Patent GB-770539-A (GB)
Title: A new or improved process for bonding synthetic resins to solid materials
IPC: C03C25/323
Filed: 1954-05-17
Abstract: Unsaturated polyester resins are bonded to other solid materials, e.g. glass, by pre-treating the solid materials with a tertiary amine salt of an ethylenically unsaturated polyester which contains free carboxyl groups and copolymerizing in situ and in the presence of a polymerization catalyst an ethylenically unsaturated polyester and a monomer, such as a vinyl or allyl compound.  The term tertiary amine includes heterocyclic bases with a tertiary nitrogen atom, e.g. pyridine and N-methyl morpholine.  The amine salts may be made by condensation of a mixture of a polyalcohol and a polycarboxylic acid, either in such porportions as to give a product containing free carboxyl groups or by using a large excess of the polyalcohol and subsequently adding saturated or unsaturated dicarboxylic anhydrides; the products are then reacted with the amine, preferably in aqueous solution.  The solid material, e.g. glass fibre, is treated with a solution of the amine salt, and the solvent evaporated; if embedded in, or placed in contact with solutions of unsaturated polyesters in e.g. vinyl or allyl compounds, and polymerization catalysts, strong bonding is obtained between the solid material and the copolymer produced.  In Examples (1) an amine salt is made by heating maleic acid dimethyl ester and diglycol, reacting the product with maleic anhydride and heating the product with pyridine.  A glass plate is sprayed with a 1 per cent aqueous solution of the amine, dried and exposed to a temperature of 150 DEG  C.  A layer of a mixture of styrene and an unsaturated polyester made from maleic acid, phthalic acid and 1,3-butylene glycol, containing benzoyl peroxide as catalyst, is applied, covered with a further clean but otherwise non-pretreated glass plate, and polymerized at 90 DEG  C.  (2) A cable of glass monofils is coated with an aqueous solution of a pyridine salt of an unsaturated polymerization product made by heating maleic acid dimethyl ester and diglycol and reacting the product with maleic anhydride.  The filaments are dried, heated and reeled. Superposed layers of a fabric made therefrom are coated with a catalysed mixture of the unsaturated polyester and styrene used in Example 1, and hotpressed.  (3) A fabric made of glass monofils interlaced with linen is heated to remove the fluxing and sizing agent and to destroy the linen component, and placed in an aqueous solution of the amine salt used in Example 2.  After squeezing, drying and heating, layers of the fabric are superposed and coated with a mixture of an unsaturated polyester prepared from maleic acid, adipic acid, phthalic anhydride, glycol and N-diphenyl-diethanolamine, together with styrene and benzoyl peroxide, pressed at 25 DEG  C. and stored at 90 DEG  C. for an hour.ALSO:Synthetic resins are bonded to other solid materials, e.g glass fibres, by pretreating the solid materials with a tertiary amine salt of an ethylenically unsaturated polyester which contains free carboxyl groups.  The synthetic resin is formed in situ by co-polymerizing, in the presence of a polymerization catalyst, an ethylenically unsaturated polyester and a vinyl or allyl compound. The term tertiary amine includes heterocyclic bases with a tertiary nitrogen atom, e.g. pyridine and N-methyl morpholine.  The glass fibre may be treated with a solution of the amine salt, and the solvent evaporated.  In example (2), a cable of glass monofils is coated with an aqueous solution of a pyridine salt of an unsaturated polymerization product made by heating maleic acid dimethyl ester and diglycol with p-toluene sulphonic acid and reacting the product with maleic anhydride.  The filaments are dried, heated and reeled. Superposed layers of a fabric made therefrom are coated with a catalyzed mixture of an unsaturated polyester and styrene and hot-pressed.  In example (3) a fabric made of glass monofils interlaced with linen is heated to remove the fluxing and sizing agent and to destroy the linen component, and placed in an aqueous solution of the amine salt used in example 2.  After squeezing, drying and heating, layers of the fabric are superposed and coated with a mixture of an unsaturated ester prepared from maleic acid, adipic acid, phthalic anhydride, glycol and N-diphenyl - diethanolamine, together with styrene and benzoyl peroxide, pressed at 25 DEG C. and stored at 90 DEG C. for an hour.