Patent GB-1185515-A (GB)
Title: Polymerisation process and product thereof
IPC: C08F2/02
Filed: 1967-03-31
Abstract: 1,185,515. Rubber modified styrene polymers. UNION CARBIDE CORP. 31 March, 1967 [1 April, 1966], No. 14949/67. Heading C3G. A continuous bulk polymerization process for the preparation of rubber modified styrene polymers comprises the steps (a) feeding a first monomeric solution containing from 0 to 1À9 parts by weight acrylonitrile per part of styrene to a first stage reactor; (b) reacting said first monomeric solution until at least 20% by weight of said solution is polymerized; (c) feeding to said first stage reactor a second monomeric solution containing from 2À5 to 19% butadiene rubber dissolved in a monomeric solution comprising 0 to 1À9 parts of acrylonitrile per part of styrene thereby precipitating said butadiene rubber; (d) dispersing the precipitated rubber as discrete droplets throughout the reaction mass before appreciable crosslinking can occur; maintaining the resulting heterogeneous mass at temperatures of from 130‹ to 160‹C.; (f) maintaining the steady state solids level in the first stage reactor at from 25 to 50% by weight solids during polymerization therein, said solids content comprising a polymeric fraction of predetermined molecular weight distribution; (g) introducing an effluent stream from said first reactor to a stirred second stage reactor maintained at from 140‹ to 160‹ C.; (h) maintaining the solids level in said second reactor at 55 to 70% solids during polymerization therein, said solids content containing a second polymeric fraction of predetermined molecular weight distribution; (i) introducing an effluent stream from said second reactor to a stirred third stage reactor maintained at from 140‹ to 185‹ C.; (j) maintaining the solids level in the third reactor at 70 to 90% during polymerization therein, said solids content containing a third polymeric fraction of predetermined molecular weight distribution; and (k) recovering the resulting polymer. In a modification of the process, 0À01 to 2% by weight of the reaction mass of an organic free radical initiator is fed to the first stage reactor, the temperature in said first reactor is maintained at 80‹ to 120‹ C. and in the second stage reactor at 130‹ to 142‹ C. The process is particularly applied to the production of ABS resins comprising a matrix of acrylonitrilestyrene copolymer and a dispersed graft phase comprising acrylonitrile - styrene copolymer grafted on to the butadiene rubber, said matrix comprising 30 to 45% solids formed in the first reactor and having a reduced viscosity of 0À8 to 1À2, 45 to 55% solids formed in the second reactor and having a reduced viscosity of 0À7 to 0À9 and 10 to 25% solids formed in the third reactor and having a reduced viscosity of 0À1 to 0À5, said graft phase containing 2 to 28% rubber and the graft phase comprising at least 80% of particles in the range 0À5 to 2À0 microns and less than 1% of particles larger than 6 microns. An organic liquid diluent may be used in the three stages. The molecular weight distribution of the product may be controlled by maintaining a constant ethyl benzene concentration in the reactors and by adding a chain transfer agent or a free radical initiator to the third reactor. ABS resins are produced in the examples, the rubber used being a butadiene-styrene copolymer.