Patent GB-847915-A (GB)
Title: Improvements in or relating to the preparation of resinous polymeric materials and aromatic compounds
Inventor: BAILES PETER
IPC: C08F10/00
Filed: 1956-03-16
Abstract: Resinous hydrocarbon polymers are obtained together with aromatic hydrocarbons in the polymerisation of acetylenes of the formula HC ­ CR where R is hydrogen or hydrocarbon (see Group IV(b)) in the presence of a catalyst comprising a Ziegler catalyst suspended in an inert non-aqueous liquid.  The catalyst may be either of the following :-I, A mixture of a compound of a metal of Group IV-VI with at least one of (a) aluminium trialkyl, (b) compound of the formula R1 R2 Al X where R1 and R2 are hydrogen and X is hydrogen, halogen, alkoxy, aralkoxy or the residue of a secondary amine or amide, mercapton, thiophenol, or carboxylic or sulphonic acid.  In this case the Group IV-VI metal may be replaced by a Group VIII metal such as Ni, Co, Pt or by Mn. (c) magnesium or zinc alkyl or Grignard compound.  II, Aluminium chloride, titanium chloride and aluminium powder.  Such catalysts are described in Specifications 833,430, 829,626, 841,822, 834,217, 801,031, 799,823 and 799,392.  The reaction is preferably carried out in iso-octane or other hydrocarbon at up to 50 atmospheres pressure and 150 DEG  C, e.g. atmospheric pressure and 30-40 DEG  C.  The resinous products are produced in greater yields at lower temperatures ; they have a hydrogen : carbon ratio between 0,7:1 and 1,3:1.  The examples describe the polymerisation of acetylene in the presence of (1) Ti Cl4 and Al(C2H5)2Cl in iso-octane (2) Ti(OC2H5)4 and Al(C2H5)2Cl in iso-octane (4) Ti Cl4 and Al(C2H5)3 in iso-octane and of phenyl acetylene in the presence of (3) Ti Cl4 and Al(C2H5)2Cl in benzene. In each case a dark resinous polymer was obtained along with benzene or triphenyl benzene.  Specification 799,394 also is referred to.ALSO:Benzene or sym-trisubstituted benzenes are prepared by the polymerisation of an acetylene of the formula HC ­ CR where R is hydrogen or a hydrocarbon radical in the presence of a catalyst comprising a Ziegler catalyst suspended in an inert non-aqueous liquid.  The catalyst may be either of the following:  I.  A mixture of a compound of a metal of Group IV-VI with at least one of  (a) aluminium trialkyl.  (b) compound of the formula R1 R2 Al X where R1 and R2 may be hydrogen or hydrocarbon and X may be hydrogen, halogen, alkoxy, aralkoxy or the residue of a secondary amine or amide, mercaptan, thiophenol, or carboxylic or sulphonic acid.  In this case the Group IV-VI metal may be replaced by a Group VIII metal, e.g. Ni, Co, Pt or by Mn  (c) Magnesium or zinc alkyls or Grignard compounds. II.  Aluminium chloride, titanium chloride and aluminium powder. Such catalysts are described in Specifications 799,392, 799,823, 801,031, 829,626, 833,430, 834,217 and 841,822.  The reaction is preferably carried out in isooctane or other hydrocarbon at atmospheric pressure and a temperature below the boiling point of the product or solvent, e.g. 30 DEG -40 DEG  C. Pressures of up to 50 atmospheres can be used and temperatures up to 150 DEG  C.  Cooling is generally necessary as the reaction is exothermic.  The Examples describe the polymerisation of acetylene to benzene in the presence of (1) titanium chloride and diethyl aluminium chloride.  (2) titanium tetraethoxide and diethyl aluminium chloride.  (4) titanium tetrachloride and triethyl aluminium, and of phenyl acetylene to 1, 3, 5-triphenyl benzene in the presence of (3) titanium tetrachloride and diethyl aluminium chloride.  A resinous polymeric product is also obtained (see Group IV(a) ).  Specification 799,394 also is referred to.