Patent GB-1108333-A (GB)
Title: Phosphite esters containing phenolic groups
IPC: C07F9/145
Filed: 1965-06-30
Abstract: Phosphite esters of polyphenols, having the general formula <FORM:1108333/C3/1> in which R is a C4-C10 hydrocarbon radical; y is 0, 1 or 2; z is 1, 2 or 3 and the sum of y and z equals 3; and A is selected from the group:- <FORM:1108333/C3/2> <FORM:1108333/C3/3> <FORM:1108333/C3/4> wherein R1 and R11 are the same or different C4 to C9 alkyl radicals, R111 is hydrogen or an alkyl radical and X is -S-, -O- or a C1-C10 saturated divalent aliphatic radical; are used as stabilizers for polymeric materials such as polyester resins and rubbers, e.g. natural rubber, cis - 1,4 - polyisoprene, polybutadiene, polychloroprene and copolymer rubbers, e.g. butyl rubber, rubbery butadiene-styrene copolymers and the rubbery copolymers of butadiene and acrylonitrile.  The compounds may be incorporated in the rubber in solution, or added to rubber, coagulated rubber or latex or mixed with rubber in masticating machines such as mills and Banbury mixing machines.  The stabilizing agents can also be incorporated in a resin by adding them to low molecular weight polyester having an intrinsic viscosity of 0.1 to 0.2 as measured in a 60/40 phenol/tetrachloroethane mixed solvent at 30 DEG  C. and condensing the low molecular weight polymer to form a high molecular weight polymer or by adding them to polyester-forming reactants such as the lower alkyl esters of the acids and a glycol and preparing the high molecular weight polymer from the reactants. Examples of such condensation polyester resins are those derived from dicarboxylic acids or ester-forming derivatives thereof and glycols, e.g. polyethylene terephthalate; copolyesters of terephthalic acids with an aromatic dicarboxylic acid; copolyesters of an aromatic dicarboxylic acid with one or more aliphatic dicarboxylic acids and the 70/10/20 polytetramethylene terephthalate/isophthalate/sebacate copolyester.  Specified catalysts used in the production of the polyester resins are zinc acetate, manganese acetate, manganese octoate, calcium acetate, the alkali metal alcoholates, soluble antimony compounds, lead compounds and titanium compounds.ALSO:Novel phosphite esters having the general formula <FORM:1108333/C2/1> in which R is a C4-C19 hydrocarbon radical; y is 0, 1 or 2; z is 1, 2 or 3 and the sum of y and z is 3; and A is selected from the group <FORM:1108333/C2/2> <FORM:1108333/C2/3> wherein R1 and R11 are the same or different C4-C9 alkyl radicals, R111 is hydrogen or an alkyl radical and X is -S-, -O-, or a C1-C10 saturated divalent aliphatic radical; are prepared by reacting phosphorus chlorides having the formula (R.C6H4)yPClz with phenols (AOH).  Both the pure products, which are light coloured resinous materials, and the unpurified products are useful as antioxidants particularly for polymeric materials (see Division C3).  The phosphorus chloride used as starting material may be obtained by reacting phosphorus trichloride with the appropriate phenol (RC6H4OH).  Nonyl phenol/formaldehyde and butylated p-cresol/dicyclopentadiene adducts used as the starting material (AOH) may be prepared (1) by reacting nonyl phenol with aqueous formaldehyde, and (2) by reacting p-cresol with dicyclopentadiene and reacting the p-cresol/dicyclopentadiene adduct produced with isobutene.