Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2002-11-14
2004-01-27
Zalukaeva, Tatyana (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S111000, C526S115000, C526S137000, C526S201000, C526S093000, C502S159000, C502S169000, C502S527140, C502S527240
Reexamination Certificate
active
06683146
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a heterogeneous polymerization catalyst containing a carrier having a specific ligand carried thereon, a process for producing an acrylic polymer by living radical polymerization conducted in the presence of the heterogeneous polymerization catalyst, and an acrylic polymer obtained by the process for producing an acrylic polymer.
BACKGROUND OF THE INVENTION
A living polymerization method having unique effects that cannot be obtained by other polymerization methods has been known, by which the molecular weight, the molecular weight distribution and the chemical structure of the resulting polymer can be precisely controlled, a multi-dimensional block copolymer can be easily produced, and the terminal modification can be easily conducted. As the living polymerization method, an anion polymerization method, a cation polymerization method and a group transfer polymerization method have been specifically known.
A living radical polymerization method is being earnestly studied in recent years as a polymerization method that is expected to provide effects that cannot be obtained by the various living polymerization methods described in the foregoing because the polymerization is difficult to be affected by impurities contained in the system, so that the polymerization operation is convenient, and the polymerization method can be applied to a wide range of monomers.
As the living radical polymerization method, the following polymerization methods have been known at the present time.
(1) A polymerization method using an organic halogen compound, RuCl
2
(PPh
3
)
3
(Ph: phenyl group) and a Lewis acid, as a polymerization catalyst (M. Kato, et al.,
Macromolecules
, vol. 28, p. 1721 (1995))
(2) A polymerization method using an organic halogen compound and a CuCl/2,2,′-bipyrydine complex, as a polymerization catalyst (Matyjaszewski,
Pure Appl. Chem
., vol. A34(10), p. 1785 (1997))
(3) A polymerization method using an organic halogen compound and RuCl
2
(PPh
3
)3, as a polymerization catalyst (T. Ando, et al.,
Macromolecules, vol.
30, p. 4507 (1997))
(4) A polymerization method using an organic halogen compound, copper halide and, as a ligand, an organic phosphite triester, as a polymerization catalyst (JP-A-10-130317)
(5) A polymerization method using an organic halogen compound and a metallic complex having a specific ligand, as a polymerization catalyst (JP-A-10-152513)
However, because polymers obtained by these polymerization methods are colored, the polymers must be subjected to a decolorization and purification treatment after completing the polymerization reaction.
Since an adsorbent is generally used in the decolorization and purification treatment, there is a problem in that the yield of the polymer finally obtained is decreased. Furthermore, since the used adsorbent is treated as a waste, it brings about another problem in that the production cost is increased.
Therefore, the conventional living radical polymerization methods are disadvantageous due to the problems although they have the excellent effects that cannot be obtained by the other polymerization methods.
On the other hand, in order to easily separate a catalyst, various techniques utilizing a complex carried on a carrier as a radical polymerization catalyst have been known as disclosed in “mer Complex Catalysts”, p. 167-193 (Japan Scientific Societies Press (1982)).
Furthermore, JP-A-10-7720 suggests, in the column of Detailed Description of the Invention, a technique for producing a polymer by the living radical polymerization method using a solid catalyst exhibiting both the advantages of a uniform catalyst and the advantages of a heterogeneous catalyst simultaneously, which is formed by carrying and grafting a metallic catalyst on a polysilane type dendrimer or a polysiloxane type polymer.
In JP-A-10-7720, however, a specific method, a constitution and an effect of the invention and performance of the living polymerization are not clearly disclosed, and the technique lacks actual practicability.
Furthermore, in the technique of carrying and grafting a metallic catalyst on a polysilane type dendrimer or a polysiloxane type polymer, a large number of steps are required, and the yield of the resulting polymer is low. Moreover, it is difficult to separate and recover the polymer from the reaction solution, and therefore the technique is not a practical production method. Accordingly, there has been no report in that a solid catalyst is successfully applied to the living radical polymerization.
As described in the foregoing, the conventional living radical polymerization method is a disadvantageous technique due to the problems although it has excellent effects that cannot be obtained by the other polymerization methods.
SUMMARY OF THE INVENTION
The invention has been made to solve the problems associated with the conventional techniques to provide a heterogeneous polymerization catalyst, a process for producing an acrylic polymer and an acrylic polymer obtained by the process.
In the invention, a polymer can be obtained that is precisely controlled in the molecular weight, the molecular weight distribution and the chemical structure thereof and is free of colorization, and therefore the invention provides a process for producing an acrylic polymer having advantages in that a step of decolorization and purification is not necessary, the yield of the resulting polymer is high, and the amount of wastes formed is small. The invention also provides a heterogeneous polymerization catalyst used for the process for producing an acrylic polymer, and an acrylic polymer produced by the process for producing an acrylic polymer.
The invention relates to, as a first aspect, a heterogeneous polymerization catalyst containing (A) a radical generating substance, (B) a metallic halide containing a metallic element selected from the group consisting of the Group 4 to Group 12 elements and a halogen element selected from the group consisting of chlorine, bromine and iodine, and (C) a carrier carrying a ligand capable of forming a coordination bond with the metallic halide (B) (which will be sometimes simply referred to as “a carrier carrying a ligand (C)”).
As the radical generating substance (A), a halogen-containing organic compound having at least one carbon-halogen bond in the molecule is preferred, provided that the halogen element is either chlorine, bromine or iodine.
As the metallic halide (B), a metallic halide represented by FeCl
2
or FeCl
2
.H
2
O (wherein n is an integer of from 1 to 6) is preferred.
In the case where the metallic halide (B) is a metallic halide represented by RuCl
3
or RuCl
3
.H
2
O, the heterogeneous polymerization catalyst preferably contains a Lewis acid.
As the carrier carrying a ligand (C), insoluble polymer particles having a phosphine as a ligand are preferred.
The carrier (C) preferably has a crosslinked structure as the molecular structure thereof. In the case where the shape of the carrier (C) is a particle form, the average diameter (D50) thereof is preferably from 1 to 100 &mgr;m. The carrier carrying a ligand (C) preferably has, in the molecular structure thereof, a unit having a ligand part and a styrene unit. The proportion of the ligand in the carrier carrying the ligand (C) is preferably from 0.1 to 3.0 mmol/g.
The invention relates to, as a second aspect, a process for producing an acrylic polymer containing a step of polymerizing a monomer containing at least an acrylate and/or a methacrylate in the presence of the heterogeneous polymerization catalyst according to the first aspect of the invention.
The invention relates to, as a third aspect, an acrylic polymer produced by the process for producing an acrylic polymer according to the second aspect of the invention.
DETAILED DESCRIPTION OF THE INVENTION
Polymerization Catalyst for Heterogeneous System
The heterogeneous polymerization catalyst according to the invention contains (A) a radical generating substance, (B) a metallic halide, and (C) a carrier carrying a ligand, an
Hiraoka Satoshi
Inaba Yoshihiro
Fuji 'Xerox Co., Ltd.
Zalukaeva Tatyana
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