Patent GB-1454345-A (GB)
Title: Process for the manufacture of polyethers containing ionic bonds
IPC: D21H17/53
Filed: 1974-02-07
Abstract: 1454345 Crosslinked polyethers containing ionic bonds CIBA-GEIGY AG 7 Feb 1974 [14 Feb 1973] 5729/74 Heading C3B [Also in Division C2] A process for the manufacture of a crosslinked macromolecular polyether containing ionic bonds comprises reacting a polyhydric mono- or poly-nuclear phenol (A) which is substituted in the o- or p-positions to the OH groups by at least 2 radicals of the formula -CH 2 -NR<SP>1</SP>R<SP>2</SP> in which R<SP>1</SP> and R<SP>2</SP> denote a saturated or unsaturated hydrocarbon radical with 1-4 carbon atoms or together with the nitrogen atom denote a morpholino radical, (such phenols being Mannich bases), with an organic compound (B) which contains at least one Cl, Br or I atom bonded to a hydrocarbon radical and at least one epoxide group, with addition of the epoxide group to the phenol group and with quaternization of the halogenated hydrocarbon radical with the radical of the formula -CH 2 -NR<SP>1</SP>R<SP>2</SP>, at a temperature of 20-200‹ C. The reaction may optionally be carried out in the presence of an epoxidefree organic compound (C) which contains at least one Cl, Br or I atom bonded to a hydrocarbon radical, and in the case of a heterocyclic or carbocyclic compound, the or each Cl, Br or I atom may be bonded to the ring either directly or via a hydrocarbon radical. If less than an equivalent amount of epoxide groups of compound (B) is present relative to the phenolic OH group of phenol (A) then a halogen-free epoxide compound (D) may be added either before, during or after the reaction of (A) and (B) and optionally (C) to bring about equivalence. The reaction may be carried out in the presence of water or an organic solvent. The reaction may take place in the manner of a bead polymerization in an aqueous medium using a protective colloid, e.g. polyvinyl alcohol or a cellulose derivative, and the product used as an ion-exchanger. Preferred phenols (A) have the formula where E and K represent hydrogen or the radical of formula -CH 2 NR<SP>1</SP>R<SP>2</SP>, a=0 or 1, and R represents -CH 2 -, -C(CH 3 ) 2 -, -SO-, -SO 2 - or -CO-. Suitable compounds (B) are haloalkyl glycidyl ethers; epoxyhaloalkanes; polyepihalohydrins containing at least one terminal epoxide group and having a degree of polymerization of 3-500; and substances of the formula where R<SP>4</SP> denotes a m-valent aliphatic or aromatic radical. X=Cl, Br or I, m=1-6, p=1-20 prepared by the addition reaction of mono- or polyhydric alcohols or phenols with more than stoichiometric amounts of epihalohydrin in the presence of Friedel-Crafts catalysts and subsequent dehydrohalogenation. Suitable compounds (C) are alkyl, alkenyl and aralkyl mono- and di-halides, cyanuric chloride, polyepihalohydrins and polyaddition products of polyhydric alcohols and epihalohydrins. Suitable compounds (D) are epoxidized cycloolefins, glycidyl esters of optionally hydrogenated phthalic acids, heterocyclic glycidyl compounds, diglycidyl ethers of bisphenol A or 1,4-butanediol or tetraglycidyl ethers of pentaerythritol. In the examples crosslinked polyethers are prepared (A) either by reacting 2,2<SP>1</SP>,6,6<SP>1</SP>- tetrakis(dimethylaminomethyl)bisphenol A with either (1) 2-chloroethyl glycidyl ether or (2) an adduct (X) of pentraerythritol and epichlorohydrin and optionally an epoxide resin of bisphenol A and epichlorohydrin; or (B) by reacting a phenol of the formula and adduct (X), and a bisphenol A epoxide resin; or (C) by reacting a phenol of the formula with either the adduct (X) or with the adduct of 2,2<SP>1</SP>,6,6<SP>1</SP>-tetramethylol cyclohexanol-1 and epichlorohydrin, and a bisphenol-A epoxy resin. In another example an anion-exchange resin is prepared by first reacting bisphenol A, aqueous dimethylamine and aqueous HCHO, then adding water and polyvinyl alcohol and heating with stirring and then reacting with epichlorohydrin and 1,3-dichloroisopropanol. The product is an infusible bead condensate. Uses.-Ion-exchangers.