JP6744538B2 - Solid composition and method for producing solid composition - Google Patents

Description

The present invention relates to a solid composition and a method for producing the solid composition, and more particularly to a solid composition that can be used as an adsorbent for rare earth elements.

Rare earth elements such as scandium (Sc), yttrium (Y), and lanthanoids (also referred to as “rare earth”) can dramatically improve the functions and physical properties of metal materials and semiconductor materials by adding a trace amount thereof, and thus have a structure. It is used for materials, electronic materials, magnetic materials, functional materials, etc. and plays a very important role in various industrial products. For example, by adding rare earth elements, strong magnets with excellent heat resistance can be manufactured, which contributes to downsizing and weight reduction of motors and higher performance, as well as phosphors, abrasives, electronic parts, exhaust gas catalysts for automobiles, etc. It is also used in.

Such rare earth elements are produced by mining and smelting specific ores, but due to the increase in global demand and the resource protection measures of exporting countries, there are times when supply and demand are imminent, and In order to stably secure rare earth elements in anticipation of demand, it is necessary to diversify rare earth element collection methods and improve the efficiency of separation and purification methods.
For example, as a separation and purification method with improved profitability, in Patent Documents 1 and 2, rare earth elements are selected by leaching a clay sample (argilete) or the like with an acid and removing aluminum ions and iron ions from the leachate. A method of automatically taking out is proposed.

Special table 2014-508863 gazette Japanese Patent Publication No. 2014-513212

It has been confirmed that certain rare earth elements such as scandium (Sc) are dissolved in a very small amount in environmental water such as hot spring water, and if such dissolved rare earth elements can be selectively recovered, It can also be established as one of the methods for producing rare earth elements. In particular, if a solid material such as a reusable adsorbent can be developed, it will be an important technology for reducing the production cost.
An object of the present invention is to provide a novel highly functional solid material, particularly a solid material that can be used as an adsorbent for rare earth elements.

（式（Ａ）中、Ｒ^１はそれぞれ独立して水素原子又はメチル基を、Ｒ^２はそれぞれ独立して炭素数２〜３０の炭化水素基を、ｎは２〜１００,０００の整数を表す。）

（式（Ｂ−１）〜（Ｂ−３）、（Ｃ−１）〜（Ｃ−５）、及び（Ｄ−１）〜（Ｄ−１４）中、Ｒ^３はそれぞれ独立して炭素数２〜３０の炭化水素基を、Ｒ^４はそれぞれ独立して水素原子又は炭素数１〜３０の炭化水素基を、Ｒ^５はそれぞれ独立して水素原子又は炭素数１〜３０の炭化水素基を、Ｒ^６はそれぞれ独立して炭素数１〜３０の炭化水素基を、Ｘは酸素原子又は硫黄原子を、ａは０〜２の整数を、ｂは０〜３の整数を、ｃは０〜４の整数を、ｄは０〜５の整数を表す。但し、化合物内に炭化水素基であるＲ^６が２以上ある場合、Ｒ^６同士が互いに結合して環状構造を形成していてもよい。）
＜２＞ 前記重合体が繊維状の形態である、＜１＞に記載の固体組成物。
＜３＞ 金属元素を吸着するための吸着材である、＜１＞又は＜２＞に記載の固体組成物
。
＜４＞ 前記金属元素が希土類元素である、＜３＞に記載の固体組成物。
＜５＞ 側鎖に下記式（Ａ）で表される構造を有する重合体を準備する準備工程、並びに
下記式（Ｂ−１）〜（Ｂ−３）で表されるリン含有化合物、下記式（Ｃ−１）〜（Ｃ−５）で表される硫黄含有化合物、及び下記式（Ｄ−１）〜（Ｄ−１４）で表される窒素含有化合物からなる群より選択される少なくとも１種の化合物を前記重合体に接触させる接触工程を含むことを特徴とする、固体組成物の製造方法。

（式（Ａ）中、Ｒ^１はそれぞれ独立して水素原子又はメチル基を、Ｒ^２はそれぞれ独立して炭素数２〜３０の炭化水素基を、ｎは２〜１００,０００の整数を表す。）

（式（Ｂ−１）〜（Ｂ−３）、（Ｃ−１）〜（Ｃ−５）、及び（Ｄ−１）〜（Ｄ−１４）中、Ｒ^３はそれぞれ独立して炭素数２〜３０の炭化水素基を、Ｒ^４はそれぞれ独立して水素原子又は炭素数１〜３０の炭化水素基を、Ｒ^５はそれぞれ独立して水素原子又は炭素数１〜３０の炭化水素基を、Ｒ^６はそれぞれ独立して炭素数１〜３０の炭化水素基を、Ｘは酸素原子又は硫黄原子を、ａは０〜２の整数を、ｂは０〜３の整数を、ｃは０〜４の整数を、ｄは０〜５の整数を表す。但し、化合物内に炭化水素基であるＲ^６が２以上ある場合、Ｒ^６同士が互いに結合して環状構造を形成していてもよい。）
＜６＞ 前記準備工程が、前記重合体の主鎖となる高分子材料に対して下記式（ａ）で表
される（メタ）アクリル酸エステルをグラフト重合することを含む、＜５＞に記載の固体組成物の製造方法。

（式（ａ）中、Ｒ^１はそれぞれ独立して水素原子又はメチル基を、Ｒ^２はそれぞれ独立して炭素数２〜３０の炭化水素基を表す。）
＜７＞ 前記高分子材料が、ポリオレフィン系高分子、スチレン系高分子、アクリル系高
分子、フッ素系高分子、ポリアミド系高分子、ポリイミド系高分子、ポリアセタール系高分子、ポリエステル系高分子、ポリカーボネート系高分子、ポリウレタン系高分子、多糖類、及びタンパク質からなる群より選択される少なくとも１種の高分子である、＜６＞に記載の固体組成物の製造方法。 The present inventors have conducted extensive studies to solve the above problems, based on a polymer having a specific structure in the side chain as a base, and further a specific compound having a functional group such as a phosphate group. The inventors have found that the contained solid composition is a highly functional solid material such as an adsorbent for rare earth elements, and completed the present invention.
That is, the present invention is as follows.
<1> A solid composition based on a polymer having a structure represented by the following formula (A) in a side chain,
Phosphorus-containing compounds represented by the following formulas (B-1) to (B-3), sulfur-containing compounds represented by the following formulas (C-1) to (C-5), and the following formula (D-1) To (D-14), a solid composition containing at least one compound selected from the group consisting of nitrogen-containing compounds.

(In the formula (A), R ^1's each independently represent a hydrogen atom or a methyl group, R ^2's each independently represent a hydrocarbon group having 2 to 30 carbon atoms, and n represents an integer of 2 to 100,000. .)

(In formulas (B-1) to (B-3), (C-1) to (C-5), and (D-1) to (D-14), each R ³ independently has 2 carbon atoms. the 30 hydrocarbon group, a hydrocarbon group of each of R ⁴ is independently a hydrogen atom or 1 to 30 carbon atoms, a hydrocarbon group of R ⁵ is a hydrogen atom or a C1-30 independently, R ⁶ is independently a hydrocarbon group having 1 to 30 carbon atoms, X is an oxygen atom or a sulfur atom, a is an integer of 0 to 2, b is an integer of 0 to 3, and c is 0 to 4. And d represents an integer of 0 to 5. However, when there are two or more hydrocarbon groups R ⁶ in the compound, R ^{6 s} may combine with each other to form a cyclic structure. )
<2> The solid composition according to <1>, wherein the polymer has a fibrous form.
<3> The solid composition according to <1> or <2>, which is an adsorbent for adsorbing a metal element.
<4> The solid composition according to <3>, wherein the metal element is a rare earth element.
<5> A preparatory step of preparing a polymer having a structure represented by the following formula (A) in a side chain, a phosphorus-containing compound represented by the following formulas (B-1) to (B-3), and the following formula: At least one selected from the group consisting of sulfur-containing compounds represented by (C-1) to (C-5) and nitrogen-containing compounds represented by the following formulas (D-1) to (D-14). A method for producing a solid composition, comprising the step of contacting the compound of claim 1 with the polymer.

(In the formula (A), R ^1's each independently represent a hydrogen atom or a methyl group, R ^2's each independently represent a hydrocarbon group having 2 to 30 carbon atoms, and n represents an integer of 2 to 100,000. .)

(In formulas (B-1) to (B-3), (C-1) to (C-5), and (D-1) to (D-14), each R ³ independently has 2 carbon atoms. the 30 hydrocarbon group, a hydrocarbon group of each of R ⁴ is independently a hydrogen atom or 1 to 30 carbon atoms, a hydrocarbon group of R ⁵ is a hydrogen atom or a C1-30 independently, R ⁶ is independently a hydrocarbon group having 1 to 30 carbon atoms, X is an oxygen atom or a sulfur atom, a is an integer of 0 to 2, b is an integer of 0 to 3, and c is 0 to 4. And d represents an integer of 0 to 5. However, when there are two or more hydrocarbon groups R ⁶ in the compound, R ^{6 s} may combine with each other to form a cyclic structure. )
<6> The preparation step as described in <5>, which comprises graft-polymerizing a (meth)acrylic acid ester represented by the following formula (a) onto a polymer material serving as a main chain of the polymer. A method for producing a solid composition.

(In the formula (a), R ^1's each independently represent a hydrogen atom or a methyl group, and R ^2's each independently represent a hydrocarbon group having 2 to 30 carbon atoms.)
<7> The polymer material is a polyolefin polymer, a styrene polymer, an acrylic polymer, a fluorine polymer, a polyamide polymer, a polyimide polymer, a polyacetal polymer, a polyester polymer, or a polycarbonate. The method for producing a solid composition according to <6>, which is at least one kind of polymer selected from the group consisting of a polymer, a polyurethane polymer, a polysaccharide, and a protein.

According to the present invention, it is possible to provide a novel highly functional solid material, particularly a solid material that can be used as an adsorbent for rare earth elements.

3 is a graph showing the relationship between electron beam dose and graft ratio when radiation-polymerized dodecyl methacrylate was applied to a polyethylene nonwoven fabric. (A) FT-IR measurement results of the polymer after radiation-induced graft polymerization of dodecyl methacrylate and (b) FT-IR measurement results of the solid composition after immersion in 2-ethylhexyl 2-ethylhexylphosphonate. 3 is a graph showing the pH dependence of scandium (Sc) adsorption rate and iron (Fe) adsorption rate of the solid composition of Example 1 and the adsorbents of Comparative Examples 1 and 2. The scandium (Sc) concentration and the iron (Fe) concentration in the discharged liquid when a mixed solution of scandium (Sc) and iron (Fe) was passed through a cylindrical column packed with the solid composition of Example 1 are shown. This is the graph.

In describing the present invention, specific examples will be described, but the present invention is not limited to the following contents without departing from the gist of the present invention, and can be appropriately modified and implemented.

（式（Ａ）中、Ｒ^１はそれぞれ独立して水素原子又はメチル基を、Ｒ^２はそれぞれ独立して炭素数２〜３０の炭化水素基を、ｎは２〜１００,０００の整数を表す。）

（式（Ｂ−１）〜（Ｂ−３）、（Ｃ−１）〜（Ｃ−５）、及び（Ｄ−１）〜（Ｄ−１４）中、Ｒ^３はそれぞれ独立して炭素数２〜３０の炭化水素基を、Ｒ^４はそれぞれ独立して水素原子又は炭素数１〜３０の炭化水素基を、Ｒ^５はそれぞれ独立して水素原子又は炭素数１〜３０の炭化水素基を、Ｒ^６はそれぞれ独立して炭素数１〜３０の炭化水素基を、Ｘは酸素原子又は硫黄原子を、ａは０〜２の整数を、ｂは０〜３の整数を、ｃは０〜４の整数を、ｄは０〜５の整数を表す。但し、化合物内に炭化水素基であるＲ^６が２以上ある場合、Ｒ^６同士が互いに結合して環状構造を形成していてもよい。）
式（Ｂ−１）〜（Ｂ−３）で表されるリン含有化合物、式（Ｃ−１）〜（Ｃ−５）で表
される硫黄含有化合物、及び式（Ｄ−１）〜（Ｄ−１４）で表される窒素含有化合物は、それぞれＲ^３として炭化水素基を有しているが、これが固体組成物内において基剤となる重合体のＲ^２の炭化水素基と疎水性相互作用によって引き合うため、本発明の固体組成物は、リン酸基等の有用な官能基を固定した機能性の高い固体材料となるのである（（Ｂ−１）で表されるリン含有化合物を含有する固体組成物の場合、下記式で示されるように炭化水素基同士が引き合って、リン含有化合物が固定化されるものと考えられる。）。
リン酸基等の活性な官能基を重合体に導入する従来法は、操作が煩雑であったり、官能基を定量的に導入することができなかったりする等の問題があった。本発明者らは、（メタ）アクリル酸エステル等を利用して基剤となる重合体の側鎖に炭化水素鎖を形成した上で、導入したい官能基と炭化水素基の両方を有する化合物を接触させることにより、炭化水素鎖同士が疎水性相互作用によって結びつき、定量的に官能基を固定化した固体材料となることを見出したのである。

また、本発明者らは、本発明の固体組成物が金属元素、特に希土類元素を選択的に吸着できることを確認しており、希土類元素の吸着材として活用できることも明らかとしているのである。
なお、「基剤」とは、固体組成物を主な構成成分であることを意味するものとし、「重合体を基剤とする固体組成物」は、固体組成物の５０質量％以上が「重合体」であることを意味するものとする。
また、式（Ａ）中の波線は、その先が重合体の主鎖に結合しているか、或いは側鎖の末端となっていることを意味するものとする。
さらに、（Ｂ−１）〜（Ｂ−３）、（Ｃ−１）〜（Ｃ−５）、及び（Ｄ−１）〜（Ｄ−１４）中の実線と破線の二重線は、単結合又は二重結合を表すものとする。 <Solid composition>
A solid composition which is one embodiment of the present invention (hereinafter, may be abbreviated as “solid composition of the present invention”) is a polymer having a structure represented by the following formula (A) in a side chain (hereinafter, It may be abbreviated as "the polymer according to the present invention."), which is a solid composition containing a phosphorus-containing compound represented by the following formulas (B-1) to (B-3) and a following formula (B-1). At least one selected from the group consisting of sulfur-containing compounds represented by C-1) to (C-5) and nitrogen-containing compounds represented by the following formulas (D-1) to (D-14). It is characterized by containing a compound (hereinafter, may be abbreviated as "the compound according to the present invention").

(In the formula (A), R ^1's each independently represent a hydrogen atom or a methyl group, R ^2's each independently represent a hydrocarbon group having 2 to 30 carbon atoms, and n represents an integer of 2 to 100,000. .)

(In formulas (B-1) to (B-3), (C-1) to (C-5), and (D-1) to (D-14), each R ³ independently has 2 carbon atoms. the 30 hydrocarbon group, a hydrocarbon group of each of R ⁴ is independently a hydrogen atom or 1 to 30 carbon atoms, a hydrocarbon group of R ⁵ is a hydrogen atom or a C1-30 independently, R ⁶ is independently a hydrocarbon group having 1 to 30 carbon atoms, X is an oxygen atom or a sulfur atom, a is an integer of 0 to 2, b is an integer of 0 to 3, and c is 0 to 4. And d represents an integer of 0 to 5. However, when there are two or more hydrocarbon groups R ⁶ in the compound, R ^{6 s} may combine with each other to form a cyclic structure. )
The phosphorus-containing compounds represented by the formulas (B-1) to (B-3), the sulfur-containing compounds represented by the formulas (C-1) to (C-5), and the formulas (D-1) to (D). Each of the nitrogen-containing compounds represented by -14) has a hydrocarbon group as R ³ , and this has a hydrophobic interaction with the hydrocarbon group of R ² of the polymer as a base in the solid composition. Therefore, the solid composition of the present invention becomes a highly functional solid material having a useful functional group such as a phosphoric acid group immobilized (containing the phosphorus-containing compound represented by (B-1)). In the case of a solid composition, it is considered that the hydrocarbon group attracts each other as shown by the following formula to immobilize the phosphorus-containing compound.
The conventional method of introducing an active functional group such as a phosphoric acid group into a polymer has problems that the operation is complicated and that the functional group cannot be quantitatively introduced. The present inventors have used a (meth)acrylic acid ester or the like to form a hydrocarbon chain on a side chain of a polymer serving as a base, and then a compound having both a functional group and a hydrocarbon group to be introduced. It was found that, by bringing them into contact with each other, the hydrocarbon chains are bound to each other by a hydrophobic interaction, and a solid material having quantitatively immobilized functional groups is obtained.

Further, the present inventors have confirmed that the solid composition of the present invention can selectively adsorb metal elements, particularly rare earth elements, and have also clarified that it can be utilized as an adsorbent for rare earth elements.
The "base" means that the solid composition is a main constituent, and the "solid composition based on a polymer" means that 50% by mass or more of the solid composition is " It is meant to be a "polymer".
Further, the wavy line in the formula (A) means that the tip thereof is bonded to the main chain of the polymer or is the end of the side chain.
Furthermore, the solid and broken double lines in (B-1) to (B-3), (C-1) to (C-5), and (D-1) to (D-14) are single lines. It shall represent a bond or a double bond.

（式（Ａ）中、Ｒ^１はそれぞれ独立して水素原子又はメチル基を、Ｒ^２はそれぞれ独立して炭素数２〜３０の炭化水素基を、ｎは２〜１００,０００の整数を表す。）
Ｒ^１はそれぞれ独立して水素原子又はメチル基を表しているが、Ｒ^１が水素原子である構造はアクリル酸エステルを、Ｒ^１がメチル基である構造はメタクリル酸エステルを構成モノマーとすることによって形成することができる。
Ｒ^２はそれぞれ独立して炭素数２〜３０の炭化水素基を表しているが、炭素数は、好ましくは４以上、より好ましくは６以上であり、好ましくは１８以下、より好ましくは１４以下である。なお、炭化水素基は、直鎖状の飽和炭化水素基に限られず、炭素−炭素不飽和結合、分岐構造、環状構造のそれぞれを有していてもよい。Ｒ^２としては、ヘキシル基
、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘプタデシル基、オクタデシル基等が挙げられる。
ｎは、２〜１００,０００の整数を表しているが、好ましくは１０以上、より好ましく
は１００以上であり、好ましくは８０，０００以下、より好ましくは５０,０００以下で
ある。 The polymer according to the present invention is a polymer having a structure represented by the following formula (A) in the side chain, but the specific type of the structure represented by the formula (A) is not particularly limited, and its purpose is It can be selected as appropriate.

(In the formula (A), R ^1's each independently represent a hydrogen atom or a methyl group, R ^2's each independently represent a hydrocarbon group having 2 to 30 carbon atoms, and n represents an integer of 2 to 100,000. .)
Each R ¹ independently represents a hydrogen atom or a methyl group, but the structure in which R ¹ is a hydrogen atom is an acrylate ester, and the structure in which R ¹ is a methyl group is a methacrylic acid ester as a constituent monomer. Can be formed by.
R ^2's each independently represent a hydrocarbon group having 2 to 30 carbon atoms, but the carbon number is preferably 4 or more, more preferably 6 or more, preferably 18 or less, more preferably 14 or less. is there. The hydrocarbon group is not limited to a linear saturated hydrocarbon group, and may have a carbon-carbon unsaturated bond, a branched structure, or a cyclic structure. Examples of R ² include hexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, heptadecyl group, octadecyl group and the like.
n represents an integer of 2 to 100,000, preferably 10 or more, more preferably 100 or more, preferably 80,000 or less, more preferably 50,000 or less.

The structure of the main chain of the polymer according to the present invention is not particularly limited, and known synthetic polymer structures and natural polymer structures can be appropriately selected and used. For example, a polyolefin-based polymer structure such as a polyethylene structure or a polypropylene structure, a styrene-based polymer structure such as a polystyrene structure, an acrylic polymer structure such as a polymethylmethacrylate structure, or a fluorine-based structure such as a polytetrafluoroethylene (PTFE) structure. Polysaccharides such as polymer structure, polyamide polymer structure such as nylon structure, polyimide polymer structure, polyacetal polymer structure, polyester polymer structure, polycarbonate polymer structure, polyurethane polymer structure, cellulose structure, etc. Structure and protein structure are mentioned. The structure of the main chain is not limited to the structure composed of one kind of monomer, and may be a copolymer formed of two or more kinds of monomers (blocks).

The molecular weight (weight average molecular weight) of the polymer according to the present invention is not particularly limited, but is usually 100 or more, preferably 1,000 or more, more preferably 10,000 or more, and usually 10,000,000 or less. ..

The form of the polymer according to the present invention is not particularly limited, and various forms such as a fibrous form and a particulate form can be used, but a fibrous form is preferable because it has a high surface area and is easy to use. Further, the polymer according to the present invention may be one having pores as a porous material, and when it is fibrous, it may be a hollow fiber.

（式（ａ）中、Ｒ^１はそれぞれ独立して水素原子又はメチル基を、Ｒ^２はそれぞれ独立して炭素数２〜３０の炭化水素基を表す。）
なお、グラフト重合の種類や条件等は、「固体組成物の製造方法」において詳細について説明する。 The method for preparing the polymer according to the present invention is also not particularly limited, and a known method can be adopted as appropriate, and it is represented by the following formula (a) with respect to the polymer material serving as the main chain of the polymer. The method of graft-polymerizing a (meth)acrylic acid ester is mentioned.

(In the formula (a), R ^1's each independently represent a hydrogen atom or a methyl group, and R ^2's each independently represent a hydrocarbon group having 2 to 30 carbon atoms.)
The type and conditions of graft polymerization will be described in detail in "Method for producing solid composition".

The content of the polymer of the present invention in the solid composition of the present invention is preferably 60% by mass or more, more preferably 65% by mass or more, further preferably 70% by mass or more, and usually 95% by mass or less, preferably Is 90% by mass or less, more preferably 80% by mass or less.

（式（Ｂ−１）〜（Ｂ−３）、（Ｃ−１）〜（Ｃ−５）、及び（Ｄ−１）〜（Ｄ−１４）中、Ｒ^３はそれぞれ独立して炭素数２〜３０の炭化水素基を、Ｒ^４はそれぞれ独立して水素原子又は炭素数１〜３０の炭化水素基を、Ｒ^５はそれぞれ独立して水素原子又は炭素数１〜３０の炭化水素基を、Ｒ^６はそれぞれ独立して炭素数１〜３０の炭化水素基を、Ｘは酸素原子又は硫黄原子を、ａは０〜２の整数を、ｂは０〜３の整数を、ｃは０〜４の整数を、ｄは０〜５の整数を表す。但し、化合物内に炭化水素基であるＲ^６が２以上ある場合、Ｒ^６同士が互いに結合して環状構造を形成していてもよい。）
Ｒ^３はそれぞれ独立して炭素数２〜３０の炭化水素基を表しているが、炭素数は、好ましくは４以上であり、好ましくは１８以下、より好ましくは１４以下である。なお、炭化水素基は、直鎖状の飽和炭化水素基に限られず、炭素−炭素不飽和結合、分岐構造、環状構造のそれぞれを有していてもよい。Ｒ^３としては、ブチル基、ヘキシル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘプタデシル基、オクタデシル基等が挙げられる。
Ｒ^４はそれぞれ独立して水素原子又は炭素数１〜３０の炭化水素基を表しているが、炭素数は、好ましくは１２以下、より好ましくは６以下である。なお、炭化水素基は、直鎖状の飽和炭化水素基に限られず、炭素−炭素不飽和結合、分岐構造、環状構造のそれぞれを有していてもよい。Ｒ^４としては、水素原子、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、へキシル基等が挙げられる。
Ｒ^５はそれぞれ独立して水素原子又は炭素数１〜３０の炭化水素基を表しているが、炭素数は、好ましくは１２以下、より好ましくは６以下である。なお、炭化水素基は、直鎖状の飽和炭化水素基に限られず、炭素−炭素不飽和結合、分岐構造、環状構造のそれぞれを有していてもよい。Ｒ^５としては、水素原子、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、へキシル基等が挙げられる。
Ｒ^６はそれぞれ独立して炭素数１〜３０の炭化水素基を表しているが、炭素数は、好ましくは１２以下、より好ましくは６以下である。なお、炭化水素基は、直鎖状の飽和炭化水素基に限られず、炭素−炭素不飽和結合、分岐構造、環状構造のそれぞれを有していてもよい。また、化合物内に炭化水素基であるＲ^６が２以上ある場合、Ｒ^６同士が互いに結合して環状構造を形成していてもよいが、Ｒ^６同士が互いに結合して環状構造を形成した具体的な化合物として、「２−プロピルベンゾイミダゾール」が挙げられる。「２−プロピルベンゾイミダゾール」は、（Ｄ−３）で表される窒素含有化合物に該当するが、この化合物は、イミダゾール構造の４位と５位に炭化水素基を有し、これらが互いに結合してベンゼン環構造を形成していると表現することもできるからである。

なお、Ｒ^６としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、へキシル基等が挙げられる。 The compound according to the present invention includes a phosphorus-containing compound represented by the following formulas (B-1) to (B-3), a sulfur-containing compound represented by the following formulas (C-1) to (C-5), and It is at least one compound selected from the group consisting of nitrogen-containing compounds represented by the following formulas (D-1) to (D-14), but the specific type of the compound is not particularly limited, and may be any purpose. It can be selected as appropriate.

(In formulas (B-1) to (B-3), (C-1) to (C-5), and (D-1) to (D-14), each R ³ independently has 2 carbon atoms. the 30 hydrocarbon group, a hydrocarbon group of each of R ⁴ is independently a hydrogen atom or 1 to 30 carbon atoms, a hydrocarbon group of R ⁵ is a hydrogen atom or a C1-30 independently, R ⁶ is independently a hydrocarbon group having 1 to 30 carbon atoms, X is an oxygen atom or a sulfur atom, a is an integer of 0 to 2, b is an integer of 0 to 3, and c is 0 to 4. And d represents an integer of 0 to 5. However, when there are two or more hydrocarbon groups R ⁶ in the compound, R ^{6 s} may combine with each other to form a cyclic structure. )
R ^3's each independently represent a hydrocarbon group having 2 to 30 carbon atoms, but the carbon number is preferably 4 or more, preferably 18 or less, more preferably 14 or less. The hydrocarbon group is not limited to a linear saturated hydrocarbon group, and may have a carbon-carbon unsaturated bond, a branched structure, or a cyclic structure. Examples of R ³ include a butyl group, a hexyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a heptadecyl group and an octadecyl group.
R ^4's each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and the carbon number is preferably 12 or less, more preferably 6 or less. The hydrocarbon group is not limited to a linear saturated hydrocarbon group, and may have a carbon-carbon unsaturated bond, a branched structure, or a cyclic structure. Examples of R ⁴ include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group.
Each R ⁵ independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and the carbon number is preferably 12 or less, more preferably 6 or less. The hydrocarbon group is not limited to a linear saturated hydrocarbon group, and may have a carbon-carbon unsaturated bond, a branched structure, or a cyclic structure. Examples of R ⁵ include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group.
R ⁶ independently represents a hydrocarbon group having 1 to 30 carbon atoms, and the carbon number is preferably 12 or less, more preferably 6 or less. The hydrocarbon group is not limited to a linear saturated hydrocarbon group, and may have a carbon-carbon unsaturated bond, a branched structure, or a cyclic structure. Moreover, when there are two or more R ^{6 s} that are hydrocarbon groups in the compound, R ^{6 s} may combine with each other to form a cyclic structure, but R ^{6 s} may combine with each other to form a cyclic structure. As a specific compound, "2-propylbenzimidazole" can be mentioned. “2-Propylbenzimidazole” corresponds to the nitrogen-containing compound represented by (D-3), which has a hydrocarbon group at the 4-position and 5-position of the imidazole structure and these are bonded to each other. This is because it can be expressed as forming a benzene ring structure.

Examples of R ⁶ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.

式（Ｃ−１）〜（Ｃ−５）で表される硫黄含有化合物としては、下記式で表される化合物が挙げられる。

式（Ｄ−１）〜（Ｄ−１４）で表される窒素含有化合物としては、下記式で表される化合物が挙げられる。

なお、これらの化合物は、市販されており、適宜入手して本発明の固体組成物に含有させることができる。 Examples of the phosphorus-containing compounds represented by the formulas (B-1) to (B-3) include compounds represented by the following formulas.

Examples of the sulfur-containing compounds represented by the formulas (C-1) to (C-5) include compounds represented by the following formulas.

Examples of the nitrogen-containing compounds represented by the formulas (D-1) to (D-14) include compounds represented by the following formulas.

Note that these compounds are commercially available, and can be appropriately obtained and included in the solid composition of the present invention.

The content of the compound according to the present invention in the solid composition of the present invention (total content when two or more kinds are contained) is usually 0.01 mmol/g or more, preferably 0.5 mmol/g or more, more preferably It is 1 mmol/g or more and usually 100 mmol/g or less.

The solid composition of the present invention may contain additives such as an antioxidant and an ultraviolet absorber, and the kind and content thereof are not particularly limited. For example, examples of the antioxidant include hindered phenol-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants and the like. Examples of the UV absorber include benzotriazole-based UV absorbers, benzophenone-based UV absorbers, salicylic acid-based UV absorbers, cyanoacrylate-based UV absorbers, and triazine-based UV absorbers.
The content of these additives is usually 0.01% by mass or more and 2% by mass or less.

The use of the solid composition of the present invention is not particularly limited and can be appropriately selected depending on the type of functional group contained in the compound of the present invention. The compound according to the present invention has an acid point, a base point, an electron pair that coordinates to a metal atom, and the like, and therefore, as an adsorbent for adsorbing a metal element, an ion exchange resin, a solid acid, a solid base, or the like. It can be used. Among these, it is preferable to use it as an adsorbent for adsorbing a metal element.
The metal element to be adsorbed when used as an adsorbent is not particularly limited, and a wide range of metal elements can be targeted, but rare metal elements (rare metals) and rare earth elements (rare earth) with high economic value are available. It is preferable to target In particular, the rare earth element can be selectively adsorbed by adjusting the pH of the solution in which the metal element is dissolved. Therefore, it is preferable to target the rare earth element. Incidentally, as rare earth elements (rare earth), in addition to scandium (Sc) and yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm). Examples of the lanthanoid include europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu).

（式（Ａ）中、Ｒ^１はそれぞれ独立して水素原子又はメチル基を、Ｒ^２はそれぞれ独立して炭素数２〜３０の炭化水素基を、ｎは２〜１００,０００の整数を表す。）

（式（Ｂ−１）〜（Ｂ−３）、（Ｃ−１）〜（Ｃ−５）、及び（Ｄ−１）〜（Ｄ−１４）中、Ｒ^３はそれぞれ独立して炭素数２〜３０の炭化水素基を、Ｒ^４はそれぞれ独立して水素原子又は炭素数１〜３０の炭化水素基を、Ｒ^５はそれぞれ独立して水素原子又は炭素数１〜３０の炭化水素基を、Ｒ^６はそれぞれ独立して炭素数１〜３０の炭化水素基を、Ｘは酸素原子又は硫黄原子を、ａは０〜２の整数を、ｂは０〜３の整数を、ｃは０〜４の整数を、ｄは０〜５の整数を表す。但し、化合物内に炭化水素基であるＲ^６が２以上ある場合、Ｒ^６同士が互いに結合して環状構造を形成していてもよい。）
前述のように、本発明に係る重合体のＲ^２の炭化水素基と本発明に係る化合物のＲ^３の炭化水素基とが疎水性相互作用によって引き合うために、式（Ａ）で表される構造を有す
る重合体を準備し、この重合体を式（Ｂ−１）〜（Ｂ−３）で表されるリン含有化合物、式（Ｃ−１）〜（Ｃ−５）で表される硫黄含有化合物、及び式（Ｄ−１）〜（Ｄ−１４）で表される窒素含有化合物に接触させることにより、リン酸基等の有用な官能基を固定した機能性の高い固体材料を製造することができるのである（（Ｂ−１）で表されるリン含有化合物を含有する固体組成物の場合、下記式で示されるように炭化水素基同士が引き合って、リン含有化合物が固定化されるものと考えられる。）。

<Method for producing solid composition>
A method for producing a solid composition, which is another aspect of the present invention (hereinafter, may be abbreviated as “production method of the present invention”), is a method for producing a solid composition based on a polymer, and has a side chain. To a polymer having a structure represented by the following formula (A) (hereinafter may be abbreviated as "preparing process according to the present invention"), and the following formulas (B-1) to (B). -3), a phosphorus-containing compound represented by the following formulas, a sulfur-containing compound represented by the following formulas (C-1) to (C-5), and a sulfur-containing compound represented by the following formulas (D-1) to (D-14). The method is characterized by including a contact step of bringing at least one compound selected from the group consisting of nitrogen-containing compounds into contact with the polymer (hereinafter, may be abbreviated as "contact step according to the present invention").

(In the formula (A), R ^1's each independently represent a hydrogen atom or a methyl group, R ^2's each independently represent a hydrocarbon group having 2 to 30 carbon atoms, and n represents an integer of 2 to 100,000. .)

(In formulas (B-1) to (B-3), (C-1) to (C-5), and (D-1) to (D-14), each R ³ independently has 2 carbon atoms. the 30 hydrocarbon group, a hydrocarbon group of each of R ⁴ is independently a hydrogen atom or 1 to 30 carbon atoms, a hydrocarbon group of R ⁵ is a hydrogen atom or a C1-30 independently, R ⁶ is independently a hydrocarbon group having 1 to 30 carbon atoms, X is an oxygen atom or a sulfur atom, a is an integer of 0 to 2, b is an integer of 0 to 3, and c is 0 to 4. And d represents an integer of 0 to 5. However, when there are two or more hydrocarbon groups R ⁶ in the compound, R ^{6 s} may combine with each other to form a cyclic structure. )
As described above, since the hydrocarbon group of R ² of the polymer according to the present invention and the hydrocarbon group of R ³ of the compound according to the present invention attract each other by the hydrophobic interaction, they are represented by the formula (A). A polymer having a structure is prepared, and the polymer is a phosphorus-containing compound represented by formulas (B-1) to (B-3) and sulfur represented by formulas (C-1) to (C-5). By contacting the containing compound and the nitrogen-containing compound represented by the formulas (D-1) to (D-14), a highly functional solid material having a useful functional group such as a phosphate group immobilized thereon is produced. In the case of a solid composition containing a phosphorus-containing compound represented by ((B-1)), hydrocarbon groups attract each other as shown in the following formula to immobilize the phosphorus-containing compound. It is considered to be.).

（式（Ａ）中、Ｒ^１はそれぞれ独立して水素原子又はメチル基を、Ｒ^２はそれぞれ独立して炭素数２〜３０の炭化水素基を、ｎは２〜１００,０００の整数を表す。） The preparation step according to the present invention is a step of preparing a polymer having a structure represented by the following formula (A) in a side chain, and a polymer having a structure represented by the following formula (A) in a side chain. Is synonymous with the above-mentioned polymer according to the present invention, and the following is similarly abbreviated as “polymer according to the present invention”.

(In the formula (A), R ^1's each independently represent a hydrogen atom or a methyl group, R ^2's each independently represent a hydrocarbon group having 2 to 30 carbon atoms, and n represents an integer of 2 to 100,000. .)

（式（ａ）中、Ｒ^１はそれぞれ独立して水素原子又はメチル基を、Ｒ^２はそれぞれ独立して炭素数２〜３０の炭化水素基を表す。）
グラフト重合の種類や条件等は、特に限定されないが、主鎖となる高分子材料の種類や形態が制限されず、また大量生産に適していることから、放射線グラフト重合であることが好ましい。また、放射線グラフト重合として、主鎖となる高分子材料と（メタ）アクリル酸エステルに対して同時に放射線を照射してグラフト重合させる同時照射法、及び主鎖となる高分子材料に対して先に放射線を照射し、これに（メタ）アクリル酸エステルを接触させてグラフト重合させる前照射法が挙げられるが、ホモポリマーの生成量が少なくなることから、前照射法が好ましい。
また、前照射法については、不活性ガス中で主鎖となる高分子材料に対して放射線を照射するポリマーラジカル法、及び酸素存在下で主鎖となる高分子材料に対して放射線を照射するパーオキサイド法の何れも使用可能である。
放射線のエネルギー量は、通常１ｋＧｙ以上、好ましくは５ｋＧｙ以上、より好ましくは１０ｋＧｙ以上であり、通常１，０００ｋＧｙ以下、好ましくは５００ｋＧｙ以下である。
放射線を照射する際の温度条件は、通常室温、好ましくは冷却下である。
放射線の照射時間は、通常は１秒以上、２４時間以下である。
上記範囲内であると、重合を十分に進めることができるとともに、高分子基剤の劣化を抑制することができる。 The method for preparing the polymer according to the present invention is not particularly limited, and the polymer may be obtained from another person or may be prepared by itself.
The preparation method for preparing the polymer according to the present invention is not particularly limited, and a known method can be appropriately adopted, but the following formula (a) can be used for the polymer material serving as the main chain of the polymer. The method of graft-polymerizing the (meth)acrylic acid ester represented by

(In the formula (a), R ^1's each independently represent a hydrogen atom or a methyl group, and R ^2's each independently represent a hydrocarbon group having 2 to 30 carbon atoms.)
The type and conditions of the graft polymerization are not particularly limited, but the type and form of the polymer material as the main chain are not limited, and the graft polymerization is preferable because it is suitable for mass production. Further, as the radiation graft polymerization, a simultaneous irradiation method of simultaneously irradiating the polymeric material to be the main chain and the (meth)acrylic acid ester with radiation to perform graft polymerization, and the polymeric material to be the main chain are previously described. A pre-irradiation method of irradiating with radiation and bringing the (meth)acrylic acid ester into contact therewith for graft polymerization may be mentioned. However, the pre-irradiation method is preferable because the amount of homopolymer produced is small.
As for the pre-irradiation method, a polymer radical method in which a polymer material forming a main chain is irradiated with an inert gas in an inert gas, and a polymer material forming a main chain in a presence of oxygen is irradiated with radiation. Any of the peroxide methods can be used.
The amount of radiation energy is usually 1 kGy or more, preferably 5 kGy or more, more preferably 10 kGy or more, and usually 1,000 kGy or less, preferably 500 kGy or less.
The temperature condition for irradiation with radiation is usually room temperature, preferably under cooling.
The irradiation time of the radiation is usually 1 second or more and 24 hours or less.
Within the above range, the polymerization can be sufficiently advanced and the deterioration of the polymer base can be suppressed.

The method of contacting the main chain polymer material with the (meth)acrylic acid ester in the case of radiation graft polymerization by the pre-irradiation method is not particularly limited, but the main chain polymer material after irradiation with radiation is (meth) A method of immersing it in a solution containing an acrylic ester may be mentioned.
As the solvent used for the solution containing the (meth)acrylic acid ester, water, dichloroethane, chloroform, N-methylformaldehyde, N-methylacetamide, N-methylpyrrolidone, γ-ptyrolactone, n-hexane, methanol, ethanol, 1-propanol, tert-butanol, toluene, cyclohexane, cyclohexanone, dimethyl sulfoxide and the like can be mentioned.
The concentration of the (meth)acrylic acid ester in the solution is not particularly limited and can be appropriately set depending on the purpose, but is usually 5% by mass or more, usually 50% by mass or less, preferably 30% by mass or less. , And more preferably 20 mass% or less.
The immersion temperature is usually 0°C or higher, preferably 20°C or higher, and preferably 80°C or lower.
The immersion time is usually 0.1 hours or longer, preferably 24 hours or shorter, and more preferably 12 hours or shorter.

Ｗ_１：グラフト重合前の主鎖となる高分子材料の乾燥質量［ｇ］
Ｗ_２：グラフト重合後の重合体の乾燥質量［ｇ］ The graft ratio of the polymer according to the present invention is usually 1% by mass or more, preferably 10% by mass or more, and usually 1000% by mass or less, preferably 300% by mass or less. Within the above range, there is an advantage that a functional group such as adsorption performance can be introduced in a sufficient amount while maintaining the characteristics of the polymer material serving as the main chain before graft polymerization.
The graft ratio (X _dg [mass %]) can be calculated using the following calculation formula.

W ₁ : Dry mass [g] of the polymer material serving as the main chain before graft polymerization
W ₂ : Dry mass of polymer after graft polymerization [g]

The polymer material serving as the polymer main chain is not particularly limited, and known synthetic polymers and natural polymers can be appropriately selected and used. For example, polyolefin polymers such as polyethylene and polypropylene, styrene polymers such as polystyrene, acrylic polymers such as polymethylmethacrylate, fluoropolymers such as polytetrafluoroethylene (PTFE), and polyamide polymers such as nylon. Examples thereof include polymers, polyimide polymers, polyacetal polymers, polyester polymers, polycarbonate polymers, polyurethane polymers, polysaccharides such as cellulose, and proteins such as silk. The polymer material is not limited to a polymer composed of one kind of monomer, and may be a copolymer formed of two or more kinds of monomers (blocks).
Among these, polyolefin polymers and polysaccharides are particularly preferable.

（式（Ｂ−１）〜（Ｂ−３）、（Ｃ−１）〜（Ｃ−５）、及び（Ｄ−１）〜（Ｄ−１４）中、Ｒ^３はそれぞれ独立して炭素数２〜３０の炭化水素基を、Ｒ^４はそれぞれ独立して水素原子又は炭素数１〜３０の炭化水素基を、Ｒ^５はそれぞれ独立して水素原子又は炭素数１〜３０の炭化水素基を、Ｒ^６はそれぞれ独立して炭素数１〜３０の炭化水素基を、Ｘは酸素原子又は硫黄原子を、ａは０〜２の整数を、ｂは０〜３の整数を、ｃは０〜４の整数を、ｄは０〜５の整数を表す。但し、化合物内に炭化水素基であるＲ^６が２以上ある場合、Ｒ^６同士が互いに結合して環状構造を形成していてもよい。） The contact step according to the present invention includes a phosphorus-containing compound represented by the following formulas (B-1) to (B-3), a sulfur-containing compound represented by the following formulas (C-1) to (C-5), And a step of bringing at least one compound selected from the group consisting of nitrogen-containing compounds represented by the following formulas (D-1) to (D-14) into contact with the polymer. 1) to (B-3), phosphorus-containing compounds represented by the following formulas (C-1) to (C-5), and sulfur-containing compounds represented by the following formulas (D-1) to (D-14). ), at least one compound selected from the group consisting of nitrogen-containing compounds has the same meaning as the compound according to the present invention described above, and the same shall be abbreviated below as “the compound according to the present invention”. ..

(In formulas (B-1) to (B-3), (C-1) to (C-5), and (D-1) to (D-14), each R ³ independently has 2 carbon atoms. the 30 hydrocarbon group, a hydrocarbon group of each of R ⁴ is independently a hydrogen atom or 1 to 30 carbon atoms, a hydrocarbon group of R ⁵ is a hydrogen atom or a C1-30 independently, R ⁶ is independently a hydrocarbon group having 1 to 30 carbon atoms, X is an oxygen atom or a sulfur atom, a is an integer of 0 to 2, b is an integer of 0 to 3, and c is 0 to 4. And d represents an integer of 0 to 5. However, when there are two or more hydrocarbon groups R ⁶ in the compound, R ^{6 s} may combine with each other to form a cyclic structure. )

The contact method in the contact step according to the present invention is not particularly limited, and a known method can be appropriately adopted. However, the polymer according to the present invention or the solution containing the compound according to the present invention is immersed in the polymer. There is a method.
When the solvent is used in the dipping method, the type of the solvent is water, ethanol, ethylene glycol, a protic polar solvent such as glycerin, acetone, dimethylacetamide (
Aprotic polar solvents such as DMA), N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP) and dimethylsulfoxide (DMSO), hydrocarbon solvents such as hexane, benzene and toluene, diethyl ether, 1 , 4-dioxane, an ether solvent such as tetrahydrofuran (THF) and a halogen solvent such as 1,2-dichloroethane and chloroform.
The concentration of the compound according to the present invention in the solution is usually 10% by mass or more, preferably 20% by mass or more, and 100% by mass or less.
The temperature of the solution is usually 0° C. or higher, preferably 20° C. or higher, preferably 80° C. or lower, more preferably 60° C. or lower.
The contact time is usually 0.1 hour or longer, preferably 24 hours or shorter, and more preferably 12 hours or shorter.

The production method of the present invention is not particularly limited as long as it includes the preparation step and the contact step according to the present invention described above, but is not limited to the washing step of washing the solid composition after the contact step, and the solid composition after the washing step. It is possible to include a drying step of drying the product.

The application of the solid composition produced by the production method of the present invention is to be used as an adsorbent for adsorbing a metal element, an ion exchange resin, a solid acid, a solid base, etc., like the solid composition of the present invention. Is mentioned.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the following specific examples.

<Electron beam dose and graft ratio in radiation graft polymerization>
Irradiation of non-woven fabric made of polyethylene, which is the main chain of the polymer, with electron beam (dose: 20 to 500 k
Gy) was carried out, and then graft polymerization was carried out by contacting it with a 20% by mass aqueous dodecyl methacrylate solution (Tween 20 (surfactant): 2%, water: 78%) at 60° C. for 6 hours. A graph showing the relationship between the electron beam dose and the graft ratio is shown in FIG.

<Production of solid composition>
(Example 1)
After irradiating electron beam (dose: 500 kGy) to the polyethylene non-woven fabric which is the main chain of the polymer, it was made into a 20 mass% dodecyl methacrylate aqueous solution (Tween 20 (surfactant): 2%, water: 78%). Graft polymerization was carried out by contacting at 60° C. for 6 hours.

The obtained polymer was dipped in mono-2-ethylhexyl 2-ethylhexylphosphonate (manufactured by Daihachi Chemical Industry Co., Ltd., hereinafter referred to as "EHEP") and shaken at room temperature for 12 hours (shaking condition: 200 revolutions/minute). did. After shaking, EHEP attached to the surface was washed to obtain a solid composition.
As a result of structural analysis of the obtained solid composition using FT-IR, a peak at 1240 cm ⁻¹ due to the P═O bond of EHEP was observed (see FIG. 2), and thus EHEP was immobilized. It is thought that it is. The amount of phosphate groups introduced into the solid composition was 1.0 mmol/g.

<Evaluation of adsorption characteristics of scandium (Sc)>
The adsorption property of scandium (Sc) of the solid composition of Example 1 was evaluated. The adsorption characteristics were evaluated by measuring the adsorption rate in both the batch method and the column method.
In the batch method, a mixed solution containing scandium (Sc) and iron (Fe) dissolved at a concentration of 1 mg/L was adjusted to pH 0 to 3, and then the solid composition of Example 1 (graft ratio:
120%, EHEP concentration: 1.0 mmol/g) was dipped and stirred for 12 hours to conduct an adsorption test. The concentrations of scandium (Sc) and iron (Fe) in the solution before and after the adsorption test were measured using ICP emission spectroscopy (ICP-OES), and the adsorption amount, adsorption rate, and scandium (Sc) adsorption selectivity were calculated. , Evaluated. The results are shown in Table 1 and FIG.

Further, in order to compare with the adsorption performance of scandium (Sc) of the known phosphoric acid type adsorbent, 2-hydroxylmethacrylic acid phosphoric acid (hereinafter, sometimes abbreviated as "HMPA") as a comparative example 1 by graft polymerization. The introduced adsorbent and, as Comparative Example 2, glycidyl methacrylate introduced by graft polymerization, and then the adsorbent in which phosphoric acid was introduced by the conversion reaction of the epoxy group (hereinafter, may be abbreviated as "GMA-PA"). It evaluated similarly. The results are shown in Table 1 and FIG.

From Table 1 and FIG. 3, all three types of adsorbents tended to have a high scandium (Sc) adsorption rate and a low iron (Fe) adsorption rate under low pH conditions. That is, it showed high adsorption selectivity for scandium (Sc) under strongly acidic conditions. The scandium (Sc) adsorption selectivity of the solid composition of Example 1 was higher than that of other adsorbents under all pH conditions, and particularly under strongly acidic conditions of pH 0-1 the iron (Fe) adsorption rate was high. Was about 6%, whereas the scandium (Sc) adsorption rate was 98% or more, showing extremely high scandium (Sc) adsorption selectivity. Also, the scandium (Sc) adsorption capacity was about 2 to 8 times higher than other adsorbents under all pH conditions.

In the column method, a mixed solution (pH 1) in which scandium (Sc) and iron (Fe) were dissolved at a concentration of 1 mg/L each was placed in a cylindrical column having an inner diameter of 7 mm filled with the solid composition of Example 1 at a space velocity of 250 h ^−. The solution was passed through the column ¹ and the concentrations of scandium (Sc) and iron (Fe) in the solution at the column outlet were quantified and evaluated. The results are shown in Fig. 4.
The solid composition of Example 1 was able to adsorb 95% or more of scandium (Sc) in the solution with respect to the passing amount of 564 times the volume. On the other hand, regarding the adsorption of iron (Fe), the iron (Fe) concentration at the column outlet sharply increases immediately after the start of liquid passage, and the iron (Fe) concentration reaches the initial concentration of 1 mg/L at the liquid passage ratio of 360. did. That is, after the liquid passage ratio of 360, iron (Fe) was not adsorbed at all, and only scandium (Sc) could be adsorbed selectively. The adsorption capacities of scandium (Sc) and iron (Fe) when passing a volume of 5000 times the adsorbent volume were 5.22 mg-Sc/g-adsorbent and 0.12 mg-Fe/g-adsorption, respectively. Since it was a material, it was found that the scandium (Sc) adsorption capacity was about 44 times larger than the iron (Fe) adsorption capacity. From the above results, the solid composition of Example 1 has a high capacity and selectively scandium (Sc) even under the condition that iron (Fe), which is dissolved in the same trivalent state as scandium (Sc) and has similar adsorption behavior, coexists. ) Can be adsorbed.

<Adsorption characteristic evaluation of dysprosium (Dy) and neodymium (Nd)>
The solid composition of Example 1 and HMPA as Comparative Example 1 were each immersed in a mixed solution (pH 2.6) in which dysprosium (Dy) and neodymium (Nd) were dissolved at a concentration of 1 ppm, respectively, and the adsorption characteristics were evaluated. The results are shown in Table 2.

The adsorbability of dysprosium (Dy) and neodymium (Nd) of the solid composition of Example 1 was confirmed.

The solid composition of the present invention is an adsorbent for adsorbing a metal element, an ion exchange resin, a solid acid, a solid base, or the like, which is an adsorbent for adsorbing a rare earth element (rare earth) metal element having a particularly high economic value. Can be used as It has been confirmed that certain rare earth elements such as scandium (Sc) are dissolved in a very small amount in environmental water such as hot spring water, and it is suitable for selectively recovering such dissolved rare earth elements. Can be used.

Claims (8)

A solid composition based on a polymer having a structure represented by the following formula (A) in a side chain and having a graft ratio of 120% by mass :
Containing mono-2-ethylhexyl 2-ethylhexylphosphonate,
The content of the polymer in the solid composition is 50 mass% or more and 95 mass% or less,
A solid composition, wherein the content of mono-2-ethylhexyl 2-ethylhexylphosphonate in the solid composition is 0.01 mmol/g or more and 100 mmol/g or less.

(In the formula (A), R ^1's each independently represent a hydrogen atom or a methyl group, R ^2's each independently represent a hydrocarbon group having 12 to 18 carbon atoms, and n represents an integer of 2 to 100,000. .) The solid composition according to claim 1, wherein the polymer is in a fibrous form. The solid composition according to claim 1 or 2, which is an adsorbent for adsorbing a metal element. The solid composition according to claim 3, wherein the metal element is a rare earth element. A preparatory step of preparing a polymer having a structure represented by the following formula (A) in a side chain and having a graft ratio of 120% by mass , and mono-2-ethylhexyl 2-ethylhexylphosphonate as the polymer. A method for producing a solid composition, comprising the step of contacting
The content of the polymer in the solid composition is 50 mass% or more and 95 mass% or less,
The method for producing a solid composition, wherein the content of mono-2-ethylhexyl 2-ethylhexylphosphonate in the solid composition is 0.01 mmol/g or more and 100 mmol/g or less.

(In the formula (A), R ^1's each independently represent a hydrogen atom or a methyl group, R ^2's each independently represent a hydrocarbon group having 12 to 18 carbon atoms, and n represents an integer of 2 to 100,000. .) The solid composition according to claim 5, wherein the preparing step includes graft-polymerizing a (meth)acrylic acid ester represented by the following formula (a) onto a polymer material serving as a main chain of the polymer. Method of manufacturing things.

(In the formula (a), R ^1's each independently represent a hydrogen atom or a methyl group, and R ^2's each independently represent a hydrocarbon group having 12 to 18 carbon atoms.) The polymer material is a polyolefin polymer, a styrene polymer, an acrylic polymer, a fluorine polymer, a polyamide polymer, a polyimide polymer, a polyacetal polymer, a polyester polymer, a polycarbonate polymer. The method for producing a solid composition according to claim 6, wherein the solid composition is at least one polymer selected from the group consisting of a polyurethane polymer, a polysaccharide, and a protein. An adsorbent having a structure represented by the following formula (A) in the side chain and having a graft ratio of 120% by mass as a base and containing mono-2-ethylhexyl 2-ethylhexylphosphonate. A method for adsorbing a rare earth element, which comprises contacting a solution containing a rare earth element,
The content of the polymer in the adsorbent is 50 mass% or more and 95 mass% or less,
The content of mono-2-ethylhexyl 2-ethylhexylphosphonate in the adsorbent is 0.01 mmol/g or more and 100 mmol/g or less,
A method for adsorbing a rare earth element, characterized in that the pH of the solution in which the rare earth element is dissolved is 0 to 3.

(In the formula (A), R ^1's each independently represent a hydrogen atom or a methyl group, R ^2's each independently represent a hydrocarbon group having 12 to 18 carbon atoms, and n represents an integer of 2 to 100,000. .)

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