Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
1999-04-14
2001-07-31
Wu, David W. (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S217000, C526S218100, C526S219000, C526S219100
Reexamination Certificate
active
06268452
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a novel process for the production of an allylamine polymer. More specifically, it relates to a process for the production of an allylamine polymer, in which an allylamine polymer useful for various purposes in the field of fine chemicals can be industrially advantageously produced in an organic solvent.
PRIOR ART OF THE INVENTION
A monoallylamine polymer is a linear olefin polymer having a side chain containing a primary amino group, and it is a cationic polymer compound which is well soluble in water and is positively chargeable. The above monoallylamine polymer has characteristic reactive polymer structure and properties, and is therefore remarkably widely used in fields of dye fixing agents for reactive dyes, dye fixing agents for direct dyes, additives for inkjet recording sheets, and the like.
Concerning the production of the above monoallylamine polymer, the following production methods are known.
(1) A method in which a monoallylamine polymer is obtained by a gas-phase polymerization using tetrafluorohydrazine as a catalyst (U.S. Pat. No. 3,062,798).
(2) A method in which a small amount of water is added to monoallylamine hydrochloride, the mixture is brought into a dissolved state at 80 to 85° C., and hydrogen peroxide is little by little added to obtain a monoallylamine hydrochloride polymer (V. V. Zykova, et al., Tr. Inst. Khim. NauK, Akad. Nauk. Kaz. SSR 89-94 (1964), Chem. Abstr., 61, 14855 (1964))
(3) A method in which a monoallylamine hydrochloride is dissolved in a tert-butyl alcohol-chlorobenzene mixed solvents in the co-presence of diethylphosphite, and the monoallylamine hydrochloride is polymerized in the presence of azobisisobutyronitrile as an initiator at a reflux temperature of the solvents (German Laid-open Patent Publication No. 2 946 550).
(4) A method in which a monoallylamine is polymerized in a protonic acid (phosphoric acid, sulfuric acid, hydrochloric acid) by irradiation with gamma ray or with ultraviolet ray in the co-presence of hydrogen peroxide (V. A. Kavanov, et al., Vysokomol, Soed, 18(9), 1957 (1976)).
(5) A method in which an inorganic acid salt of a monoallylamine is polymerized in a polar solvent in the presence of a radical polymerization initiator having a molecule containing an azo group and cationic nitrogen (e.g., JP-A-58-201811 and JP-B-2-14364).
Of the above methods, clearly, the methods (1) to (4) cannot be said to be practical since they are difficult to carry out industrially or a polymerization solution is extremely colored. The above method (5) is practiced in industry. Generally, water is used as a polar solvent, and when the above method (5) is carried out in an organic solvent, the yield from the polymerization decreases, and it has not been industrially carried out in an organic solvent.
Practically at present, there is known no simple practical method of producing a monoallylamine polymer in an organic solvent.
An N,N-dialkylallylamine polymer is considered a remarkably interesting practical polymer as compared with the above monoallylamine polymer. As described in Comparative Example 12 on pages 8 and 9 of JP-B-2-14364, even polymerization of a monomer such as N,N-dimethylallylamine in the presence of a radical polymerization initiator having a molecule containing an azo group and cationic nitrogen can give only a trace amount (yield 5%) of a polymer, and no reports have said that N,N-dialkylallylamine polymer can be obtained at high yields by polymerization in the presence of a radical polymerization initiator including other polymerization initiators.
As a method for producing N,N-dialkylallylamine polymer, there are known only methods in which some polymer other than the N,N-dialkylallylamine polymer is used as a starting material and substituents of side chain of the polymer are chemically converted to obtain an N,N- dialkylallylamine polymer. Among them is a method of producing N,N-dialkylallylamine polymer in which poly(N,N-dialkylacrylamide) such as poly(N,N-dimethylacrylamide) is reacted with sodium-bis(2-methoxyethoxy)aluminum hydride (U.S. Pat. No. 4,053,512). However, the defect of the above method is that a special reducing agent is used, and so it is difficult to industrially produce the intended polymer. There is another method of producing N,N-dialkylallylamine polymer, in which formic acid and formaldehyde are reacted with a polyallylamine to produce N,N-dimethylallylamine polymer (JP-A-60-108405). This method cannot necessarily be said to be satisfactory since two-step reactions are required for obtaining the end product from a monoallylamine as a starting material.
As described above, it is considered that N,N-dialkylallylamine itself does not easily undergo polymerization. In reality, further, no reports have said that copolymers of N,N-dialkylallylamine and allylamines are produced by polymerization.
Concerning N-monoalkylallylamine polymer, JP-A-61-179211 and JP-A-2-80681 describe the production thereof by polymerizing N-monoalkylallylamine hydrochloride in an aqueous solution in the presence of a specific radical polymerization initiator having a molecule containing an azo group and cationic nitrogen. However, almost no polymerization in an organic solvent is known.
Meanwhile, if industrial polymerization of allylamines in an organic solvent is feasible, it is considered that an anhydrous allylamine polymer can be easily obtained and is therefore useful in the field of hydrophobic applications or for using it in an anhydrous reaction.
SUMMARY OF THE INVENTION
Under the circumstances, it is an object of the present invention to provide a process for industrially advantageously producing allylamine polymers from various allylamines as raw materials in an organic solvent with ease at high yields.
For achieving the above object, the present inventors had made diligent studies and as a result have found that the above object can be achieved by polymerizing addition salts of various allylamines in a medium containing an organic solvent in the presence of a radical polymerization initiator which is a specific azo compound. The present invention has been completed on the basis of the above finding.
That is, according to the present invention, the above object of the present invention is achieved by a process for the production of an allylamine polymer, which comprises polymerizing an addition salt of at least one selected from allylamines in a medium containing an organic solvent in the presence of at least one radical polymerization initiator selected from an azo compound of the general formula (I),
wherein each of R
1
to R
4
is independently a hydrocarbon group, provided that R
1
and R
2
may bond to each other to form a ring and that R
3
and R
4
may bond to each other to form a ring, and each of R
5
and R
6
is independently an alkyl group,
and an azo compound of the general formula (II),
wherein each of R
11
to R
14
is independently a hydrocarbon group, provided that R
11
and R
12
may bond to each other to form a ring and that R
13
and R
14
may bond to each other to form a ring, and each of R
15
and R
16
is independently a hydrogen atom or an alkyl group.
Specifically, according to the present invention, there are provided;
(1) a process for the production of an allylamine polymer, which comprises polymerizing a monoallylamine addition salt,
(2) a process for the production of an allylamine polymer, which comprises polymerizing an N,N-dialkylallylamine addition salt,
(3) a process for the production of an allylamine polymer, which comprises copolymerizing an N,N-dialkylallylamine addition salt and an addition salt of at least one selected from a monoallylamine, an N-monoalkylallylamine and a dialylamine.
(4) a process for the production of an allylamine polymer, which comprises polymerizing an N-monoalkylallylamine addition salt,
(5) a process for the production of an allylamine polymer, which comprises copolymerizing an N-monoalkylallylamine addition salt and an addition salt of at least one selected from a monoallylamine and
Endo Tadao
Hayashi Ikuo
Kato Tadashi
Nakata Yasuhito
Choi Ling-Siu
Nitto Boseki Co. Ltd.
Nixon & Vanderhye
Wu David W.
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