Patent GB-804057-A (GB)
Title: Novel esters and vinyl chloride polymer compositions containing the same
IPC: C07C45/74
Filed: 1956-09-05
Abstract: Polyvinyl chloride and copolymers of vinyl chloride with a monomer copolymerizable therewith, such as vinyl acetate and other olefinic esters of monocarboxylic acids, acrylonitrile, vinylidene chloride and fluoride, which contain at least 70 per cent by weight of vinyl chloride, are plasticized with an ester of 2-ethyl-4-methyl-2-pentenoic acid, 2-ethyl-4-methyl-2-penten-1-ol or 2-ethyl-4-methyl-1-pentanol having from 10 to 45 carbon atoms in the molecule and containing only carbon, oxygen and hydrogen. The 2-ethyl-4-methyl-2-pentenoic acid may be esterified with a monohydric alcohol or glycol containing 2 to 15 carbon atoms such as monohydric alcohols in the series ethyl up to pentadecyl alcohol and their isomers, 2-ethyl hexanol, the cyclohexanols, tetrahydrofurfuryl alcohol, 2-ethoxyethyl alcohol, 2-(n-butoxy) ethyl alcohol, 1,5-pentamethylene glycol and pentaerythritol, 2 - ethyl - 4 - methyl - 2 - penten - 1 - ol and the corresponding pentanol may be esterified with a mono-, di-, tri- or tetra-carboxylic acid having 2 to 15 carbon atoms, such as acetic, propionic, pentadecanoic, succinic, maleic, fumaric, glutaric, adipic, pimelic, suberic, azelaic, sebacic, phthalic, terephthalic, tetrahydrophthalic, trimesic, trimellitic, hemimellitic, pyromellitic, citric and tricarbollylic acids.  (For the preparation of these esters see Group IV (b).)  The plasticizers are blended with the vinyl polymer in conventional manner, as by mixing on a rolling mill or a Banbury-type mixer 5 to 60 per cent by weight of plasticizer being generally adequate. In an example, polyvinyl chloride resins are plasticized by the use of 40 per cent of the ester with 60 per cent by weight of the resin using the phthalic ester, the adipic ester and the sebacic ester of 2-ethyl-4-methyl-1-pentanol.  The plasticized compositions are compared with similar compositions using butyl benzyl phthalate and dioctyl phthalate as the plasticizers.ALSO:The invention comprises an ester of 2-ethyl-4-methyl-2-pentenoic acid, 2-ethyl-4-methyl-2-pentenol, or 2 - ethyl - 4 - methyl - 1 - pentanol having from 10 to 45 carbon atoms and containing only carbon, hydrogen and oxygen.  All three types of ester are obtainable via an intermediate 2-ethyl-4-methyl-2-pentenol which may be prepared by condensation of n-butyraldehyde and iso-butyraldehyde in the presence of aqueous alkali hydroxide, such as sodium hydroxide, at temperatures of from 25 DEG  to 80 DEG  C. 2-Ethyl-4-methyl-2-pentenoic acid may be obtained by liquid-phase oxidation of 2-ethyl-4-methyl-2-pentenal with air, oxygen or other oxygen-containing gas and oxidation catalysts, such as salts of cobalt and manganese may be employed.  The acid may be esterified with alcohols or glycols containing 2 to 15 carbon atoms in the molecule, such as the aliphatic monohydric alcohols from ethyl up to pentadecyl alcohol, the cyclohexanols, tetrahydrofurfuryl alcohol, 2-ethoxyethyl alcohol, 2-(n-butoxy)-ethyl alcohol, 2-ethyl hexanol, 1,5-pentamethylene glycol, pentaerythritol, in the presence of catalysts such as sulphuric acid or toluenesulphonic acid, water being removed azeotropically by solvents such as benzene or toluene. 2-Ethyl-4 - methyl - 2 penten - 1 - ol may be obtained by the reduction of 2-ethyl-4-methyl-2-pentenal with aluminium isopropylate or other aluminium alkylate preferably in the presence of a solvent. The alkenol may be esterified with aliphatic or aromatic, mono-, di-, tri- or tetra-carboxylic acids, such as acetic, propionic, pentadecanoic, succinic, maleic, fumaric, glutaric, adipic, pimelic, suberic, azelaic, sebacic, phthalic, terephthalic, tetrahydrophthalic, trimesic, trimellitic, hemimellitic, pyromellitic, citric and tricarballylic acids, or anhydrides such as tetrahydrophthalic anhydride.  2-Ethyl-4-methyl-1-pentanol may be obtained by the catalytic hydrogenation of 2-ethyl-4-methyl-2-pentenal or 2-ethyl-4-methyl-2-pentenol in the liquid phase, with or without a solvent, using catalysts such as nickel, cobalt, platinum, palladium, copper chromite or supported catalysts such as nickel or kieselguhr.  The alcohol may be esterified with the same acids as for the alkenol.  The products are useful as plasticizers for vinyl chloride polymers (see Group IV (a)).  Detailed examples describe the preparation by the above methods of 2-ethyl-4-methyl-2-pentenal, 2-ethyl - 4 - methyl - 2 - pentanoic acid and its esters with 1,5-pentamethylene glycol, 2-ethylhexanol and pentaerythritol, 2-ethyl-4-methyl-2-penten-1-ol and its adipic acid ester, and 2-ethyl-4-methyl-1-pentanol and its sebacic and phthalic acid esters.