Patent GB-873065-A (GB)
Title: Hydrocarbon polymers
Inventor: GOLDSBROUGH LESLIE NEWTON
IPC: C07C2/30
Filed: 1959-02-11
Abstract: In a process for the production of hydrocarbon polymers an olefin having in the molecule at least 6 but not more than 25 carbon atoms is purified by treatment with urea to form an olefin-urea adduct and the urea-extracted olefin obtained from the adduct is polymerized in the presence of a catalyst comprising (A) a compound of a metal of Group IV(a), V(a), VI(a) or VII(a) of the Mendeleeff Periodic Classification or iron and (B) a Group I metal or alloy thereof or an organometallic compound or hydride of a Group I, II or III metal, tin or lead.  The olefins are preferably straight-chain 1-olefins, or mixtures containing a large proportion thereof.  The olefins may be obtained by thermal or catalytic cracking of hydrocarbon feed stocks, such as those produced in the refining of crude petroleum oils, or by the dehydration of alcohols.  Treatment with urea may be effected in aqueous and/or alcoholic solution in the presence of diluents, wetting agents, ammonium salts such as ammonium carbonate, and potassium chromate, and the adduct separated and decomposed by heating or distillation; or the treatment otherwise effected by the methods described in Specifications 657,496, 671,456, 671,457, 671,458, 681,246 and 725,598.  The olefins may be further purified by distillation over sodium or treatment with a catalyst component, e.g. titanium tetrachloride or triethyl aluminium, or with sulphuric acid, washing with water, dried over calcium chloride, silica gel or molecular sieves.  Polymerization may be effected batchwise or continuously in solvents, e.g. n-hexane, n-pentane, isooctane, n-decane, petroleum fractions and cyclohexane.  Catalyst residues may be inactivated by treatment with methanol or isopropanol and removed by washing with dilute hydrochloric acid and sodium carbonate solution.  Many suitable components and reactants are listed and examples describe the polymerization in the presence of titanium tetrachloride and aluminium triethyl of (I, II, III, IV and VI) cracked wax C9-17 olefins; (V, VII, VIII and IX) cracked wax C9 olefins; (X) C14, C15, C16 and C17 cracked wax olefins; (XI) C11 cracked wax olefins and (XII) C8, C10 and C15 olefins; and the polymerization of C9 cracked wax olefins in the presence of titanium tetrachloride and (VIII) aluminium ethyl dichloride, aluminium triisobutyl and zinc diethyl and (VIII and XIII) gallium triethyl; and in the presence of aluminium triethyl and (IX) tintetrachloride, lead tetrachloride and vanadium oxychloride. Polymers prepared with catalyst mole ratio B/A less than 1 may be used as lubricating oils, and those prepared with higher ratios as lubricating oil additives, e.g. V.I. improvers.  The polymers may be mixed with paraffinic and naphthenic hydrocarbon oils, copolymers of alkylene glycols and alkylene oxides, di-(2-ethylhexyl) sebacate, dinonyl sebacate, dinonyl adipate, dioctyl phthalate, trioctyl phosphate, tricetyl phosphate, tricresyl phosphate, tetrahydrofuran polymers, polyalkyl silicone polymers, e.g. dimethyl silicone polymers, polymers of the methyl, ethyl, n-propyl, isopropyl, isobutyl, lauryl, phenyl and benzyl esters of acrylic and 2-alkylacrylic acids, zinc and calcium salts of benzoic acid, naphthoic acid, phenol, alkylated phenols and alkylate salicylic acids, and antioxidants such as alkylated phenols and diphenols, and phenothiazine and derivatives thereof, e.g. 10-benzylphenothiazine.  Specifications 820,681, 851,113, 851,119 and 873,064 also are referred to.ALSO:Lubricating oils and oil additives are prepared by a process in which an olefin having at least 6 but not more than 25 carbon atoms in the molecule is purified by treatment with urea to form an olefin-urea adduct and the urea-extracted olefin obtained from the adduct is catalytically polymerized (see Group IV(a)).  The olefins are preferably straight chain 1-olefins, or mixtures containing a large proportion thereof, and may be obtained by thermal or catalytic cracking of hydrocarbon feed stocks, such as those produced in the refining of crude petroleum oils, or by the dehydration of alcohols.  Treatment with urea may be effected in aqueous and/or alcoholic solution in the presence of diluents, wetting agents, ammonium carbonate and potassium chromate; and the adduct separated and decomposed by heating or distillation; or the treatment otherwise effected by the methods described in Specifications 657,496, 671,456, 671,457, 671,458, 681,246 and 725,598.  Specifications 820,681, 851,113, 851,119 and 873,064 also are referred to.ALSO:Lubricating oils and oil additives (e.g. viscosity index improvers) are prepared by a process in which an olefin having at least 6 but not more than 25 carbon atoms in the molecule is purified by treatment with urea to form an olefin-urea adduct and the urea-extracted olefin obtained from the adduct is catalytically polymerised (see Group IV(a)).  The oils thus obtained may be blended with mineral oils, copolymers of alkylene glycols and alkylene oxides, di-(2-ethylhexyl) sebacate, dinonyl sebacate, dinonyl adipate, dioctylphthalate, trioctylphosphate, tricetyl phosphate, tricresyl phosphate, tetrahydrofuran polymers, polyalkyl silicone polymers such as dimethyl silicone polymers, polymers of the methyl, ethyl, n-propyl, isopropyl, isobutyl, lauryl, phenyl and benzyl esters of acrylic and 2-alkylacrylic acids, zinc and calcium salts of benzoic acid, naphthoic acid, phenol, alkylated phenols and alkylated salicylic acids, and antioxidants such as alkylated phenols and diphenols and phenothiazine and its derivatives, e.g. 10-benzyl phenothiazine. Specifications 820,681, 851,113, 851,119 and 873,064 are referred to.