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United States Patent Office Patented Oct 3,213,159 United States Patent Office Patented Oct. 19, 1965 1. 2 percent, higher styrene contents leading to greatly re 3,213,159 duced impact strength of the final composition. Such METHOD OF BLENDING POLYSTYRENE AND homopolymers or copolymers of butadiene and styrene GRAFT COPOLYMER OF STYRENE WITH are commercially available, or may be prepared by BUTADENE POLYMER polymerization in emulsion in a manner known to the Domas Adomaitis, Chicago, Ill., assignor to Standard Oil art, employing peroxide catalysts or "redox” catalyst Company, Chicago, Ill., a corporation of Indiana Systems. No Drawing. Filed Apr. 26, 1962, Ser. No. 190,211 The graft copolymer component of the compositions 4. Claims. (C. 260-876) produced by the process of the present invention is pre This invention relates to the preparation of polystyrene 10 pared by effecting free radical polymerization of styrene molding compositions. More particularly, it concerns a in the presence of a previously prepared pre-coagulated process for preparing such compositions to afford homo latex of butadiene homopolymer or copolymer with geneous blends of polymeric styrene and rubbery polymers styrene. The amount of styrene which is grafted upon having improved impact properties and which are easy the butadiene containing backbone can be varied from to mold and/or extrude to smooth, glossy uniform 5 about 10 to about 80% by weight based upon the weight articles. The invention is especially concerned with of graft copolymer, desirably 30-50%. In general, processes for the preparation of useful high impact poly polymerization techniques known to the art, employing styrene compositions by compounding certain rubbery free radical generating catalysts can be employed, to graft copolymers with hydrocarbon solutions of polysty gether with such known polymerization ingredients as rene, and to the compositions prepared thereby. 20 emulsifying agents, chain transfer agents and the like for It has hitherto been known to prepare ternary com effecting complete and rapid graft polymerization of the positions comprising mixtures of (1) styrene-type resins, monomeric styrene. In the graft polymerization reac (2) graft copolymers of styrene on a rubbery butadiene tion, it appears that a substantial portion of the poly polymer or copolymer backbone, and (3) rubbery buta styrene becomes attached to the backbone chain, and that diene polymers or copolymers, as for example in U.S. 25 a relatively minor amount of free polystyrene is formed. Patent 2,755,270 of Robert A. Hayes. Such composi As previously discussed, the graft polymerization of tions, especially those containing from 80-95% of poly styrene is effected in the presence of the pre-coagulated styrene based on the weight of polymeric ingredients in polybutadiene or rubbery copolymer of butadiene and the resinous composition are particularly useful for in styrene. The latex of the butadiene homopolymer or jection molding applications in that they combine the 30 copolymer, which comprises a finely divided emulsion of excellent strength and hardness of polystyrene with a polymer, is pre-coagulated by the addition of mineral high degree of resistance to impact. acids, such as sulfuric acid, hydrochloric acid, etc., or by It has now been found that thermoplastic compositions the addition of salts which have a coagulating effect on having good molding characteristics and high impact the latex, e.g., aqueous solutions of sodium chloride, strength can readily be prepared from polystyrene and a 35 calcium chloride and the like. graft polymer of styrene on a rubbery butadiene polymer In grafting styrene onto the rubbery polymer of buta or copolymer by employing a graft copolymer of the diene, the pre-coagulated latex is charged to a polymeriza aforesaid type which has been prepared in a particular tion reactor. Mechanical mixing may be employed for way. The process of the present invention, and the this purpose, and it is obvious that while the pre-coagulum binary compositions produced thereby, are much simpler 40 will be distributed into smaller particles, it does not revert to prepare than those of the prior art which require the to the extremely finely divided, emulsified form, in which presence of three separate and distinct polymeric com it is originally prepared. Styrene to be used in the graft ponents in the final resin composition. polymerization step may be added to the reactor contain The first step in the preparation of the plastic com ing the pre-coagulate just prior to polymerization or it positions of this invention is to provide an aqueous emul 45 may be contacted with the pre-coagulate for a period of sion of polymerized butadiene or of a rubbery copolymer time prior to polymerization to permit swelling of the of butadiene and styrene containing at least 50% buta pre-coagulate with the monomer and thus more intimate diene in the molecule. The next step in the preparation contact of the monomer with all parts of the pre-coagul of the composition is to polymerize styrene monomer lated rubber. in the presence of the aforesaid butadiene resin. This 50 Graft polymerization is effected at temperatures be step is essentially a graft polymerization, in which styrene tween 0° and about 100° C., preferably 20° C. to 80 C., becomes chemically combined as side chains on the poly in the presence of well-known peroxide catalysts, and butadiene base or "backbone' polymer. An essential under autogeneous pressure. feature of the present invention is the step of first pre The graft polymer prepared as described above is then coagulating the polybutadiene or rubbery copolymer of 55 separated from the watery phase and homogeneously dis polybutadiene, and subsequently effecting the graft po persed in a hydrocarbon solution of polystyrene, in which lymerization of styrene on the precoagulum. Finally, the case water accompanying the coagulum can be separated graft copolymer, prepared by reaction of styrene with by azeotropic distillation. The separation of graft copol pre-coagulated rubbery butadiene polymer, is dispersed ymer may be accomplished by addition of coagulating in a hydrocarbon solution of polystyrene to effect homo 60 agents of the type described for coagulation of the poly geneous distribution of the graft polymer in polystyrene, butadiene latex, and the coagulum washed free of adherent and the resultant solution treated for recovery of the catalyst and salts. Polystyrene ordinarily useful for binary graft copolymer-polystyrene composition. molding or for incorporation into molding compositions The rubbery polymer employed to prepare the com can be used as one component of the compositions pro positions described herein comprises a conventional “hot” 65 duced by our process. Such polystyrene resins may be or “cold" rubbery homopolymer of butadiene or a co obtained by bulk or emulsion polymerization of styrene polymer of butadiene and styrene containing at least 50% using peroxidic or other known catalysts. Since the butadiene together with up to 50% styrene. It has present process requires the use of a hydrocarbon solution been found that the proportion of styrene in the 70 of polystyrene, it is preferred to employ a resin solution copolymer is critically maintained below 50 weight prepared by polymerization of styrene in an aromatic sol percent, preferably from about 10 to about 30 weight vent, for example hydrocarbon solutions of polystyrene 3,213,159 3 4. which are obtained in accordance with the processes de polybutadiene was effected by employing the same por scribed in U.S. Patents 2,813,089 and 2,920,065. It is portions of ingredients used in the formula above, the to be understood, however, that solutions of polystyrene monomeric butadiene being substituted by polybutadiene obtained by dissolving polystyrene, prepared in accord and styrene. Styrene in an amount equal to the weight ance with methods well known to the art, in an aromatic of polybutadiene employed (dry basis) was added during hydrocarbon solvent are equally applicable to the present a period of one hour while maintaining the reactor con process. tents with stirring at 60° C. Reaction at 60° C. was Preferred polystyrene resins have an intrinsic viscosity effected over a period of about four hours to practical (measured in benzene at 30° C.) of from about 0.8 to completion. about 1.5 dil./g. and are characterized by impact strength O Upon completion of the polymerization, the reactor in the range of from about 0.25 to 0.40 ft. lbs./in. notch contents were cooled and 1% (based on weight of graft (ASTM D256-56). The polystyrene solution comprises copolymer) of Ionol (butylated-hydroxy-toluene) anti from about 10 to about 50% by weight polystyrene, pref oxidant added to the prepared latex. erably 15-25% polystyrene dissolved in an aromatic hy Example 2 drocarbon such as benzene, toluene, ethylbenzene, xylenes, 15 and the like. The particular solvent employed is not A second portion of the polybutadiene latex prepared critical. The graft copolymer is added in an amonut which as hereinbefore described was employed for preparation will provide, upon removal of water and solvents, a com of a graft polymer without prior pre-coagulation of the position comprising from 5 to 30 parts, preferably 15 to latex. In this example, polybutadiene latex containing 20 parts graft polymer per 100 parts of resin. 20 50 parts (dry basis) polybutadiene was charged together Addition of the graft polymer to the polystyrene solu with 50 parts monomeric styrene and 1.0 part potassium tion yields a suspension which may contain some dis persulfate as catalyst to a closeable polymerization reac solved polymer. This suspension of graft polymer is pref tor. The reactor was purged of air by means of nitrogen, erably homogenized to obtain a more uniform distribu the reactor sealed and the contents heated to 50° C. with tion of the added resin, and to disperse large particles of 25 stirring.
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