Patent GB-661367-A (GB)
Title: Improvements in or relating to polyvinyl chloride plasticisers
IPC: C08K5/11
Filed: 1947-09-11
Abstract: Polyvinyl chloride is plasticized with an ester of an aliphatic or aromatic polybasic carboxylic acid with an alcohol having a number a of carbon atoms in the molecule less than eight and also an alcohol having a boiling point of not less than 160 DEG  C. and having a number b of carbon atoms in the molecule not less than eight, neither alcohol group having a double bond sufficiently close to the acid group to give a polymerizable compound, the ester having the formula <FORM:0661367/IV (a)/1> where X is a hydrocarbon group of an aliphatic or aromatic polybasic acid and R and R1 are different alcohol residues as above defined, but where both are alkyl groups at least one is a straight chain carbon group and n and m the number of each esterified alcohol group in the ester, the alcohols being selected so that the value of n.a+m.b/n+m is greater than 3 but less than 10.  Intermediate plasticizing effects may be obtained by preparing the ester by alcoholysis from an ester of a lower boiling alcohol (cf. Specification 654,842), and stopping the reaction before completion.  Most suitable esters are those of dibasic acids, e.g. phthalic and sebacic acids.  Esters may be made from the following higher alcohols having at least 8 C atoms m the molecule: hydration products of C8 to C20 olefines or mixtures thereof; Oxo synthesis alcohols from olefines, e.g. tri-propylenes, and especially nonyl alcohols from di-isobutylene; alcohols made by reacting formaldehyde with olefines; straight chain alcohols C8 to C18 made by reducing naturally occurring fatty acids; alcohols from Fischer - Tropsch "Gotch"; alkoxy-ethanols; secondary alcohols made by reducing oxidation products of hydrocarbons, e.g. phenyl methyl carbinol, and secondary alcohols, e.g. cyclohexanols made by hydrogenating phenols. Stress-elongation graphs are given for mixtures of equal quantities of P.V.C. and either methyl-nonyl- or methyl-hexahydro-xylenyl phthalates.  Ethyl-decyl- and methyl-heptadecyl phthalates are also specified.  Specifications 630,338 and 638,567 are referred to.ALSO:Esters are described of an aliphatic or aromatic polybasic carboxylic acid with an alcohol having a number a of carbon atoms in the molecule less than eight and also an alcohol having a boiling point of not less than 160 DEG  C. and having a number b of carbon atoms in the molecule not less than eight, neither alcohol group having a double bond sufficiently close to the acid group to give a polymerizable compound, the ester having the formula (COOR1)mX(COOR)n where X is a hydrocarbon group of an aliphatic or aromatic polybasic acid and R and R1 are different alcohol residues as above defined but where both are alkyl groups at least one is a straight chain carbon group and n and m the number of each esterified alcohol group in the ester, the alcohols being selected so that the value of <FORM:0661367/IV (b)/1> is greater than 3 but less than 10.  They are used as plasticizers for P.V.C. (cf. Group IV (a)).  Esters may be derived from phthalic or sebacic acids and higher alcohols listed are made by hydrating C8 to C20 olefines or mixtures thereof; oxo-synthesis alcohols from olefines such as tripropylenes and in particular nonyl alcohols from di-isobutylene; alcohols from reacting formaldehyde with olefines; straight chain alcohols C8-C18 made by reducing naturally occurring fatty acids or similar alcohols from Fischer-Tropsch "Gotsch"; alkoxy-ethanols; sec. alcohols made by reducing oxidation products of hydrocarbons, e.g. phenyl methyl carbinol and also by hydrogenating phenols, e.g. cyclohexanols. Specified esters are methylnonyl-, methyl-hexahydro-xylenyl-, ethyl-decyl and methyl-heptadecyl-phthalates.  The esters are preferably prepared as in 654,842 in which a fully esterified ester of the carboxylic acid with the lower or lowest boiling of the alcohols is reacted with the higher boiling alcohol or alcohols in order of boiling points, or an ester of an alcohol of lower boiling point than either or any of the alcohols selected to form the desired ester is reacted first with the lower and then with the higher alcohol, or alcohols, in order of boiling points, the reaction being effected in the absence of moisture at a temperature not above 90 DEG C.  Specifications 630,338 and 638,567, [both in Group IV (a)], also are referred to.