Condensation polymers chloromethylation

A survey of the reaction conditions required to quaternize chloromethylated condensation polymers in a homogeneous media revealed that mixed solvent systems would be required to handle poly(oxy-2,6-dimethyl-3-chloromethyl-1,4-phenylene), The reaction of triethylamine with chloromethylated polysulfone proceeded cleanly in pure DMSO, and a model compound was easy to synthesize. Therefore, we focused our initial attention on polysulfone derivatives. 

The chloromethylated polymers are very reactive substrates for nucleophilic attach further elaboration can be accomplished under homogeneous conditions In aprotlc solvents, or under heterogeneous conditions In the presence of phase transfer catalysts. The following examples are representative of approaches to functionalized condensation polymers via chloromethylated Intermediates. 

CAS 52932-31-7 25212-19-5 Synonyms Adipic acid, diethylenetriamine, epichlorohydrin polymer Adipic acid, diethylenetriamine, epichlorohydrin resin Diethylenetriamine, epichlorohydrin, adipic acid polymer Epichlorohydrin, adipic acid, diethylenetriamine polymer Hexanedioic acid, polymer with N-(2-aminoethyl)-1,2-ethanediamine and (chloromethyl) oxirane Classification Condensation polymer Uses Antistat, film-former in cosmetics hair care resin in permanent sol ns. and hair sprays dye fixing agent in paper/paperboard in contact with aq./fatty foods Regulatory FDA 21CFR 176.170 Trade Name Synonyms Delsette 101 t[Hercules http //www.herc.com], Hercosett 57 [Hercules http //www.herc.com]... 

B) Modification of condensation polymers - Although the mechanical properties of condensation polymers are often superior to those of PS, little work has been done on the introduction of functional groups by chemical modification of condensation polymers. For example, chloromethylation of polymers con-... 

Daly, W.H., Chotiwana, S., and Nielsen, R., Chloromethylation of condensation polymers containing an oxy-1,4-phenylene backbone, in Polym. Prepr., Am. Chem. Soc., Div. Polym. Chem. 1979. p. 835-8. 

Platinum-group metals (qv) form complexes with chelating polymers with various 8-mercaptoquinoline [491-33-8] derivatives (83) (see Chelating agents). Hydroxy-substituted quinolines have been incorporated in phenol—formaldehyde resins (84). Stannic chloride catalyzes the condensation of bis(chloromethyl)benzene with quinoline (85). 

A functional group is introduced to the polystyrene 10 by chloromethylation Blanc reaction) in order to allow for reaction with the substrate 11. The polymer-bound diester is then treated with base to initiate the Dieckmann condensation. 

An imidazolide-supported polymer was used for transacylation of phosphatidylcholine. The polymer was obtained from a chloromethylated polystyrene with two mol-% divinylbenzene. The imidazolide group was anchored by reaction with 3-hydroxymethyl-1-tritylimidazole, cleavage of the trityl group, and condensation with palmitic acid 122]... 

For poly silanes made by Wurtz reaction, the presence of functional groups in polysilane polymers is limited by the vigorous conditions of the sodium condensation reaction. Any substituents that react with molten sodium metal must therefore be introduced after the polymer is synthesized. Halogen atoms can be introduced into alkenylpolysilanes by HBr or HC1 addition reactions, as shown for the 3-cyclohexenyl-ethyl polymers in equation (21).37 Chlorine atoms have also been introduced into arylpolysilanes by chloromethylation, in which -CH2C1 groups are substituted onto phenyl rings in the polymer.38... 

As Patchornik (54,55) showed the competitive self-condensation of an ester can be avoided if the ester molecules are separated by fixation on the polymer. According to Scheme 3,0.1 to 0.2 meq ester groups were fixed at the chloromethylated polymer. Pure monoalkylation can be achieved and no self-condensation is observed if the load is kept small. 

The asymmetric phosphorus-containing ligand DIOP, 2,2-0-isopropylidene-2,3-dihydroxy-l,4-bis(diphenylphosphino)butane, was incorporated into the chloromethylated polymers according to a literature procedure (20). The chloromethyl function was initially converted into the aldehyde, which was subsequently condensed with a tosylated diol, and the tosyl groups were ultimately converted into diphenylphosphine groups. 

Into a 500-ml three-neck round-bottom flask, equipped with a thermometer, reflux condenser and mechanical stirrer, were placed the chloromethylated crosslinked polystyrene beads or membranes. DMSO (300 ml—this amount should be sufficient to cover the enmeshed membranes) and 15 g of sodium bicarbonate were added to the flask, and the entire system was heated and stirred at 150°C for 6 hr. When the mixture had cooled, the newly formed aldehydic polymers were washed with water, THF, toluene, ethanol, and acetone. The supports were then dried for 4 hr at 120°C under vacuum. 

Reaction of 4 with 5-chloromethyl-8-hy-droxyquinoline hydrochloride at pH = 2 in water (5-chloromethyl-8-hydroxyquinoline is stable at reflux in 0.01 M HCl. but when the pH is increased over 5, an insoluble oligmer settles, making it easy, therefore, to note when self-condensation begins) yields the hydroxyamine polymers 7A (XE-305, Z = H. 43%... 

There is an alternative method of making functional derivatives for polymerization. Durene can be condensed with formaldehyde in the presence of hydrochloric acid and zinc chloride to give the bis-chloromethyl durene(75). This can be converted into a number of derivatives from which polymers can be made, e.g. durene-1,4-dicarboxylic acid for polyamides(76), the diacetic acid for polyesters(77,78) or for polyamides(79), the diisocyanatomethyl derivative for polyureas and polyurethanes(80,81), the dimethanol derivative for polyurethanes(82) and for epoxies(83), while the bis chloromethyl derivative has also been proposed for making polyethers (with bisphenol A)(84). In each case, the attraction from the durene derivative has been the introduction of higher melting points and inproved softening properties. None of these polymers have been commercialized, possibly in part because of the difficulty of obtaining durene at suitable-prices. 

Condensations of pyrroles with aldehydes and ketones occur easily by acid catalysis but the resulting pyrrolylcarbinols cannot usually be isolated, for under the reaction conditions proton-catalysed loss of water produces 2-alkylidenepyrrolium cations which are themselves highly reactive electrophiles. Thus, in the case of pyrrole itself, reaction with aliphatic aldehydes in acid inevitably leads to resins, probably linear polymers. Reductive trapping of these cationic intermediates produces alkylated pyrroles all free positions react and as the example shows, acyl and alkoxycarbonyl substituents are unaffected," A mechanistically related process is the clean 4-chloromethylation of pyrroles carrying acyl groups at C-2." ... 

Positive interactions between cationic species, including protons, with aromatic structures comprise an intensively examined and already well-documented phenomenon [142, 143], In the hypercrosslinked polystyrene these interactions may well be enhanced by a possible presence of condensed aromatic systems. As was shown in Chapter 6, Section 4.4, anthracene-type structures may easily be formed by the condensation of two chloromethylated styrene repeating units, followed by a subsequent oxidation. However, the early elution of pure HCl in Fig. 12.1 does not imply any retentive interactions between protons and the polymer. The retention of HCl occurs only in the presence of a salt. But why would the properties of HCl in the polymeric phase change so dramatically in the presence of metal chlorides, while no association of HCl with LiCl or CaCl2 takes place in solution The version (i) of attractive interactions of protons with the polystyrene phase thus cannot be accepted without serious doubt. 

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