Patent GB-902620-A (GB)
Title: Aromatic condensation polymer and method for its production
Inventor: DOEDENS JAMES DIRK
IPC: C08J9/02
Filed: 1959-08-19
Abstract: Solid polymers are produced by thermal condensation of at least one nuclear halomethylated diaromatic ether which may be mixed with one or more aromatic compounds having at least two labile hydrogen atoms per molecule but no halomethyl groups.  Halo is defined as chloro or bromo.  Hydrogen halide is split out during reaction.  It may be neutralized, permitted to escape or caught as bubbles in the reaction mixture resulting in a foamed product. Friedel-Crafts catalysts, e.g. aluminium iron or zinc chloride help the condensation.  Suitable halomethylated starting materials are chloro- or bromo-methyl diphenyl or ditolyl oxides, or halomethyl bis-(biphenyl) oxide.  They may be prepared by reacting in the presence of a catalyst the aromatic ether with a halomethylating agent, e.g. methyl chlormethyl ether, bis-chlormethyl ether or a mixture of formaldehyde and hydrogen chloride.  The reaction mixture with residual catalyst may be used directly for the condensation.  It may contain an average of one or more halomethyl groups per molecule.  Suitable non-halomethylated aromatic substances are the aromatic ethers corresponding with the halomethylated compounds, e.g. diphenyl oxide or phenylbiphenyl ethers, benzene, toluene or biphenyl.  Unreacted halomethyl groups in the products may be reacted with modifying agents.  If desired fillers, e.g. fibrous glass, perliteplaster agglomerate, exploded mica or magnesia, mica, silica, alumina or magnesia, may be incorporated before or during polymerization into the starting material.  The monomers may be used in solution, e.g. in aromatic hydrocarbons or halohydrocarbons, or as oil-in-water emulsions.  A list of suitable emulsifying agents is given. Polymerization may be in a mould.  It is preferably at 90 DEG -400 DEG C. and atmospheric pressure.  Plasticizers may be present.  The hydrogen halide present in solid foams may be displaced, e.g. with air by application of vacuum or gas pressure.  In examples, (1) A thermoplastic filament-forming polymer of mono-chlormethyl-diphenyl oxide is formed by heating the monomer with a little zinc chloride. (2) The product of reaction of 2 mols. of chloromethyl methyl ether and 1 mol. of diphenyl oxide in presence of zinc chloride was polymerized to a hard solid.  (3) A solid foam was produced from bis-chloromethylated diphenyl oxide.  (4) is similar to (3) but uses mixtures of mono- and di-chloromethyl-diphenyl oxide.  (5) A solid foam is produced from a mixture of bis(chlormethyl)diphenyl oxide and diphenyl oxide with zinc chloride or zinc oxide as catalyst.  (6) A eutectic mixture of diphenyl oxide and biphenyl was chloromethylated in presence of zinc chloride and the washed product was condensed to a solid foam.  (7) A mixture of o- and p-phenyl-biphenyl ether was chlormethylated with chloromethyl methyl ether and zinc oxide, washed and condensed to a solid foam. (8) 2,21-ditolyl oxide was chlormethylated and condensed. HCl escaped leaving a clear thermoplastic resin.  (9) Bis-(chlormethyl) diphenyl oxide heated with alkali gave a solid unfoamed resin.  (10) Bis-(chlormethyl) diphenyl oxide was condensed to a solid foam in the absence of a catalyst.  In other examples, test rods, foamed boards, fibreglass laminates or fireresistant materials were made by condensing starting materials according to the invention with filling or reinforcing substances such as perlite-plaster aggregate, fibre glass cloth, fibre glass rovings, exploded mica, magnesium oxide or silica. Some physical and chemical properties of the products, especially resistance to burning are demonstrated.ALSO:Chloro- or bromo-methylated diaromatic ethers are made by reacting a halomethylating agent such as methyl chloromethyl ether, bis chloromethyl ether, or a mixture of formaldehyde and hydrogen chloride with a diaromatic ether such as diphenyl or ditolyl oxide in presence of a catalyst, e.g. zinc chloride, aluminium chloride, ferric chloride or boron trifluoride.  Products mentioned are mono-, di-, tri-, and tetra - (chloromethyl)diphenyl oxide; mono-, and di-(bromomethyl)diphenyl oxide; mono-, and di-(chloromethyl)ditolyl oxide; and mono-(bromomethyl)-ditolyl oxide.  In Example 2, chloromethyl methyl ether is reacted with diphenyl oxide in the presence of zinc chloride.  In Example 6 a eutectic mixture of diphenyl oxide and biphenyl is similarly chloromethylated, and in Example 7 a mixture of the o- and p-isomers of phenyl-biphenyl ether. In Example 8 2,21 ditolyl oxide is similarly chloromethylated.ALSO:Solid polymers are produced by thermal condensation of at least one nuclear halomethylated diaromatic ether which may be mixed with one or more aromatic compounds having at least two hydrogen atoms per molecule but no halomethyl groups.  Halo is defined as chloro or bromo.  Hydrogen halide is split out during reaction. It may be trapped, as bubbles in the reaction mixture resulting in a foamed product.  Friedel-Crafts catalysts, e.g. aluminium iron or zinc chloride help the condensation.  Suitable halomethylated starting materials are chloro- or bromo-methyl diphenyl or ditolyl oxides, or halomethyl bis-(biphenyl) oxide. Suitable non-halomethylated aromatic substances are the aromatic ethers corresponding with the halo-methylated compounds e.g. diphenyl oxide or phenyl-biphenyl ethers, benzene, toluene or biphenyl.  If desired fillers, e.g. fibrous glass, perlite-plastic agglomerate, exploded mica or magnesia, mica, silica, alumina or magnesia may be incorporated before or during polymerization into the starting material.  The monomers may be used in solution e.g. in aromatic hydrocarbons or halohydrocarbons, or as oil-in-water emulsions. A list of suitable emulsifying agents is given.  Polymerization may be in a mould.  It is preferably at 90-400 DEG C and atmospheric pressure.  Plasticizers may be present.  The hydrogen halide present in solid foams may be displaced, e.g. with air, by application of vacuum or gas pressure.  In Examples, (3) A solid foam was produced from bis-chloromethylated diphenyl oxide.  (4) is similar to (3) but uses mixtures of mono- and di-chloromethyl-diphenyl oxide.  (5) A solid foam is produced from a mixture of bis(chlormethyl) diphenyl oxide and diphenyl oxide with zinc chloride or zinc oxide as catalyst.  (6) A eutectic mixture of diphenyl oxide and biphenyl was chloromethylated in presence of zinc chloride and the washed product was condensed to a solid foam.  (7) A mixture of o- and p-phenylbiphenyl ether was chlormethylated with chloromethyl methyl ether and zinc oxide, washed and condensed to a solid foam. (10) Bis-(chlormethyl) diphenyl oxide was condensed to a solid foam in the absence of a catalyst.  In other examples, foamed boards, containing fillers, foamed fibre glass laminates or foamed fibre glass mats were made by condensing starting materials according to the invention with filling or reinforcing substances such as perlite-plastic aggregate, fibre glass cloth, fibre glass rovings, exploded mica, magnesium oxide or silica.  Some physical and chemical properties of the products especially resistance to burning are demonstrated.