Carboxylated polymers, process for the production of the same, a

Compositions – Water-softening or purifying or scale-inhibiting agents – Plant or organic material containing

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423DIG14, 516102, 516108, 524916, 525919, 526258, 526260, 526286, 526288, 5263171, C02F 510, C08F 2806, C08F22612, C08F22802

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061397679

DESCRIPTION:

BRIEF SUMMARY
This application is a 35 U.S.C. .sctn. 371 of PCT/JP97/01669, filed May 16, 1997.


FIELD OF THE INVENTION

The present invention relates to carboxylic acid polymers, manufacturing methods thereof, and gel prepared by swelling the carboxylic acid polymers in a dispersion medium. The carboxylic acid polymers and gel are chelating and can be suitably used, for example, for recovery of metals and disposal of metal-containing waste liquids and as catalysts.


BACKGROUND OF THE INVENTION

Examples of well-known, conventional, and highly metal-chelating resins include "Duolite ES466" (product name of an ion-exchange resin available from Rohm & Haas Co.) and "Diaion CR11" (product name of an ion-exchange resin available from Mitsubishi Chemical Corp.). These resins contain an iminodiacetic acid group, and further contain a carboxylic group and an highly electron-donative nitrogen atom in a principal chain of a functional group.
However, those conventional resins undergo proton exchanges under low pH and therefore decline in metal-chelating ability. In addition, the amount of metal ions scavenged (chelated) by the resins of a unitary weight is not satisfactory. Hence there is a large demand for a resin with a superior metal-ion-scavenging ability (chelating ability).


DISCLOSURE OF THE INVENTION

In view of the problems with old arts, an object of the present invention is to offer carboxylic acid polymers with a superior metal-ion-scavenging ability (chelating ability) and gels thereof as resins with a superior metal-ion-scavenging ability (chelating ability).
The inventors of the present invention have diligently worked to accomplish the object, and as a result, have found that carboxylic acid polymers of a particular structure and gels prepared by swelling the carboxylic acid polymers in a dispersion medium exhibit a superior metal-ion-scavenging ability (chelating ability), which has led to the completion of the invention.
The present invention relates to unconventional carboxylic acid polymers containing a carboxylic group and having at least one kind of bond selected from the group consisting of an amino bond, an ether bond, and a thioether bond in a side chain.
An example of carboxylic acid polymers of the above mentioned structure is unconventional carboxylic acid polymers containing a functional group represented by General Formula (1): integer from 0 to 6, and m4 is an integer from 0 to 6.
Another example of carboxylic acid polymers of the above mentioned structure is unconventional carboxylic acid polymers containing a functional group represented by General Formula (2): ##STR2## where Z is a hydrogen atom, a --(CHR.sub.4).sub.c --W.sub.2 --(CHR.sub.5).sub.d --COOR.sub.6 group, or a --(CH.sub.2).sub.f --X group, each of R.sub.1, R.sub.2, R.sub.3 R.sub.4, R.sub.5, and R.sub.6, independent of the others, is either a hydrogen atom or an alkyl group of a carbon number from 1 to 6, each of W.sub.1 and W.sub.2, independent of the other, is either an --NH-- group, an --S-- group, or an --O-- group, X is the principal segment of the carboxylic acid polymers, and each of a, b, c, d, e, and f, independent of the others, is an integer from 0 to 6.
The carboxylic acid polymers can be readily prepared by polymerizing monomer components containing a carboxylic acid monomer that contains an allylamino group and a carboxylic group and that has at least one kind of bond selected from the group consisting of an amino bond, an ether bond, and a thioether bond. An example of such a carboxylic acid monomer includes carboxylic acid monomers represented by General Formula (3): ##STR3## where Y.sub.4 is a hydrogen atom, an allyl group, or a --(CHR.sub.4).sub.c --W.sub.2 --(CHR.sub.5).sub.d --COOR.sub.6 group, each of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, and R.sub.6, independent of the others, is either a hydrogen atom or an alkyl group of a carbon number from 1 to 6, each of W.sub.1 and W.sub.2, independent of the other, is either an --NH-- group, an --S-- group, or an --O-- group, and each of a, b, c, and d, independe

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