
and R8 represents wherein B4 and B5 each independently represents a hydrogen atom or a C1-C5 hydrocarbon residue;
or based on the total weight of the recurring units of Formula(I'), Formula (V) and Formula (VI).

17. The cross-linked copolymer according to claim 16 which comprises 97 to 60% by weight of the recurring units of Formula (I') and 3 to 40% by weight of either or both of the recurring units of Formula (V) and Formula (VI) based on the total weight of the recurring units of Formula (I'), Formula (V) and Formula (VI).

18. The cross-linked copolymer according to claim 16, wherein the position of the imidazol-1-ylmethyl group relative to the vinyl moiety in the recurring units of Formula (I') is the meta- or para-position.

13. The cross-linked copolymer according to claim 16, wherein R1 and R2 each independently represents a hydrogen atom, a methyl group, an ethyl group, a benzyl group, a pyridyl group or a nitro group.

20. The cross-linked copolymer according to claim 16, wherein either R1 or R2 is located at the 2 position of the imidazole ring.

21. The cross-linked copolymer according to claim 16, wherein R6 in the recurring units of Formula (V) represents .

22. The cross-linked copolymer according to claim 16, wherein R6 in the recurring units of Formula (V) represents or .

23. The cross-linked copolymer according to claim 16, wherein R6 in the recurring units of Formula (V) represents , or .

24. The cross-linked copolymer according to claim 16, wherein R6 in the recurring units of Formula (V) represents -?OCH2CH2O?- .

25. The cross-linked copolymer according to claim 16, wherein R6 in the recurring units of Formula (V) represents -?NHCH2CH2NH?- .

26. A process for the preparation of a cross-linked copolymer according to claim 16 which comprises copolymerizing 93 to 60% by weight of a basic compound of Formula (II), (II) wherein R1 and R2 each independently represents a hydrogen atom, a straight chain or branched alkyl group having 1 to 17 carbon atoms, a phenyl group unsubstituted or substituted with one or more sub-stituents selected from C1-C8 straight chain or branched alkyl groups, halogen atoms and an amino group, a naphthyl group, an aralkyl group having as an alkyl moiety a C1-C4 straight chain or branched alkylene group and as an aryl moiety a phenyl group unsubstituted or substituted with one or more substituents selected from halogen atoms and an amino group, a pyridyl group unsub-stituted or substituted with one or more substituents selected from C1-C4 straight chain or branched alkyl groups, halogen atoms and an amino group, or a nitro group, with 1 to 40% by weight of at least one of a monomer of Formula (VII) and a monomer of Formula (VIII), (VII) (VIII)

27. A process according to claim 26, wherein the co-polymerization is performed in the presence of a polymeriza-tion initiator.

28. A process according to claim 26, wherein the co-polymerization is performed in the presence of an inert solvent.

29. A method of metal extraction which comprises contact-ing the linear homopolymer according to claim 1 with a metal ion.

30. The method according to claim 29, wherein the contact is conducted in an oxidative atmosphere.

31. The method according to claim 29, wherein the metal ion is Fe3+.

32. A method of metal extraction which comprises contact-ing the linear copolymer according to claim 8 with a metal ion.

33. The method according to claim 32, wherein the contact is conducted in an oxidative atmosphere.

34. The method according to claim 32, wherein the metal ion is Fe3+, Cu2+, MnO42+, C?O3-, Sn4+, UO22+, PtC?62-, Hg2+, AuC?4-, Mn3+, Ce4+ and Pr4+.

35. The method according to claim 34, wherein the metal ion is Fe3+.

36. A method of ion exchange which comprises contacting the cross-linked copolymer according to claim 16 with a metal ion.

37. The method according to claim 36, wherein the contact is conducted in an oxidative atmosphere.
38. The method according to claim 36, wherein the metal ion is Fe3+, Cu2+, MnO42+, C?O3-, Sn4+, UO22+, PtC?62-, Hg2+, AuC?4-, Mn3+, Ce4+ and Pr4+.
39. The method according to claim 38, wherein the metal ion is Fe3+.

37. The method according to claim 36, wherein the contact is conducted in an oxidative atmosphere..

38. The method according to claim 36, wherein the metal ion is Fe3+, Cu2+, MnO42+, C?03-, Sn4+, UO22+, PtC?62-, Hg2+, AuC?4-, Mn3+, Ce4+ and Pr4+.

39. The method according to claim 38, wherein the metal ion is Fe3+.