Process for polymerization of allylic compounds

Details Process for polymerization of allylic compounds Process for polymerization of allylic compounds

1999-10-27

2001-10-16

Richter, Johann (Department: 1621)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S219000, C564S160000, C564S288000

Reexamination Certificate

active

06303723

ABSTRACT:

BACKGROUND OF THE INVENTION
Allylic and vinylic compounds can be polymerized via a free radical addition process. However, while vinyl monomers (e.g., acrylamide, acrylic acid, acrylic acid esters, vinylamine) can be easily polymerized to obtain polymers of suitable size and in high yield, the same is not true for allylic monomers. The difficulty encountered with the polymerization of allylic monomers is due primarily to the stability of allyl radicals relative to vinyl radicals. Consequently, an initiating radical often abstracts a H-atom from the allylic monomer rather than adding to the C═C bond, resulting in a competing self-termination reaction between the allylic hydrogen atoms and the initiating free radical often referred to as allylic degradative chain transfer. The same difficulties are encountered when allylic monomers are copolymerized with vinylic monomers. Thus, to polymerize allylic monomers large quantities of a free radical initiator are usually required, resulting in the production of low molecular weight polymers which comprise relatively high quantities of terminal catalyst residues. Polymers of allylamines (e.g., allylamine, diallylamine, triallylamine) are particularly difficult to prepare due to a further decreases the reactivity of the allylic bond in polymerization reactions and unwanted side-reactions, both resulting from the presence of the amino functionality.
Several processes for polymerizing allylamine which use cationic water soluble diazo free radical initiators and/or additives such as multivalent metal ions are known (see, for example, U.S. Patent Nos. 4,504,640, 4,540,760 and 4,528,347, to Harada et al.; 4,927,896 to Blocker et al.). However, improvements in the current processes for polymerizing allylamine are needed. For example, the cationic charge on a diazo free radical initiator can improve the solubility of the compound in water. However, the ionic charge can also destabilize the radicals generated upon decomposition of the initiator and thus may adversely affect the process (e.g., result in polymers having high polydispersity). Furthermore, regulators or additives (e.g., multivalent metal ions) can be difficult to remove from the final polymer products and can render the polymer unacceptable for many uses, such as in the pharmaceutical industry.
A need exists for a process for polymerizing allylic amine compounds which reduces or eliminates the referenced problems.
SUMMARY OF THE INVENTION
The invention related to a process for preparing polymers of allylic amine monomers. In one embodiment, the process comprises:
a) preparing a reaction mixture comprising:
i) a polar reaction solvent;
ii) at least one salt of an allylic amine compound; and
iii) a free radical initiator comprising a water soluble non-ionic diazo compound represented by:
 wherein:
R
1
, R
2
, R
3
and R
4
are the same or different lower alkyl groups;
R
5
, and R
6
are each represented by
wherein X is a C
1
to C
12
alkylene group; and
b) polymerizing the reaction mixture.
The process can be used to prepare homopolymers of an allylic amine compound and to prepare copolymers comprising an allylic amine compound and one or more additional monomers. In one embodiment, the oxygen content of the reaction mixture is reduced to facilitate polymerization. In another embodiment, the solvent has a pH of less than about 3. In another embodiment, the invention is a process for polymerizing an allylic amine, for example, allylamine, diallylamine, triallylamine or combinations thereof. In another embodiment, the invention is a process for copolymerizing an allylic amine and a multifunctional comonomer to prepare a crosslinked polymer.


REFERENCES:
patent: 3888928 (1975-06-01), Willis et al.
patent: 3990958 (1976-11-01), Sasse
patent: 4121986 (1978-10-01), Battaerd
patent: 4256636 (1981-03-01), Roos et al.
patent: 4329441 (1982-05-01), Bergthaller
patent: 4452737 (1984-06-01), Schmidt et al.
patent: 4504640 (1985-03-01), Harada et al.
patent: 4528347 (1985-07-01), Harada et al.
patent: 4540760 (1985-09-01), Harada et al.
patent: 4605701 (1986-08-01), Harada et al.
patent: 4680360 (1987-07-01), Ueda et al.
patent: 4713431 (1987-12-01), Bhattacharyya et al.
patent: 4746715 (1988-05-01), Dworczak et al.
patent: 4749759 (1988-06-01), Shimizu et al.
patent: 4812540 (1989-03-01), Kageno et al.
patent: 4864007 (1989-09-01), Schleusener
patent: 4916216 (1990-04-01), Tanaka et al.
patent: 4927896 (1990-05-01), Blocker et al.
patent: 4950742 (1990-08-01), Ichiriki et al.
patent: 5422408 (1995-06-01), Cramm et al.
patent: 5665843 (1997-09-01), Iio
patent: 0 142 962 (1985-05-01), None
patent: 0 197 022 A1 (1986-10-01), None
patent: 0 280 445 A1 (1988-08-01), None
patent: 0 398 490 A2 (1990-11-01), None
Patent Abstracts of Japan, for Publication No. 09291493, Nov. 11, 1997, “Agent for Making Recording Paper Waterproof.”.
Patent Abstracts of Japan, for Publication No. 11263813, Sep. 28, 1999, “Preparation of Allyltrialkylammonium Salt Copolymer and Allytrialkylammonium Salt Copolymer.”.
Patent Abstracts of Japan, for Publication No. 62172007, Jul. 29, 1987, “Production of Low-Molecular-Weight Polymer of Monoallylamine Hydrochloride.”.
Bolto, B.A. et al., “Synthesis of Cross-Linked Polyallylamines Which Are Resistant to Sulfite Attack,”J. Macromol. Sci.-Chem. A17 (1): 153-166 (1982).
McLean, C.D. et al., “Cyclopolymerization. VI. Preparation and Properties of Crosslinked Polyamines by Cyclopolymerization,”J. Macromol. Sci. -Chem. A10(5): 857-873 (1976).
VA-086 Technical Information, Wako Chemicals U.S.A., Inc. 1995.
V-50 Technical Information, Wako Chemicals U.S.A., Inc. 1994.

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