aisaisa United States Patent 0 " Patented July 20, 1955

1 2 pointed out above, their ratio, and the conditions of reac 3,196,139 PULYMEREZATEGN PROCES§ AND CATALYSTS tion. In certain preferred areas of the invention, the poly Chris E. Best, Akron, ()hio, assignor to The Firestone mers obtained are crystalline and high~melting. The cat T ire & Rubber Qornpany, Akron, ?hio, a corporation alysts of the invention, being based upon the inexpensive of @hio and widely available phosphides, arsenides and stibides, No Drawing. Filed Jan. 5, 1962, Ser. No. 164,668 have substantial economic advantage over the catalysts of 33 Claims. (Q1. 260-935) the prior art, and are superior to many of such catalysts in point of catalytic eiliciency and quality of product. This invention relates to a process for the polymeriza THE OLEFINIC COMPOUNDS TO BE tion of ole?nic compounds to yield macromolecular poly 10 mers, and to certain novel catalysts for use in that process. POLYMERIZED In recent years there have been developed catalytic proc The process of the invention is applicable to the polym esses for the polymerization of ole?ns which may be op erization of any of the ethylenically unsaturated mono erated at moderate pressures and temperatures and which mers commonly polymerized, but ?nds especial applica~ in many cases, depending upon the constitution of the cat 15 tion in the polymerization of unsaturated ole?nic hydro alysts used and the conditions of the polymerization reac carbons which are in general less readily polymerizable tion, yield high polymers of more or less predetermined than the more polar ethylenically unsaturated compounds. chemical structure. Unfortunately, the catalysts used in Ole?nic hydrocarbons which may be polymerized in ac these processes are constituted from, or involve as com cordance with this invention include the mono-ole?ns, par ponents, various organometallic compounds and/or vari ticularly such as contain an alpha-methylene group of the ous metallic oxides which are inherently costly and are formula HZICI. in general it is preferred to use ole available from only a few sources. Moreover, certain of lins containing not over 10 carbon atoms. ‘Propylene is these components may leave persistent toxic residues in the one monomer which is advantageously handled in the polymeric products. Further, although the stereospecilic process of this invention, since the product under preferred action of these processes has made possible the produc 25 conditions will have a high degree of crystallinity. Other tion of polymers of specialized structure, the possible varia suitable mono-ole?ns include for instance ethylene, butene tions in this ?eld have by no means been exhausted. l, isobutylene, pentene-l, heXene-l, octene-l, Z-methyl Accordingly, it is an object of this invention to provide butene-l, Z-methyl pentene-l, 3-methyl pentene-l, 3-ethyl a novel catalytic process for the polymerization of ole?nic pentene-l, cyclopentene, cyclohexene, styrene, alpha compounds, and in particular ole?nic hydrocarbons, to methyl styrene, chlorostyrene, divinylbenzene, vinylnaph form useful and valuable high polymers. thalene and the like. Also amendable to the process of Another object is to provide such a process which is op this invention are polyole?nic hydrocarbons such as buta erable at moderate pressures and temperatures in inexpen— diene, isoprene, chloroprene, ?uoroprene, l-cyanobutadi sive equipment. ene, 3-methyl pentadiene-1,3,Z-phenylbutadiene, cyclopen A further object is to provide such a process in which 35 tadiene, 2-methoxybutadiene, l,4~pentadiene, 1,4,7-octa the catalysts used are independent of the relatively expen triene, 2,3-dimethyl butadiene, piperylene and the like. sive and restricted metal allryls and specially treated oxides Likewise there may be employed non-hydrocarbon mono employed in prior art processes. mers including polar monomers such as methyl meth A still further object is to provide such a process which acrylate, vinyl acetate, vinylidene chloride, vinylidene is capable of stereospeci?c erlects not achieved in the prior ?uoride, vinylidene cyanide, chlorotriiluoroethylene, vinyl art. pyrrolidone, the lower alkyl acrylates, the lower alkyl Still another object is to provide novel catalytic com methacrylates, the lower alkyl ethacrylates, vinyl ethers, positions for use in the above and other processes. vinylpropionate, acrylonitrile, cinnamic acid esters, meth~ Still another object is to provide such catalysts, the com acrylonitrile, vinyl pyridine, vinyl carbazole and the like. ponents of which will not leave deleterious residues in the 45 The polymers produced from these monomers in accord polymeric products produced by the use thereof. ance with this invention are of unbranched and regular SYNSPSlS OF THE INVENTION structure, which latter may be adjusted to various ap propriate desired con?gurations by proper choice of the The above and other objects are secured, in accordance reaction parameters. The invention can be used to make with this invention, in a process of polymerizing an ole?nic 50 copolyrners or interpolyrners of any of the monomers compound by contacting it with a catalyst comprising a indicated above. Likewise the invention can be utilized to mixture or" (A) a phosphide, arsenide or stibide of a metal polymerize a prcpolymer or partially polymerized com of Groups i-A, ILA, Il-B, Ill-A, or lV-A of the Periodic pound with itself or with another ethylenically unsaturated Table 1 plus (B) a compound such as a salt or an oxide compound. of a heavy metal. The resultant polymers have molecular 55 weights in the macromolecular range, and are of regular THE METAL PHOSI’HIDES, ARSENIDES structure, the structures in any particular case being pre— AND STIBIDES determined by the exact reagents used within the ?elds These may be any of the arsenides, phosphides or stibides of any of the metals of Groups I-A, ll-A, II-B, 1 The version of the Periodic Table referred to is that given 60 Ill-A or IV-A as listed in the Periodic Table given in in Lange’s “Handbook of Chemistry,” ?fth edition, Handbook Publishers, Inc., 19%, pages "54 and 55 ; and by the term Lange’s “Handbook of Chemistry,” ?fth edition, Hand “heavy metals” it is intended to designate all of the elements book i’ublishers, Inc., 1944, pages 54 and 55. In general embraced by the heavy black lines within the bracket entitled “Heavy Metals,” including the lanthanldes or rare earth these are metals of high reducing potential and include elements Nos. 57-71. for instance lithium, sodium, potassium, rubidium, 3,196,139 as 4 cesium, beryllium, magnesium, calcium, strontium, zinc, reduced valence compounds are desirably formed by're cadmium, mercury, barium, aluminum, gallium, indium, ducing a higher valence compound ‘of the IV-B or V~B thallium, germanium, tin, lead, and equivalents such as metal by contact with a metal above the IV-B or V-B ammonium, mono-, di- and tri-hydrocarbon substituted metal in the electromotive series or other powerful re ammoniums, tetrahydrocarbon - substituted ammonium ducing agent under conditions so as to provide a ?nely (i.e. quaternary ammonium), and the like. Any of the dispersed catalyst. Speci?c suitable heavy metal com phosphides, arsenides or stibides of these metal (cations) pounds for use in this invention include for instance ti may be used, such as lithium phosphide (Li3P), sodium tanium tetrachloride, zirconium tetrachloride, zirconium phosphide (NaaP), mixed metal phosphides such as lithi acetylacetonate, titanium tetrabutoxide, vanadium oxy um magnesium phosphide (LiMgP), condensed phos 10 trichloride, ferric chloride, ferrous chloride, antimony pen phides such as those of the formulae 1212135, Na2l35, K2795, tachloride, bismuth trichloride, titanium trichloride, stan and the like, magnesium phosphide (MgaPz), calcium nic chloride, oobaltous chloride, antimonyl chloride, tung phosphide (Ca3P-2), barium phosphide (Ba3P2), zinc sten pentachloride, chromium chloride, nickel chloride, phosphides (ZnP2 and Zn3P2), aluminum phosphide and the like. It Will be understood that mixtures of com (AlP), gallium phosphide (GaP), the tin phosphides 15 pounds above indicated as suitable may also be used. phosphide($115132, SHZP, (PbPg), S1131), SUP,lithium SHPZ, arsenide, SH3P4, S114P3,sodium SHP3), arsenide, THE PREPARATION OF THE CATALYSTS AND potassium arsenide, magnesium arsenide, calcium arsenide, CONDUCT OF THE POLYMERIZATION REACTION aluminum arsenide, gallium arsenide, tin arsenide, lead arsenide, zinc arsenide, lithium stibide, calcium stibide, The catalysts of this invention are prepared, by mixing potassium stibide, sodium stibide, magnesium stibide, and agitating the selected phosphide, arsenide or stibide aluminum stibide, zinc stibide, tin stibide, tetramethyl and heavy metal compound together, preferably in a ammonium phosphide, and the like. saturated aliphatic ‘or an aromatic liquid hydrocarbon In general the more salt-like the nature of the com vehicle such as petroleum ether, heptane, kerosene, min— pound (Van Wazer), “Phosphorus and its Compounds,” 25 eral oil, diesel oil, benzene, toluene or the like. Usually Interscience Publishers, Inc., 1958, pp. 123~125), the the phosphide, arsenide or stibide will be insoluble in the greater is its catalytic e?'iciency. Thus, the phosphides medium, and in many cases the heavy metal compound have the highest catalytic activity and the stibides the will also be insoluble. It may be advisable, in order lowest. Also, the more strongly basic the compound, the to promote the reaction with the solids, to subject the greater is its catalytic activity. Preferred are the phos 30 catalyst mass to grinding, as in a ball mill. Temperature phides, arsenides, and stibides which react with an active of mixing may vary Within wide limits, usually between hydrogen-containing compound, particularly Water, to ~—10° C. or lower, as down to -——100° C., up to tempera liberate hydrides of the phosphorus, arsenic or antimony tures on the order of 150° C. Preferably the temperature respectively. A particularly preferred group of com will be in the range 20° C.—100° C. As to the relative pounds possessing this property are the phosphides, ar 35 proportions of the ingredients, usually a su?icient quantity senides and stibides formed by the metals of Groups I-A of the phosphide, arsenide or stibide will be used so as and II-A. to supply at least about 0.1 gram-atom of phosphorus, It will be understood that mixtures of phosphides, ar arsenic or antimony for each mol of the heavy metal com senides and stibides such as above indicated as being suit pound. The upper limit is not critical, and is set mainly able may also be employed. The various phosphides, ar by economic considerations of cost of supplying unneces senides' and stibides are known compounds and in general sary phosphide, arsenide or stibide. It will usually be are very simply prepared bydirect reaction at moderately desirable to operate in the range of 1.0 to 3.0 gram-atoms elevated temperatures of. elemental phosphorus, arsenic of phosphorus, arsenic or antimony (in the arsenide, stib or antimony with the free metal Whose phosphide, arsenide ide or phosphide), per mol of heavy metal compound. tor stibide is desired. These compounds will be Widely Additives such as hexamethyl phosphoramide may be in— available, or indeed can be made in any establishment de corporated in the catalysts, and will enhance the yield of siring to practice the invention. A method of produc crystalline polymers in the products, if this is desired. ing these compounds, particularly the phosphides of the A preferred class of polymerization modi?ers are the Group I~A metals having enhanced catalytic activity 50 tetrakis (dimethylamino) silane, hexakis (dimethylamino) has been discovered and is described infra. The com slloxane, etc., as described by Alfred R. Cain in US; pounds may also be prepared ,by heating the elements patent application S.N. 126,788. The catalyst may either thereof together in an inert atmosphere. be prepared in a separate vessel, or may be prepared in the vessel in which the polymerization proper is to take THE HEAVY METAL COMPOUNDS place, and in this latter case may optionally be prepared 1n the presence of the monomers to be polymerized. The The heavy metal salts and oxides forming the other polymerization is carried out by contacting the monomers components of the catalysts of this invention are those with the catalyst, preferably in a saturated liquid hydro of the heavy metals, (i.e., those metals embraced by the carbon vehicle such as suggested above, preferably with heavy black lines Within the brackets entitled “Heavy 60 su?icient agitation to insure contact of the catalyst and Metals” including the lanthanides or rare earth elements monomers and to avoid segregation of the product. A Nos. 57-71 in the Periodic Table on pages 54 and 55 of preferred process for preparing highly reactive disper Lange’s Handbook cited above). In general the com sions of phosphides, arsenides and stibides which are pounds used will be oxides of these metals or salts thereof particularly adapted for reaction with the heavy metal ‘such as the ?uorides, chlorides, bromides, iodides, cyclo 65 compounds to form the instant catalysts is exempli?ed pentadienyl compounds, acetylacetonates, acetates, alk in Examples I and III in the case of sodium phosphide. oxides or the like, it being understood that the salts need The amount of vehicle employed should be, preferably, not be simple salts but may be the oxy-salts or salts con sufficient to avoid diiiiculty in agitation during the re taining different anions. Particularly preferred are the 70 action, i.e., so that the concentration of the ?nal polymer compounds of the transition metals, that is, the com product will not be over 50%, based on the total weight pounds of the metals of Groups IV-B and V-B of the of polymer plus vehicle. The amount of catalyst should Periodic Table cited supra. It is further preferred to use be such that it will reach economic exhaustion at about such compounds’ in a lower valence state, i.e., in a valence the sametime that the vehicle contains all of the polymer below the highest normal valence of the metal. Such it can carry without dif?culty in agitation. Ordinarily 3,196,139 5 6 it will be expected that each gram of catalyst will produce mic needle until the balance again was in equilibrium. from 15 to 100 grams of polymer. The polymerization The back pressure at this point was about 40 p.s.i.v. may be carried out batchwise, or in a continuous manner The sodium phosphide and AA suspensions were then wherein the catalyst (or ingredients thereof), vehicle and hypodermically injected, and the bottle was placed on monomer are continuously supplied to a reactor system a polymerizer wheel which revolved and dipped the bottle and the resultant polymer solution or dispersion is con in a water bath at 50° C. for 64 hours. At the end of tinuously discharged from the reactor system. The poly this time the bottle was removed from the wheel, cooled meric products are puri?ed by any suitable treatment, as to 25° C., and the pressure thereon determined to be by washing with alcohols, acids, ammonia and the like. 20 p.s.i.g. by means of a hypodermic gauge. The bottle The portions of the catalyst residues derived from the was then vented and opened, and the polymer separated phosphides, arsenides, stibides, particularly when they from the liquid vehicle by decantation. The solid product involve metals of Groups I—A, magnesium and calcium was then reslurried in heptane, the slurry poured into and aluminum, are readily removable from the polymer, methanol and the mixture agitated for 15 minutes. The and in any event, are innocuous. slurry mixture was then ?ltered, and the solid resinous With the foregoing general discussion in mind, there product removed from the ?lter and dried in open air for are given herewith detailed examples of the practice of 24 hours. This solid isotactic resinous product amounted this invention. All parts and percentages are given on to 10.7 grams, and was evaluated as follows. the basis or" weight, unless the contrary is speci?cally indi~ Percent hot-heptane insoluble-A sample of the poly cated. 20 mer was extracted for 48 hours in a Soxhlet extractor with EXAMPLE I boiling heptane. The solution was evaporated to dry ness, and the residue weighed. The difference between (A) Preparation of sodium phosphz'de the weight or" the sample and of the residue was taken as the hot~heptane insoluble material, and amounted to Sodium paste dispersion (35% so 87.7% based on the Weight of sample. In the succeeding dium, in petrolatum) ______98.5 g. (1.5 g.-atom). examples this is referred to as “Heptane Insoluble.” Red phosphorus ______15.5 g. (0.5 g.-atom). Mechanical properties-htandard test specimens were White mineral oil1 ______250 ml. molded at 180° C. and then annealed 2 hours at 125° C. The specimens had a bending modulus of 38,900 p.s.i. 1“S0hio light oil 72” a 72 Saybolt viscosity mineral oil 30 distributed by the Standard Oil Company of Ohio. All further (referred to hereafter as “Modulus”) and a Rockwell references in this and other examples to follow are intended to refer to this oil. hardness (R-scale) of 38 (referred to hereafter as “Rock well”). The product was suitable for fabrication into For this preparation there was provided a 500 ml. three objects such as luggage casings, automotive panels, trans necked ?ask equipped with a nitrogen inlet, a vent, a parent ?lms, and the like. rotary stirrer and a heating mantle. The mineral oil The liquid decanted from the polymerization mixture and sodium dispersion were charged ?rst, followed by and ?ltrate from the re-slurrying operation (a two-phase the phosphorus, after which the ?ask was purged with system) was diluted with methanol and then heated to nitrogen, the how of which was continued throughout the drive off the volatile material, leaving as a residue 10.1 reaction to followystirring commenced and the tempera grams of rubbery (i.e. atactic) material. It is assumed ture was raised to 95° C. This was continued for 4 that a greater or lesser proportion of the mineral oil ac hours, at the end of which the temperature was raised to companying the catalyst ingredients (about 2.9 g. of oil) 195° C. for 18 hours. The reaction mass was cooled to is in the rubbery material. 25 ° C., and transferred to a storage bottle, Which was 45 purged with nitrogen, and the contents made up with min EXAMPLE 11 eral oil to provide a solution 1.0 molar in NasP, based on the phosphorus charged. Example I was precisely repeated, except that 2.0 milli mois of the sodium phosphide were used. There were obtained 7.7 grams of a resinous isotactic product and 50 (B) Polymerization 10.2 grams of a rubbery atactic product. The resinous product had a modulus of 46,600 p.s.i. and a Rockwell Heptane ______250 ml. of v44. Sodium phosphide suspension EXAMPLE III (prepared as described at A 55 above) ______1.5 ml. (1.5 millimols (A) Preparation 0]‘ sodium phosphide The reaction product produced by NaaP). reaction of TiClg with metallic Mineral oil ______250 ml. aluminum, followed by intensive White phosphorus ______l2.lg.(.39g.-atom). grinding. This product, termed 60 Sodium paste dispersion (in petro- > “AA” is produced by the Stanf latum, 35% Na) ______77 g. (1.17 g.-atom fer Chemical Co., 1 molar sus of‘ Na). pension, in mineral oil. lere _ A 560ml. three-necked ?ask provided with a nitrogen after it is referred to as AA ___. 2 ml. (2.0 millimols). 65 inlet, a nitrogen vent and a stirrer was used in the prepa Propylene ______25 grams. ration. The phosphorus and mineral oil were charged The heptane was charged into a 28-ounce beverage ?rst, and the flask heated to 150° C. with nitrogen flow bottle, which was then flushed with nitrogen and sealed to purge moisture. The phosphorus dissolved complete with a butadiene-acrylonitrile rubber-lined crown cap ly. Considerable condensation of phosphorus was noted provided with a perforation for the hypodermic injec in the nitrogen vent. The flask was then cooled to 25° C. tion of reactants. The bottle was then inverted and placed The sodium paste was added in increments, evolution in a cradle on a balance which was ?rst brought to of heat being observed at each addition. The reaction equilibrium and overweighted with a 25-grarn weight. mass was then stirred for 1 hour at room temperature, Propylene was injected through a conduit and hypoder and thereafter at temperatures rising to 120° C. for a 75 further hour. The reaction mass was then cooled to 25° 3,196,139 "fa C. and transferred to a storage bottle which was ?ushed tadiene-acrylonitrile rubber-lined crown cap provided ‘with nitrogen and sealed with a crown cap provided with with a perforation for the hypodermic inieotion. of re TABLE 1

Catalyst In- Pressure1 in gradients Used Temperature Bottle (p.s.i.g.) Yield (millimols) Polym- after—- (Grams) of Atactic 1 Run erization Isotactic Polymer No. (° C.) Resin N as]? AA 20 78 hours hours

0. 5 2. 0 50 41 30 4. 8 5. 2 1 1. 0 2. 0 50 37 23 6. 8 6. 7 2 2. 0 2. 0 50 40 23 7. 1 8. 4 3 0. 5 4. 0 50 39 21 7. 3 8. 5 4 1. 0 4.0 50 33 12 13. 4 11.0 5 2. 0 4.0 50 32 8 13. 0 10. 9 6 4. 0 4. 0 50 34 8 11. 9 13. 3 7 3 2. 0 2. 0 52 16 3 l5 ______8

1'Measured with contents of bottle at the-temperature of polymerization. ,2 May include a greater or less proportion of the mineral oil introduced with the catalyst ingredients. 3 0.1 millimol of hexamethylphosphoramide added in this run. a perforation for hypodermic withdrawal of the contents. actants. Hydrogen in varying amounts, as shown in the The volume of the suspension was 465 ml., from which Table 1, was then injected, followed successively by 2.0 the concentration of Natal) was calculated to be 0.765 N, millimols of AA, 1.5 millimols of TDSI, and 1.0 millimol ‘based on the phosphorus charged and assuming 10% loss. of sodium phosphide. The bottle was then inverted and 25 placed in a cradle on a balance which was ?rst brought (B) Polymerization to equilibrium and over-weighted with a 25-grarn weight. A series of polymerizations was run according to the Propylene was injected through a conduit and hypoder procedure of “Example I~B—Polymerization,"’ except mic needle until the balance was. again in equilibrium. that the preparation of sodium phosphide described im .The back pressure at this point was about 40 p.s.i. The mediately herein-above under “l1I-—A—Prepar-ation of So 30 bottle was placed on a polymerizer wheel which revolved dium Phosphide” was used in place of the correspond and dipped the bottle in a water bath at 50° C. for 41 ing preparation of Example I. The amounts of the so hours. At the end of this time, the bottle was removed dium phosphide and of the'AA used, and the temperature from the wheel, cooled to room temperature, vented, of polymerization, were varied vfrom run to run as set opened, and the mixture decanted into250 ml. of metha forth herewith in Table 1. The pressure in the bottles 35 nol, stirred for ?ve minutes, ?ltered, stirred with an addi was determined at intervals, and the decrease thereof tional 250 ml. of methanol containing 025 gram of a ‘from the original pressure taken as a measure of the de stabilizer, ?ltered, and dried at room temperature. The gree to which polymerization had taken place. The solvent residue was evaporated and the amount of atactic products of polymerization were recovered as described resin determined. The amount of hydrogen added, the in Example I. 40 number of grams of isotactic polymer, the number of In Table 1 above are particulars of the several runs. grams of atactic polymer, the melt index, the modulus in pounds per square inch, and the Rockwell (R-scale) of EXAMPLE IV the isotactic portion of the polymer are shown below. The polymerization procedure of Example 1 was dupli TABLE 2 cated except that 2.0 millimols ‘of the sodium phosphide 45 of Example 111 was used, butene-l was used in place H2 Isotactic Atactic Rockwell Modulus Melt of propylene, and the polymerization was terminated ' Index after 40 hours. . , EXAMPLE V None ______13. 2 ______89 116, 200 ' 19. 5 1. 4 85 95, 800 17. 1 l. 3 87 105, 600 (A) Example -IV was repeated excepting that 1.0 millimol 10 co. (36 p.p.m.)____ 21.0 2. l 92 108, 300 of tetrakis (dimethylamino) silane (hereafter TDSI) 20. 7 1. 2 92 121, 600 20. 0 ...... 1 _ 92 122, 300 were hypodermically. injected with the catalyst. Upon 25 cc. (90 p.p.m.) ____ 20.0 1.8 98 148, 900 ?ltering the methane slurry, there was separated 6.5 20. 3 1. 8 98 166, 200 0. 08 grams of isot-actic polybutene and on ?ashing off the sol 19. 6 ______99 159, 300 55 50 cc. (180 p.p.m.)___ 16. 3 ______102 166, 900 vent from the residual liquor, there was obtained 2.5 19. 3 1. 3 102 165, 100 0. 27 . 17. 6 1. 4 102 172, 200 grams of atactic polybutene. 100 cc. (360 p.p.m.)__ 16. 8 1. 7 104 194, 500 0.77 16. 4 1. 5 104 175, 800 1. 33 EXAMPLE VI - 14. 7 1.8 105 167, 800 15. 0 1. 4 105 207, 900 0. 98 An autoclave with a stainless steelliner was ?ushed V with nitrogen, then charged with 200 ml_ of heptane, 2 60 millimols of sodium phosphide, one millimol of TDSI, 1 Too low to measure on equipment. V and 2 millimols ofAA through a vent hole. The auto EXAMPLE VII-1 clave liner was then placed in a rocking bomb which had A ZS-ounce beverage bottle was charged with 250 ml. three times been ?ushed with nitrogen to 700 p.s.i. and of heptane,_?ushed withnitrogen, andsea'led with a buta the liner pressured to 600 psi. with OP. grade ethylene. diene-acrylonitrile rubber-lined crown cap provided with The mixture was heated to 50° C. 'over night and all-owed 'a perforation for the hypodermic injection of reactants. 'to cool slowly to room temperature the next day. The Then 2.0 millimols of AA and varying amounts of TDSI contents were then poured into 250 ml. of methanol and as shown in Table 3 ‘were hypodermically injected and the resulting precipitate ?ltered, washed with additional 70 the bottle placed on a polymerizer wheel which revolved methanol and dried. The highly crystalline polyethylene and dipped the bottle in a water bath at 50 C. for 4 hours. so formed was then pressed into a tough clear ?lm. The bottle was then inverted and placed in a cradle on a EXAMPLE V11 balance which was ?rst brought to equilibrium and then A 28-ounce beverage bottle was charged with 250ml. overweighted with a ZS-gram weight. Propylene was in of heptane, flushed with nitrogen, and sealed with a bu jected through a conduit and hypodermic needle until the 3,196,139 $ 1% balance again was in equilibrium. Varying amounts of ' ' ’ EXAMPLE XI a 1.0 molar suspension of sodium phosphide were then Example 1y was duplicated using magnesium P1105 hypodermically iIIj€Ct€CL th? number Of in each (pr?par?d by heating equiv/Q1691‘, amgunlts of mag 1' uh h?ihg ShOWh ‘in Table 3~ The home was Then Plac?d nesiurn and phosphorus under an argon blanket) in place on the phlymefilef-wheel which reVOh/hd a11d dipped the 5 of the potassium phosphide. In each run there were used bottle in the Water ‘bath at 50° C. fDr 65 h?ufs- Al the 2 millirnols of TDSI, 2 millirnols of AA and in the three End Of this “time, the home Was femhved from The Wheh], runs, one 11/2 and 2 millimols respectively of magnesium cooled to room temperature, vented and opened. The phosphide. In each case there was obtained an isotactic reaction product was then treated as in Example VII. polypropylene. TABLE 3

l N331) Hoptane (milli- TDSI AA Isotactic Atactic Modulus Rockwell Insol. 111015)

I 1.0 0.5 2.0 21.3 6.5 87,000 74 97.2 1. 0 1.0 2.0 21.6 1.1 125,600 83 s .0 1.0 1.5 2.0 ' 23.9 1.9v 115, 000 as a 07.7 1. 0 2. 0 2. 0 21. 7 0. 7 140, 400 02 l 00. 5 1.5 0.5 2.0 20.2 8.5 as, 500 57 05.3 1. 5 1. 0 2. 0 2o. 9 4. 3 0s, 300 7:1 as. 7 1. 5 1. 5 2. 0 20. 5 1. 2 117, 000 as as. 2 1. 5 2. 0 2. 0 22. 3 0. 0 1:3, 000 s7 s7. 5 2.0 0,5 2.0 19.3 5.3 73,300 55 90.0 2.0 1.0 2.0 16.7 3.5 77,300 66 97.0 2.0 1.5 2.0 20.0 3.7 00, 300 76 07.3 2. 0 5 2. 0 2.0 214 1.5 100 000 32 90. 0

EXAMPLE IX EXAMPLE XII 33381111316 VH1 was duplicated With the ‘following 6X‘ Example 1X was duplicated using lithium phosp'hide 9691101151 in place of the potassium phosph-ide, except that the (1) Potassium phosphlde was substituted for the sodium 30 polymerization was carried out for only 41 hours. The phosphide; results are shown in the following table. TABLE 0

L531’ Hcptaue (milli- TDSI AA Isotactic Atactic Modulus Rockwell Insol. mols) i 1.0 I 1.0 2.0 10 i 1.85 [ 123,600 I 85 I 95 l (2) The AA and TDSI were reacted for 2 hours prior EXAMPLE XIII to charging W1tl1_ propylene; . Two polymerization runs were carried out as in EX (3) Th5 Polymenzahh? Was Carried out fol‘ 70 hom's- ample Ill, except for the treatment of the reaction prod The results are set forth in Table 4. not. In the one case the reaction product was poured TABLE 4

K3? ' Heptane (millL TDSI AA Isotactic Atactic Modulus Rockwell Insol. 111015)

1. 0 1. 0 2. 0 21. 4 2. 3 111, 000 32 95. 1 1. 5 1. 0 2. 0 23. 2 3. s 108, 900 73 s3. 8

EX‘MPLE X _ 50 into 250 ml. of methanol which had previously been re A 2843111195 beverage hht?e Was Charged with 250 m1‘ acted with 0.125 g. of sodium to form sodium methylate. 0? h?ptane, ?flshed Wlt? nlifogeh, and sealed with 3 Mia‘ The mixture was stirred for 15 minutes, ?ltered, washed 1d1611e-aCTY1Oh1tY11e Iuhhehhhed Crown $211J PTOVlded Wlth with 100 ml. of methanol and dried overnight at room a Perforatloh for Th9; 'hYPOdBTImC lhl?ch?ll of reactants- temperature. The other reaction product used as a con The bottle was then inverted and Place? 111.3 cradle 011 a 55 trol was treated in precisely the same manner except that balance which Was ?rst brought ‘50 eqhlhlllrluh'l and Over- the 250 ml. of methanol contained no sodium methylate. Weighted With a 2‘5-g1’am Whight- Propylene W515 i?iacihd The control had a de?nite odor of phosphine and was a 'ihlough a whdlllt and hypodermic 11865112 Hnhl the b?l- light yellow while the other run resulted in a polymer ance was again in equilibrium. Two millimcl-S of AA having a slight cit-white color and an almost undetec were then hypodermically injected followed successively 60 table odor of phosphine. 51h 1 millimol Of TDSI and Varying amounts of Sodium T he novel catalysts of the instant invention may be afsehide (Pf?pared by haah'hg equivalent amounts of 80- :analogized to the “Ziegler-type” catalysts recently de d'hlm and arsenic llhdel‘ an argon blanket) as Shown in veloped for producing highly crystalline and isotactic Table 5- The 16365011 Products were treated as in the polymers of alpha-monoole?ns in that they comprise the above examples. The results of these runs are set forth 65 reaction of two different species of compounds. In the in Table 5. case of the Ziegler catalyst, one of the species is a transi TABLE 5 tion metal compound and the other an organometallic NMAS Heptane compound. In the inst-ant invention, one species is again (mm? Isomctic Mame Modulus Rockwell Insol' a transition metal compound, preferably in a lower val mols) 7 0 ence state, and the other a phosphide, arsenide or sti-bide as described hereinabove. In general, the procedures pg ?g igg and materials found useful for deactivating and removing 10. mo. 36.1) 136,300-. 92 95,;. catalyst residues- from the Z1egler- polymerizationi . prod 2.0 18.5 2.7 128.500 89 96-5 nets are also useful herein. While the preferred ma 75 terial to deactivate the catalyst is methanol added to the amazes ill 32 polymerization product'prior to contact with air, other sure and temperature and which makes use of novel and materials such as ethanol, isopropanol, butanol, water inexpensive catalytic compositions. The macro-molecu alcohol mixtures, etc., may be used. Other procedures lar products obtained are useful resins, rubbers and the for treating the polymer products to improve the purity like, and may be used to produce molding resins, ?bers, and clarity thereof, such as treatment with alkali, particu ?lms, rubber cements, etc. larly alcoholic alkali solutions (i.e. sodium methyl-ate), The instant application is a continuation-in-part of my ammonia, sodium hydroxide, etc., acids, steam, chelating co~pending application, Serial No, 102,957. agents such as ethanolamine, citric acid, ethylene-diamine What is claimed is: tetra-acetic acid, etc., may be used. 1 l. The process which comprises polymerizing an ethyl The novel catalysts of the instant invention are ge enically unsaturated compound by contacting the same nerically useful to polymerize materials which contain at with a catalyst comprising (A) a compound selected least one active ethylenic unsaturat-ion per molecule. Par ‘from the group consisting of phosphides, arsenides and ticularly preferred monomers are alpha-ole?nic hydro sti‘bides of a cation selected from the class consisting of carbons having no more than ten carbon atoms. These the metals of Groups LA, II-A, II-B, III—A and IV-A monomers include particularly ethylene, propylene, 15 of the Periodic Table, plus (B) a compound of the butene-l, isobutene, pentene-l, 3-methylbuteneel, hexene heavy metals. 1, styrene, 3,3-dimethylbutene-l, 4-methylpentene-1, de 2.. A process according to claim 1 wherein said cation cene-l, etc. . is a Group I-A metal. > In the case of copolymers, some monomers have a far 3. A process according to claim 1 wherein said cation greater rate of polymerization than others utilizing the 20 is a Group II~A metal. catalysts of the instant invention. In such cases, the 4. Process according to claim 1 wherein said com monomers are advantageously added incrementally to pound (A) is an arsenide. the polymerization reaction as polymerization proceeds 5. A process according to claim 4 wherein said arse so as to maintain the desired ratio of the monomers in nide is one which reacts with water to liberate arsine. the resulting copolymer. ' .6. A process according to claim 4 wherein said cation The catalyst may be used in any known manner. Al is a Group I—A metal. though all of the examples herein employ the catalyst in 7. A process according to claim 4 wherein said cation the solvent in which the catalyst was produced, the cata is a Group ll-A metal. lyst may be ?rst puri?ed, dried, and used in that state. 8. Process according to claim 1 wherein said com For instance, thephosphide, arsenide or stibide may be pound (A) is a phosphide. interacted with a solid transition metal compound, placed 9. A process according to claim 8 wherein said phos on a suitable support, and used in a ?xed bed reactor for phide is one which reacts with water to liberate phos a continuous polymerization process. This catalyst may phine. also be employed in the solid state in a ?uidized bed proc 1%. A process according to claim 8 wherein said cat ess, using the ole?n monomer as'the supporting fluid. ion is .a Group LA metal. The chemical literature indicates that de?nite com ‘11. A process according to claim 8 wherein said cation pounds, such as the phosp-hides, arsenides, and stibide‘s is a Group ILA metal. shown above, are produced by reaction of any of the 12. ‘Process according to claim 1 wherein said com~ metals taught herein with the Group V-A elements men pound (A) is a stibide. tioned above. However, the catalysts of the invention 4:0 1?]. A process according to claim 12 wherein said sti include such reaction products regardless of their exact bide is one which reacts with Water to liberate stibine. chemical constitution. 14. A process according to claim 12 wherein said cat— Another characterization of suitable solvents for the ion is a Group I—A metal. polymerization reaction of the invention is that they are 15. A process according to claim 12 wherein said cation is a Group lI-A metal. ’ non-protic, i.e., the preferred solvents do not supply pro 45 tons (which would react with the catalyst) under usual 16. Process of claim 1 wherein said compound of the conditions of polymerization. heavy metals is a titanium compound. The titanium trichlor-ide-aluminum reaction product 17. Process of claim 8 wherein said ethylenically un referred to above as “AA” is produced at moderately saturated compound is an ole?n. elevated temperatures in the order of 90° C. in approxi 50 18. The process which comprises polymerizing an ole mately the mol ratio of 3 mols of titanium tetrachloride tin by contacting the same with a catalyst comprising to one gram-atom of metal. The reaction product has (A) sodium phosphide, plus (B) a compound of the the empirical formula Ti3AlCl12, and appears to be a true heavy metals. compound of all of these elements, since any excess of 19. The process which comprises polymerizing propyl titanium tetrachloride may be leached there from down 55 ene by contacting the same with a catalyst comprising to, but not beyond, the composition of the formula given. (A) sodium phosphide, plus (B) a compound of the The sample reaction product prepared, as just described, heavy metals. should preferably be subjected to an. “activation” proc 20. The process which comprises polymerizing propyl ess, after which it is known as an “activated” preparation ene by contacting the same with a catalyst comprising and is suitable for use in this invention. The interme (A) sodium phosphide, plus (B) the reaction product diate sample reaction product is subjected to intensive of titanium tetrachloride and aluminum. grinding as in a ball mill, edge runner, roll mill, disc mill, 241. The process which comprises polymerizing pro "impact mill, or the like. In general, the extent of the pylene by contacting the same with a catalyst compris grinding should be such that the power consumed in the ing (A) sodium phosphide, plus (B) a titanium chloride. process will amount to at least about .03 kilowatt hours 122. A process comprising polymerizing an ethylenical per gram of material. The function or this grinding is ly unsaturated compound by contacting the same with a not alone to reduce the particle size, but seems also to de catalyst comprising an. alloali metal phosphide, plus a velop certain hyperactive, strained, crystal defect areas in transition metal compound. ' the material as the crystalline X-ray defraction pattern .23. A process comprising polymerizing an alpha-ole changes progressively during the grinding. 70 iinic hydrocarbon having no more than 10 carbon atoms From ‘the foregoing general discussion and detailed ex by contacting the samewith a catalyst comprising an perimental examples, it will be evident that the present in ‘alkali metal phosphide, plus a transition metal com vention provides a novel process for the polymerization pound. of ethylenically unsaturated compounds, and particularly 24. A process comprising polymerizing a conjugated ole-?ns, which is operable under mild conditions or" pres 75 diole?n by contacting the same with a catalyst compris 3,196,139 13 ing an alkali metal phosphide plus a transition metal phosphide, plus (B) a compound of the heavy metals. compound. 30. A catalytic composition comprising an alkali metal 25. A process comprising polymerizing a conjugated phosphide, plus the reaction product of aluminum and diole?n by contacting the same with a catalyst compris titanium tetrachloride. ing a phosphide of a Group Il-A metal plus a transition metal compound. 31. A catalytic composition according to claim 26 in 26. A catalytic composition comprising (A) a com cluding a polymerization modi?er. pound selected from the group consisting of phosp'hides, ‘32. A catalytic composition according to claim 38 in arsenides, and stibides of the metals of Groups I-A, II—A, cluding a polymerization modi?er. ILB, III-A and lV-A of the Periodic Table, plus (B) 33. A catalytic composition comprising (A) sodium a compound of the heavy metals. phosphide, plus (B) titanium trichlor-ide. 27. Catalytic composition according to claim 26 where in said compound (A) is a phosphide. References tilted by the Examiner 28. Catalytic composition according to claim 26 where UNITED STATES PATENTS in said heavy metal compound (B) is a titanium com pound. 3,026,309 3/ 62 Coover ______260—93.7 29. A catalytic composition comprising (A) sodium EOSEPH L. SCHOFER, Primary Examiner.