Patent GB-822608-A (GB)
Title: Addition products of alkyl linoleates and alkyl fumarates and vinyl chloride polymers plasticised therewith
Inventor: DAZZI JOACHIM
IPC: C08K5/11
Filed: 1956-01-19
Abstract: Vinyl chloride polymers or copolymers containing at least 70% by weight of vinyl chloride and up to 30% of a copolymerizable olefinic co-monomer such as vinyl acetate or vinylidene chloride are plasticised by means of the addition products of a dialkyl fumarate having 1-8 carbon atoms in each alkyl group with an alkyl linoleate or a mixture of alkyl linoleate and alkyl oleate, each having 1-8 carbon atoms in the alkyl group, 2-4 mols. of dialkyl fumarate being combined with each mol. of alkyl linoleate or of alkyl linoleate plus alkyl oleate.  The adducts are cyclic compounds containing one to three 1,2-bis-(carbalkoxy)-ethyl groups in the molecule.  Their preparation is described (see Group IV (b)).  The plasticised resin normally contains 5-50% by weight of the addition product.  Other plasticisers and heat and light stabilizers may be present. Reference is made to plasticised polyvinyl resins containing 40% of adducts of 2-4 mols. of butyl fumarate with butyl linoleate or butyl esters of tall oil fatty acids (linolenic and oleic) or, for comparative purposes, of an adduct of butyl oleate with butyl fumarate and to plasticised vinyl chloridevinyl acetate copolymers containing 40% of the adduct of methyl or ethyl fumarate and 2-ethyl hexyl linoleate or n-propyl or amyl fumarate and the ethyl esters of the tall oil unsaturated fatty acids.  Numerous other adduct - components are specified.  U.S.A. Specification 2,687,421 is referred to.ALSO:The invention comprises addition products of a dialkyl fumarate having 1-8 carbon atoms in each alkyl group and an alkyl linoleate or a mixture of an alkyl linoleate and an alkyl oleate, having 1-8 carbon atoms in each alkyl group, from 2-4 mols. of dialkyl fumarate being combined with each mol. of alkyl linoleate or alkyl linoleate plus alkyl oleate.  The addition products may be prepared by heating the alkyl linoleate or mixture of alkyl linoleate and alkyl oleate, e.g. the C1-8 alkyl esters of a tall oil unsaturated fatty acid fraction from which the resin acids and unsaponifiable materials have been removed, with 2-4 mols. of the di-alkyl fumarate.  The reaction is preferably effected at 150-300 DEG  C. at ordinary pressure.  Sub- or super-atmospheric pressures may be used.  Inert high-boiling diluents and polymerization inhibitors, e.g. pyrogallol or tert.-butyl catechol may be present. The reaction is stated to result in the alkyl linoleate combining with 1 mol. of the dialkyl fumarate to give an adduct having an unsaturated cyclic structure to which the additional mols. of fumarate ester present add on with consequent introduction of 1,2-bis-(carbalkoxy)ethyl groups. When mixtures of alkyl linoleates and oleates are used, the product also contains adducts of the oleate with the fumarate esters.  Reaction times of 3-30 hrs. may be used to obtain a product in which the adducts are predominantly those having more than 2 mols. of fumarate combined in the molecule.  The adducts are useful as plasticizers for polymerized and copolymerized vinyl chloride (see Group IV (a)).  A comparative experiment describes the preparation of an adduct of butyl oleate and butyl fumarate averaging more than 2 combined mols. of the fumarate by the above method. U.S.A. Specification 2,687,421 is referred to.