Insoluble, only slightly swellable polymers containing amino gro

Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From carboxylic acid or derivative thereof

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528315, 528317, 528319, 528340, 528345, 521 25, 521 31, 521 32, 521 38, 5263031, 5263071, 5263072, C08G 6908, C08G 7310

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055998984

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BRIEF SUMMARY
This application is a 371 of Pct/EP 93/03019 filed Oct. 29, 1993.
The present invention relates to insoluble, only slightly swellable polymers containing amino groups, to a process for their preparation by popcorn polymerization of open-chain N-vinylcarboxamides and hydrolysis of the copolymerized N-vinylcarboxamides to vinylamine units, and also to the use of the hydrolyzed popcorn polymers as ion exchangers.
DE-C-2,255,263 describes a process for preparing insoluble, crosslinked and only slightly swellable polymers of N-vinylpyrrolidone, in which N-vinylpyrrolidone is polymerized in aqueous solution in the presence of from 0.5 to 10% by weight, based on N-vinylpyrrolidone, of a cyclic acid amide that contains at least two ethylenicallyunsaturated groups, at least one of which is bound to the amide nitrogen atom, as crosslinking agent. The polymerization reaction is started by heating the reaction solution to at least 80.degree. C. and is continued to completion at the boiling point of water.
US-A-3,277,066 relates to a process for preparing insoluble polymers of N-vinyllactams by heating N-vinyllactams in the presence of oxides and hydroxides of alkali metals or alkaline earth metals as catalysts, and water. The polymerization is started at elevated temperatures, for example at 140.degree. C., and is then continued at a lower temperature (100.degree. C.).
US-A-4,451,582 describes a process for preparing insoluble, only slightly water-swellable, granular polymers from basic vinyl heterocyclics having a pKa of greater than 4 and their copolymers having up to 30% by weight of copolymerizable monomers, in which the monomers are polymerized in the presence of from 0.1 to 10% by weight, based on the total amount of monomers, of a crosslinking agent with exclusion of oxygen and polymerization initiators. The polymers are preferably prepared by precipitation polymerization in water. However, they can also be obtained in the absence of solvents for the monomers by heating the monomers at preferably 150.degree. to 180.degree. C. This reaction is however difficult to control and produces only low space-time yields and relatively highly contaminated products.
EP-A-0,088,964 describes a process for preparing insoluble, only slightly water-swellable, granular polymers wherein monomers of a basic vinyl heterocycle, such as vinylimidazole, vinylpyridines or N-vinyllactams, are polymerized in the presence of from 0.1 to 10% by weight, based on the total amount of monomers, of a crosslinking agent with exclusion of oxygen and polymerization initiators. The polymers obtainable in this way are used, for example, as ion exchangers or for the adsorptive immobilization of enzymes.
It is also known to prepare insoluble, only slightly swellable polymers of acrylic acid, known as popcorn polymers, by polymerizing acrylic acid in aqueous solution in the presence of small amounts of 2,2'-azobisisobutyronitrile, cf. J. W. Breitenbach et al., Makromol. Chemie 177, (1976), pp 2787 to 2792. However, polymer mixtures are obtained that contain as principal constituent a glassy polymer (gel) and minor amounts of popcorn polymers of acrylic acid. It is not technically possible to separate the polymer mixtures without substantial effort and expenditure.
It is known from Houben-Weyl, Vol. 14, Makrom. Stoffe, Part 1 (1961), p. 98, that popcorn polymers are formed from mixtures of styrene and divinylbenzene. Such polymers are also formed in the industrial polymerization of butadiene and styrene. Methyl acrylate also tends to form popcorn polymers. Popcorn polymers have the property that, on contact with the monomers of which they are composed or with other monomers, they can convert these into popcorn polymers. They act, as it were, as a nucleus for the polymerization. However, the activity is lost if they come into contact with air.
It is known from Ullmanns Encyklopadie der Techn. Chemie, 4th Edition, Vol. 19, 1980, p. 385, that an insoluble polymer only slightly swellable in water is formed in a spontaneous reaction on heating N-vinylpyrrol

REFERENCES:
patent: 3277066 (1966-10-01), Grosser et al.
patent: 4451582 (1984-05-01), Denzinger et al.
patent: 4647637 (1987-03-01), Tschang et al.
patent: 4658002 (1987-04-01), Tschang et al.

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