Patent GB-713081-A (GB)
Title: Polymerisation of ethylene
IPC: C07F5/00
Filed: 1951-06-21
Abstract: Ethylene or a mixture thereof with other mono- or di-olefins is polymerized by heating at about 60-250 DEG C. in the presence of an activator Me (R)n, where Me is Be, Al, Ga or In; R is hydrogen, alkyl or aryl; and n the valency of the metal, or molecular compounds or complexes thereof with, e.g. ethers, thioethers or amines, alkali metal hydrides, alkyls or aryls. Pressures from normal up to 2,000 atm. or more may be used.  By control of reaction time conversion up to about 60 per cent. is effected.  By complete conversion at above 200 DEG C., olefins with intermediate double bonds are formed.  With the activator in a molar ratio to ethylene not exceeding 1:20 at about 60-160 DEG C. and 10-2000 atm. solid polymers are formed.  The activators may combine with the products, the metals being removed by washing with water, alcohol, acids or alkalis, when hydrogen replaces them.  Other agents such as halogen or oxygen may also decompose the activators present.  The olefins polymerized with ethylene include a and other olefins, poly-olefins, diallyl, butadiene polymers, and cyclic olefins such as vinylcyclohexenes, cyclohexene, cyclopentene and dicyclopentadiene.  Polyethylenes of high M.W. are obtained using very small amounts of activator, temperatures of 80-90 DEG C. and pressures of 10-2000 atm.  The ethylene should be purified by pre-treating with the activator, alone or in a solvent or with organo-metallic compounds such as zinc alkyls.  Examples describe the polymerization of ethylene with Al(C2H5)3, Al(C6H5)3, LiAlH4, Al(C2H5) 3/4 (C2H5)2O, Al(C18H37)3, Al(C6H13)3, Be(C2H5)2, In(C2H5)3, In(C6H5)3, Ga(CH3)3 or Ga(C6H5)3, and co-polymerization of ethylene with propylene, butene, pentene, hexene, dodecene or hexadecen-1, in which case one olefin may first be absorbed by the activator, excess removed, a second olefin reacted and so on.ALSO:Ethylene or a mixture thereof with other olefins is polymerized by heating at about 60-250 DEG  C. in the presence of an activator Me(R)n, where Me is Be, Al, Ga or In; R is hydrogen, alkyl or aryl; and n the valency of the metal, or molecular compounds or complexes thereof with, e.g., ethers, thioethers or amines, alkali metal hydrides, alkyls or aryls. Pressures from normal up to 2000 atmos. or more may be used.  By control of reaction time so that conversion up to about 60 per cent is effected using the metal alkyls, normal a -olefins are obtained. The same products may be obtained using compounds of Al trialkyls eith ethers, thioethers or amines or with alkali alkyls or hydrides. By complete conversion at above 200 DEG  C., olefins with intermediate double bonds are formed.  With the activator in a molar ratio to ethylene not exceeding 1 : 20, at about 60-160 DEG  C. and 10-2000 atm., solid polymers are formed.  The activators may combine with the products, the metals being removed by washing with water, alcohol, acids or alkalis, when hydrogen replaces them.  Other agents such as halogen or oxygen may also decompose the activators present. The olefins polymerized with ethylene include a - and other olefins, poly-olefins, diallyl, butadiene polymers, and cyclic olefins such as vinylcyclohexenes, cyclohexene, cyclopentene, and dicyclopentadiene. Polyethylenes of high M.W. are obtained using very small amounts of activator, temperatures of 80-90 DEG  C. and pressures of 10-2000 atmos.  The ethylene should be purified by pretreating with the activator, alone or in a solvent or with organo-metallic compounds such as zinc alkyls.  Examples describe the polymerization of ethylene with Al(C2H5)3, Al(C6H5)3, LiAlH4, Al(C2H5)3. 3/4 (C2H5)2O, Al(C18H37)3, Al(C6H13)3, Be(C2H5)2, In(C2H5)3, In(C6H5)3, Ga(CH3)3 or Ga(C6H5)3, and copolymerization of ethylene with propylene, butene, pentene, hexene, dodecene or hexadecen-1, in which case one olefin may first be absorbed by the activator, excess removed, a second olefin reacted and so on.