Patent GB-828496-A (GB)
Title: Acrylates of phenoxy alcohol ethers and polymers thereof
IPC: C08F20/16
Filed: 1957-11-14
Abstract: The invention includes a lubricant containing a mineral motor oil and, to increase the viscosity index, a small proportion of a polymerized acrylate or methacrylate of the general formula <FORM:0828496/III/1> where R is an aliphatic hydrocarbon radical containing 8 to 24 carbon atoms, where each R1 is a divalent hydrocarbon group containing 2 to 8 carbon atoms, Y is hydrogen or a methyl group and x is an integer between 0 and 5, the preferred compounds being those with a pentadecyl group in the 3-position.  A small proportion, generally 0.3 to 5% by weight, of the polymeric acrylates or methacrylates is found to improve the viscosity index of the oil and an example describes the addition of 2% of (a) poly [b  - acrylato (3 - pentadecyl phenoxy) ethane], (b) poly [a  - acrylato - b  (3 - pentadecyl phenoxy) propane], (c) poly [b -acrylato-b 1 (3-pentadecyl phenoxy) diethyl ether] and (d) poly [b  - methacrylato - (3 - pentadecyl phenoxy) ethane] to an S.A.E. 10 additive-free mineral motor oil.  The monomeric acrylates or methacrylates of the general formula above or their homopolymers may be used as a coating composition on a base.  In Example (12) a solution of a  - acrylato - b  - (3 - pentadecylphenoxy)-propane in xylene containing cobalt naphthenate is brushed on to a piece of tin plate, the xylene allowed to evaporate, and the plate heated 4 hours at 180 DEG  C. to convert the acrylate to the solid state.ALSO:The invention comprises acrylic esters of phenolic alcohol ethers of the general formula <FORM:0828496/IV (b)/1> where R is an aliphatic hydrocarbon radical of 8 to 28 carbon atoms, where each R1 is a divalent hydrocarbon group of 2 to 8 carbon atoms, Y is hydrogen or a methyl group and x is an integer from 0 to 5.  The preferred compounds are those having a pentadecyl group in the 3-position.  The esters may be prepared by reacting a suitably substituted phenol with a cyclic ether such as ethylene, propylene, butylene or octylene oxide under etherification conditions to yield an alcohol ether of the formula P-O-(R1-O)x-R1OH, where P is the phenol residue and R1 and x are as defined above, the value of x depending on the amount of alkylene oxide introduced, and subsequently esterifying the alcohol ether under known conditions with acrylic or methacrylic acid or a derivative such as an ester or acid chloride.  An alternative method comprises treating an alkali metal salt of the phenol with two or more mols. of a halogenated hydrocarbon such as dibromoethane to give a b -bromoethyl phenol ether which may then be treated with an acrylic or methacrylic salt to give the desired product.  In the examples: (1) 3-pentadecyl phenol is treated with methanolic KOH and then with ethylene oxide at 163 DEG  C., the resulting alcohol ether is purified and then subjected to a transesterification reaction with methyl acrylate in the presence of p-toluene sulphonic acid and hydroquinone as a polymerization inhibitor, this gives a product m\C15H31.C6H4.O.CH2 CH2.OCO.CH =CH2; (2) 3-pentadecyl phenol is treated with sodium hydroxide and then propylene oxide and the purified alcohol ether reacted as before using ethyl acrylate to give a product m-C15H31.C6H4.OCH2CH(CH3)O.CO. CH=CH2; (3) is similar to (1) but uses more ethylene oxide to give a product m-C15H31.C6H4.OCH2 CH2 OCH2CH2O.CO.CH=CH2; (4) the alcohol ether obtained as in (1) is transesterified using methyl methacrylate to give a product m-C15H31.C6 H4. O.CH2CH2O.CO.C(CH3)=CH2; the reaction of 3-pentadecyl phenol with a mixture of 1 : 2- and 2 : 3-butylene oxide and 1 : 2- and 2 : 3-octylene oxide is also described.  The esters may be polymerized or copolymerized; the monomeric esters may be used as motor oil additives and the monomers or polymers may be used as epoxy curing agents, as plasticizers for natural or synthetic rubbers or as a coating composition (see Groups III and IV (a)).ALSO:The invention comprises polymers or copolymers among themselves of acrylic esters of phenolic alcohol ethers of the general formula <FORM:0828496/IV (a)/1> where R is an aliphatic hydrocarbon radical of 8 to 24 carbon atoms, where each R1 is a divalent hydrocarbon group of 2 to 8 carbon atoms, Y is hydrogen or a methyl group and x is an integer from 0-5. The preferred monomers are those having a pentadecyl group in the 3-position.  The monomeric esters may be polymerized thermally or by using a catalyst such as boron trifluoride, aluminium trichloride or peroxides such as benzoyl peroxide, cumene peroxide or dicumyl peroxide with or without the aid of heat.  In examples: (5) b -acrylato (3-pentadecyl phenoxy) ethane is sealed in a tube with heptane and benzoyl peroxide and the tube heated at 60 DEG  C. for 185 hours to yield a viscous semi-solid polymer; the same procedure is used to polymerize (6) a -acrylato-b -(3-pentadecylphenoxy) propane, (7) b -acrylato-b 1-(3-pentadecyl phenoxy diethyl ether, (8) b -methacrylato - a  - (3 - pentadecyl phenoxy) ethane.  The invention includes plasticized compositions comprising natural rubber, reclaimed rubber, normally solid copolymers of butadiene-1 : 3 and styrene, normally solid copolymers of butadiene-1 : 3 and acrylonitrile, normally solid homopolymers of butadiene-1 : 3, normally solid homopolymers of isobutylene or normally solid homopolymers of chloroprene and a plasticizing amount of one or more monomeric acrylates or methacrylates or polymers thereof described above.  In general the composition may contain 0.5-40% by weight of the monomeric or polymeric acrylate.  In Example (11) the original and aged properties are given of a synthetic rubber composition containing butadiene/styrene rubber, carbon black, zinc oxide, stearic acid, a diphenylamine-acetone reaction product, n - cyclohexyl - 2 - benzolthiazole sulphenamide and sulphur and varying amounts of a -acrylato-b -(3-pentadecyl phenoxy)-ethane as plasticizer.  The invention also includes a composition comprising an epoxy resin (defined as a glycidyl polyether of an aliphatic polyhydric alcohol or a polyhydric phenol which has a 1 : 2-epoxy equivalency greater than 1 and which is liquid below 300 DEG  F.) and between 2 and 75% by weight of the epoxy resin of a monomeric or polymeric acrylate or methacrylate described above.  These monomeric or polymeric acrylates or methacrylates may be used as curing agents for the epoxy resins which are found to have enhanced properties when cured with these agents.  In the examples mixtures containing b  p  - acrylato - a  - (3 - pentadecyl phenoxy) propane, triethylene tetramine and (9) a 2 : 2-di-(p-hydroxy-phenyl) propaneepichlorohydrin condensate, and (10) a condensate of epichlorohydrin and the bisphenol reaction product of 3-pentadecadienyl phenol (cardanol) and phenol are prepared and cured and their properties compared with similar resins cured in the absence of the monomeric acrylates.  Uses.-Epoxy resin compositions containing the monomeric or polymeric acrylates may be used for coating paper, nylon, silk, asbestos, glass, cotton and polyethylene terephthalate which may be in the form of fibres, matting or woven fabric to provide good weatherproof and electrical insulating materials.  They may also be used as electrically insulating casting resins.