Mannich polymers

Mannich polymers Cationic, solution polymer flocculants with a MW of 5 to 8 M. Very high viscosity at only 4 to 8% active strength solution liquid. A hydrolyed polyacrylamide, it is very useful for general municipal waste water treatment. The dose rate normally is 200 to 300 ppm or more. 

Mannich polymers Cationic, solution polymer flocculants... 

Ryan M, Pawlowska L. Quaternary mannich polymer microemulsion (QMM) with rapid standard viscosity (SV) development. US patent 5789472.1998. 

The resihency and dyeabihty of poly(vinyl alcohol) fibers is improved by a process incorporating -hydroxybenzaldehyde to provide a site for the formation of a stable Mannich base. Hydroxyl groups on the fiber are converted to acetal groups by -hydroxybenzaldehyde. Subsequent reaction with formaldehyde and ammonia or an alkylamine is rapid and forms a stable Mannich base that is attached to the polymer backbone (94). 

Benzimidazolinone, 1,3-dimethyl-Friedel-Crafts reaction, 5, 429 Benzimidazolinone, 1,3-divinyl-synthesis, 5, 393 Benzimidazolinone, 6-methyl-Friedel-Crafts reaction, 5, 429 Benzimidazolin-2-one polymers, 1, 281 Benzimidazolinones alkylation, 5, 390 Friedel-Crafts reaction, 5, 429 Mannich reaction, 5, 390 nitration, 5, 429 reactions, 5, 442... 

Mannich reactions, 3, 21 polymers, 1, 288 ring contraction, 3, 29 Pyridazinones, amino-diazotization, 3, 35 reaction... 

Poly(2,6-dimethyl-l,4-oxyphenylene) (poly(phenylene oxide), PPG) is a material widely used as high-performance engineering plastics, thanks to its excellent chemical and physical properties, e.g., a high 7 (ca. 210°C) and mechanically tough property. PPO was first prepared from 2,6-dimethylphenol monomer using a copper/amine catalyst system. 2,6-Dimethylphenol was also polymerized via HRP catalysis to give a polymer exclusively consisting of 1,4-oxyphenylene unit, while small amounts of Mannich-base and 3,5,3, 5 -tetramethyl-4,4 -diphenoquinone units are always contained in the chemically prepared PPO. 

An impressive diastereoselective domino Mannich/Michael condensation of polymer-bound (polystyrene) glycosylimines 10-32 with 1,3-butadiene 10-33 has been reported by Kunz and coworkers [11]. These authors obtained dihydropiperid-inones 10-34 in good yield and high diastereoselectivity (Scheme 10.8). 

Scheme 7.56 One-pot Mannich reaction utilizing polymer-supported piperazine.

Phosphorous acid has also been of use for additions to imines. Originally investigated by Moedritzer and Irani,241 who developed a Mannich-type procedure for the preparation of phosphorus-centered species, the approach was found later to be useful for both primary and secondary amines in reaction with formaldehyde and phosphorous acid. The approach was later used for the preparation of a cationic exchange resin using a polymer substrate.242... 

Amino-substituted (Mannich base) polymers can be prepared by reacting amide-containing polymers with formaldehyde and a suitable amine. Sugiyama and Kamogawa (16) treated PAM in aqueous solution with excess paraformaldehyde (50°C, lh) followed by excess dimethylamine (50°C, lh). This procedure gave 68% conversion to amine. Schiller and Suen (9) used a similar procedure with monomeric formaldehyde and various amines, but with excess PAM. Muller et al. (17) prepared monomeric amines from... 

The "Mannich" adduct synthesized from the condensation of formaldehyde, 2-(methylamino)ethanol and poly-4-vinylphenol as shown in Structure I, has been evaluated as a function of molecular weight versus corrosion resistance as measured by salt spray and humidity tests on Bonderite 1000, an iron phosphate conversion coating. The molecular weight of the polymer was varied from approximately = 2,900 to 60,000. The corrosion resistance results were essentially equivalent over the molecular weight range evaluated. 

Oxazolidin-2-one (202) has been attached to poly(ethylenimine) (203) by Mannich reaction with formaldehyde (Scheme 97) (72NKK1179). The resultant polymer (204) was a... 

With amine initiators the so-called self-catalyzed polyols are obtained, which are used in the formulation of rigid spray foam systems. The rigidity or stiffness of a foam is increased by aromatic initiators, such as Mannich bases derived from phenol, phenolic resins, toluenediamine, or methylenedianiline (MDA). In the manufacture of highly resilient flexible foams and thermoset RIM elastomers, graft or polymer polyols are used. 

A second method of producing polyamines starting with the QH4—CO copolymer involves the following reaction, Eq. (20)67). The Mannich reaction has also been carried out on CO—C2Ht—C3H6 and CO—C2H4—C3H6—methyl vinyl ketone ter-polymers 47 ... 

Recently, three research groups independently disclosed that benzotriazoles 18 attached through various linkers to a polymeric support react with aldehydes and amines to form polymer-anchored Mannich-type adducts 19 (Scheme 7) [29]. These intermediates are cleaved under reducing conditions and in the presence of organomagnesium or organozinc reagents to provide libraries of secondary and tertiary amines in moderate yield (11-65%) and with acceptable purity (13->99%) [29]. 

Formaldehyde is not available as a pure monomer because it forms trimers and tetramers in the pure state (Chapter 52). The aqueous solution formalin used to preserve biological specimens is available—it is 37% formaldehyde and mostly consists of the hydrate CH2(OH)2 see Chapters. A pure dry polymer paraformaldehyde is also available and was mentioned in Chapter 9, Neither of these is particularly useful in aldol reactions. The aqueous solution is used in the Mannich reaction that we describe shortly. It is possible to make the short-lived monomer and capture it with a lithium enojate, but this is not trivial experimentally. 

When a Mannich reaction is carried out between a substrate containing at least two active hydrogen atoms and a primary or a bis-secondary amine, a polycondensation takes place with production of a polymeric derivative. Fhe polycondensation can also occur when both an NH group and one active hydrogen atom arc present in the same molecule. The reaction product is thus characterized by the presence of the methylene moiety, whieh is derived from the formaldehyde, and forms the polymer backbone, with the consequent possibility of polymer degradation by deamination or dcaminomethy-lation both of these reactions are typical of Mannich bases (Chap. II, A). 

Reactions of type (a) are among the most extensively studied, as they include the. synthesis of polyacrylamide Mannich bases, widely employed in water-purification processes. Many other polymeric substrates are, however, succe.ssfully subjected to Mannich reaction (Table 33). Moreover, some polymeric substances need to be suitably functionalized in order to undergo the aminomethylation reaction, as reported for polymeric ketones obtained by oxidation of polyenes." Further macromolecular carbonyl substrates could be provided by interesting vinyl monomers purposely designed to give polymers suitable for Mannich reaction." ... 

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