Formation of a latex from an organic solvent dispersion of a water insoluble polymer
United States Patent 1 Burke, Jr.  
 1 Apr. 22, 1975 1 FORMATION OF A LATEX FROM AN ORGANIC SOLVENT DISPERSION OF A WATER INSOLUBLE POLYMER Oliver W. Burke, .lr., Fort Lauderdale. Fla.  
 [75] Inventor:  
 [73] Assignee: Exxon Research and Engineering Company, Linden. NJ.  
 [22] Filed: Feb. 15, 1972 [21] Appl. No.: 226,419  
 Related US. Application Data [63] Continuation-impart of Ser. No. 817.494. April 18. 1969. abandoned. which is a continuation-in-part of [58] Field of Search 260/29.6 R. 29.7 R. 29.6 XA. 260/29.6 PT. 29.6 PM  
 [56] References Cited UNITED STATES PATENTS 2.403.966 7/1946 Brown et a1. 260/29.7 B 2.959.561 11/1960 Kelley 2611/29] B 3.007.852 11/1961 Hunter et a1. 260/29.7 B 3.129.132 4/1964 Gudheim 260/29.7 PT 3.244.660 4/1966 Herold 260/34.2 3.277.037 10/1966 Halpcr et a1 260/29.6 OL 3.281.386 10/1966 Moss 260/29.7 R 3.287.301 11/1966 Fysh ct a1. 260/29.6 OL 3.294.719 12/1966 Halpcr et al 260/29.6 0L 3.310.515 12/1966 Halper et a1 260/29.6 OL 3.432.483 3/1969 Moss 260/29.7 R 3.445.414 5/1969 Glymph ct a1. 260/29.6 PT 3.503.917 3/1970 Burke 260/296 R 3.644.263 2/1972 Burke... 260/29.7 R 3.652.482 3/1972 Burke 260/29.6 R  
 Primary E.\&#39;aminer--Harold D. Anderson Attorney. Agent, or FirmHall &amp; Houghton [5 7] ABSTRACT The preparation of stable aqueous latices from solvent dispersions of elastomers and other high polymer compositions has presented problems including excessive viscosity during processing and foaming, which have produced losses and increased costs. Herein combinations of steps are disclosed which reduce or eliminate various of these problems and enable the preparation of stable latices of high solids content. The process is characterized. inter alia. by the establishment of a flow of steam as a continuous phase into which an emulsion of a cement of the polymer is dispersed as an aerosol of latex droplets in a solvent-vapor continuum. followed by coalescence of the latex droplets and separation of the resulting coalesced liquid phase from the resulting solvent-vapor phase. In one embodiment of the present method an aqueous emulsion is prepared the dispersed phase of which principally comprises particles of precursor latex particle size and which may contain a lesser proportion of particles of greater than precursor latex particle size. This emulsion is converted to a stable latex by subjecting the same to special conditions which cause selective agglomeration of the particles of greater than precursor latex particle size. and removing the so agglomerated particles to yield a latex essentially free of particles of greater than colloidal size.  
 The separation of the gaseous and liquid latex phases is effected by impinging the same on a liquid body. preferably a flow of partially concentrated liquid latex; and other features of said copending applications may also be employed.  
 In the present disclosure. in addition. special provisions are made for eliminating from the latex particles of greater than colloidal size by controlling the heating and stripping operations so that in combination. such larger particles or the precursors thereof are coagulated and removed without coagulation of the latex of colloidal sized particles. Furthermore. special provisions are made for coagulum removal and recovery. and to contribute to a more expeditious processing of the materials into stable latices and a reduction in coagulum losses and increase in efficiency.  
 21 Claims, 18 Drawing Figures HXENTEE 3,879.32?  
 SHZU 8 BF 9 I N VENT OR ours? m aux/(.5, JR.  
 ATTORNEY PATENTEDAPRZZ I975 suznsur INVENT OR LII &#34;WP gok ATTORNEY FORMATION OF A LATEX FROM AN ORGANIC SOLVENT DISPERSION OF A WATER INSOLUBLE POLYMER Cross Reference to Related Applications This application is a continuation in part of my application Ser. No. 817,494 filed Apr. 18, 1969, now abandoned in favor hereof, and is an improvement over and continuationin-part of my applications Ser. No. 621,997, filed Mar. 7, 1967, US. (Pat. No. 3,503,917 issued Mar. 31, 1970); Ser. No. 691,823, filed Dec. 19, 1967, abandoned after the filing of application Ser. No. 70,949, (now US. Pat. No. 3,652,482 issued Mar. 28, 1972), on Sept. I0, 1970 to replace said Ser. No. 691,823; Ser No. 767,790, filed Oct. 15, 1968, and Ser. No. 784,596 filed Dec. 18, 1968, (now US. Pat. No. 3,644,263 issued Feb. 22, 1972), 784,596 filed Dec. 18, 1968, (now US. Pat. No. 3,644,263 issued Feb. 22. 1972), the disclosures of all of which are herein incorporated by reference.  
 BACKGROUND OF THE INVENTION 1. Field of the Invention This invention like those of my aforesaid copending applications relates to the production of high solids content aqueous latices with reduced polymer losses from solvent dispersions of high polymer compositions. and aims generally to provide improved method and apparatus combinations therefor, and new products produced thereby.  
 2. Description of the Prior Art To date, in the practical art, synthetic latices of high polymers have been primarily prepared by emulsion polymerization, which can produce latices of uniform colloidal particle size. ln contrast, such result is very difficult to obtain when employing high polymers made by essentially anhydrous catalyst polymerizations. In this latter case it has been proposed to prepare aqueous latices of high polymers from solvent solutions thereof by processes of the type which comprise the general steps of (l) providing a dispersion or cement of the polymer in a volatile organic solvent for the polymer. (2) adding to such dispersion water and an aqueous emulsifier therefor and emulsifying the same to produce an emulsion, (3) stripping the volatile organic solvent from the said emulsion, and (4) recovering the resulting latex product. However, in the practical art difficulty has been experienced in attempting to render such proposed processes commercially feasible, inter alia, in that 1 aqueous emulsification and stripping of solvent dispersions or cements of the high polymer materials, especially when dilute, have yielded latices of only medium solids content at high viscosity which render them commercially impractical; (2) in that the emulsions have tended to foam excessively during stripping; and (3) in that the emulsions have tended to form coagulum by coalescence of the polymer phase as well as by drying out especially on contact with heated surfaces, during the stripping and/or concentrating processes, and (4) in that such processes have tended to yield latices of poor mechanical stability, i. e. latices which when subjected to mechanical shear during blending with other materials in the industrial applications thereof, are apt to undergo coagulation thereby rendering the blended materials unsuitable for their intended latex applications.  
 SUMMARY OF THE INVENTION The particular improvements distinguishing the present invention from those of my aforesaid copending applications may be employed in practicing any of the several embodiments of process and apparatus set forth in said applications.  
  In all of such embodiments, while the emulsification and homogenization under ideal conditions can produce an aqueous emulsion having substantially all of its dispersed particles of precursor latex particle size; considerations of economy, storage, or other factors, may result intentionally or unintentionally in the production of a fine emulsion that, while principally comprising dispersed particles of precursor latex particle size which on removal of solvent therefrom yield latex particles in the colloidal size range, may contain a smaller proportion of particles of greater than precursor latex particle size. Such particles when relieved of their solvent and included in the latex product, do not appear to have much effect on the shelf life or storage stability of the latex, but do seem to act as initiators of coagulation when the latices containing them are subjected to mechanical working,  
  Accordingly, it is highly desirable that latices for uses in which they will be subjected to mechanical working be essentially free of such non-colloidal sized particles. and that such essential freedom be evidenced by the ability of the latex to pass a standardized mechanical stability test. Any of several such standardized tests may be employed, but the test preferred and referred to in the present specification is made as follows:  
 a. A 50 gram sample of 20% solids latex is placed in a 300 ml tall form beaker (Pyrex No. 1040) and agitated for 30 minutes with a Hamilton Beach (trade name) mixer (Model No. 930).  
 b. The so agitated latex is then poured through a 200 mesh stainless steel screen and any retained coagulum is washed with water, dried at C and weighted.  
 c. A mechanically stable latex should yield by this test less than 5% of its solid content as coagulum, and preferably essentially no coagulum.  
  One of the improvements of the present invention affords a method and means for insuring the production of such mechanically stable latices from aqueous emulsions of solvent polymer cements notwithstanding less than ideal preparation of the initial aqueous emulsion of solvent polymer solution, by&#39;a treatment which differentiates the susceptibility of the colloidal sized and non-colloidal sized resulting particles to heat, and then applies heat and mechanical treatment thereto in a manner to selectively coagulate the particles of greater than colloidal size without coagulating the colloidal sized particles, so that the latex will be essentially free of particles detrimental to its mechanical stability.  
  Another improvement of the present invention provides for recovery and reuse of the so selectively agglomerated and removed polymer coagulum.  
  Another improvement of the present invention resides in the adaptation of the first improvement just discussed for treating latices prepared from emulsions of solvent polymer solutions and having poor mechanical stability, to improve the mechanical stability thereof as measured by the aforesaid test.  
  Another improvement of the present invention resides in the provision of apparatus for facilitating the practice of the aforesaid process improvements.  
  In a first embodiment of the invention the formation of a latex from an organic solvent dispersion of a composition of an organic solvent soluble or dispersible polymer is effected by a process of the type which com- Pl&#39;lSeSI 1. providing a dispersion of the polymer composition, preferably one having a dry solids content within the range of 8 to 50% by weight, in an essentially water-immiscible volatile solvent which itself or as an azeotrope with water has a boiling point lower than that of water at atmospheric pressure,  
 2. adding water and emulsifier to said dispersion in proportions to form an emulsion having water as its continuum and emulsifying the same so that the discontinuous phase thereof is in particles at least principally of precursor latex particle size, such proportions preferably being in the range of 0.4 to emulsifier by weight based on the cement, and 0.4 to 2.5 parts by volume of water per part of cement,  
 3. stripping the solvent from the emulsion to form a latex, and  
  4. recovering the latex product, and which comprises the further steps of:  
 5. providing a moving flow of gas comprising steam as an initial continuous phase,  
 6. dispersing the said emulsion into the flow of steam as the initial continuous phase while subjecting the phases to a decrease of pressure and maintaining the temperature thereof below the limiting temperature for stability of the emulsion of particles of precursor latex particle size, thereby vaporizing solvent from the dispersed droplets and forming latex and vapor,  
 and in this embodiment mechanical stability of the latex is assured by the combination in the process of the further steps of:  
 7. subjecting the latex prepared by step (6) to an increase in temperature for a period of time only sufficient to destabilize, and permit coagulation from the latex of, particles of greater than colloidal size that may be present therein without such time period being sufficiently long to substantially effect coagulation of the latex particles of colloidal size, and  
 8. separating from the latex any coagulum formed.  
  In particular species of this first embodiment: step (7) may be practiced by passing the latex formed in step (6) in contact with a surface heated in the range of 212 to 260 F., preferably 225 to 245 F., for a sufficient time to effect the destabilization of such particles of greater than colloidal size, and this practice may be carried out in the presence of solvent vapor produced in step (6). In other species of this first embodiment, step (7) may be practiced by bringing into contact with the latex formed in step (6) a quantity of steam sufficient in amount and temperature to effect the selective destabilization of such particles of greater than colloidal size. and this practice may also be car ried out in the presence of solvent vapor produced in step (6), as by introducing such quantities of steam into the aerosol of latex droplets and vapor continuum formed in step (6) at a zone downstream from the zone of dispersion of the emulsion into the first flow of steam as the initial continuous phase. And in the several species of this first embodiment, the process preferably further includes the step of recycling the coagulum separated in step (8) to form part of the material employed in forming the emulsion in step (2), and preferably in this step the coagulated polymer is dissolved in solvent the same as that used in step l and the resulting solution is employed to form a part of the solvent dispersion of polymer composition produced in step (I). Also, in the several species of this first embodiment step (4) is preferably practiced by establishing a separating zone maintained at sub-atmospheric pressure, establishing a flow of latex through said separating zone, introducing into said separating zone the latex droplets and vapor produced by step (6) and impinging said droplets upon the flow of latex therein, withdrawing vapor from said separating zone, and withdrawing the combined latices from said separating zone, with or without other cooperating steps hereinafter disclosed, or disclosed in the aforesaid copending applications, e. g., when a very fine latex is being produced, and being augmented in particle size by grafting as in 27 herein (or by treating in an orifice type homogenizer as described in my copending application Ser. No. 767,790 (now U.S. Pat. No. 3,622,127) in connection with elements 26, 326, and 1226 therein) the selective coagulation of particles of greater than colloidal size from the latex may be facilitated by forming such very fine latex, and in turn the removal of the larger than colloidal size particles from the very fine latex contributes to the production from the latter of a more uniform latex of augmented particle size.  
  In a second embodiment, the process aspect of the invention is applied for separating non-colloidal sized particles of polymeric material from an aqueous latex of colloidal sized particles of such polymeric material, by practicing the following steps:  
 I. diluting the latex with water, if needed, and from 0 to 50% by weight based on the polymer of a solvent imbibable in said polymeric material, said solvent being a water immiscible volatile organic solvent which itself, or as an azeotrope with water, has a boiling point lower than water at atmospheric pressure,  
 2. providing a moving flow of gas comprising steam as an initial continuous phase, and thereafter,  
 3. subjecting the mixture prepared in step (1) to dispersion in said initial continuous phase and to further treatment as described in steps (6) and following of the first embodiment described above, which&#34; further treatment steps may be practiced in accordance with any of the species of said first embodiment described above or hereinafter disclosed.  
  And in addition to the above process improvements the invention provides new apparatus combinations permitting continuous operation of the above processes, or of processes disclosed in the aforesaid copending application.  
  Thus, objects of the invention, severally and interdependently, are to provide new apparatus features and new combinations of steps, which enable the production of improved latices. Other objects and advantages of the invention will be apparent from the above general description and the following more particular descriptions of preferred embodiments thereof, which, however, are illustrative but not restrictive of the invention, the scope of which is more particularly pointed out in the appended claims.  
  By the term latex&#34; as used herein is meant an aqueous suspension of colloidal polymer particles and emulsifier material and the polymer thereof may be selected from the following types and combinations thereof:  
 i. homopolymer.  
 ii. interpolymer including block and graft polymer.  
 iii. hydrocarbon polymer.  
 iv. polar polymer.  
 v. polymer composition comprising polymer material selected from (i) through (iv) above and compounding ingredients including reinforcing fillers and/or nonreinforcing fillers.  
  By the term colloidal particle&#34; or colloid&#34; as used herein is meant particles in the size range of 500 A to 10,000 A diameter. and by the term upper portion of the colloidal size range is meant particles in the size range of above 2,000 A, preferably 3,000 to 5,000 A, diameter.  
  By the term precursor latex particle size is meant a particle of polymer composition and solvent of such a size that when relieved of its solvent content the resulting particle is a colloidal particle as above defined.  
  By the term greater than precursor latex particle size&#34; is meant a particle of polymer composition and solvent which when relieved of its solvent yields particles ofgreater than colloidal size, which reduce the me chanical stability of the latex. Such particles are usually from to 1,000 times as large as particles of precursor latex particle size.  
  By natural resin&#34; as used herein is meant those inflammable amorphous vegetable products of secretion or disintegration usually formed in special cavities of plants and such resins are generally insoluble in water and soluble in alcohol, fusible and of concoidal fracture and are usually oxidation or polymerization products of terpenes.  
  By the term synthetic resin as used herein is meant organic oxidation, polymerization or condensation products not produced in nature but produced synthetically and having resin-like properties and which term does not include the synthetic rubbers. Synthetic resins include (l) the resinous polymers produced from unsaturated petroleum compounds by oxidation and/or polymerization such as resinous alpha-olefin polymers, (2) condensation resins such as the phenolic resins, the aminoplast resins, alkyd resins, glycerol-phthalate resins and the like; (3) the non-rubber-like resinous polymers produced by cyclizing, hydrogenating or halogenating unsaturated rubber polymers such as cyclized polyisoprene, chlorinated polyisoprene and the like, (4) resins derived from coal tar chemicals such as the cumarone-indene resins; (5) resinous materials pre pared from vinyl, vinylidene and vinylene monomers; (6) resinous copolymers prepared from vinyl. vinylidene and vinylene monomers with conjugated diene monomers such as the high styrene-butadiene resins; (7) resinous copolymers prepared from vinyl. vinylidene, and vinylene monomers and alpha-olifins such as the ethylene-vinyl acetate copolymers. As used herein the terms &#34;synthetic resins&#34; is restricted to those synthetic resins which are soluble in at least one solvent essentially water immiscible and which itself or as its azeotrope with water has a boiling point lower than that of water at atmospheric pressure.  
 &#39;alia. include. severally and in cooperating combinatrons:  
  l. The use of particular solvents for the polymers which are essentially immiscible with water in liquid phase. and which have boiling points less than the boiling point of water at atmospheric pressure, or which form azeotropes with water which have boiling points less than the boiling point of water at atmospheric pressure. Such solvents include the C to C acyclic hydrocarbon solvents, cyclohexane and methylcyclohexane, the C to C aromatic hydrocarbon solvents. and the less desirable halo-substituted C to C hydrocarbon solvents when required and combination of two or more members of the foregoing groups. Preferred are such solvents which have boiling points higher than that of water but which form azeotropes with water that have boiling points lower than that of water. which preferred group comprises especially the aromatic solvents including toluene, the xylenes, ethyl benzene. cumene, etc.  
  2. The formation of relatively high solids cements of the polymer composition and the solvent therefor selected as aforesaid. which cements preferably have viscosities of over 1000 centipoises and more preferably over 7.000 to 10,000 centipoises. and even over 10.000 to 20,000 centipoises, which high viscosities can be tolerated because of other cooperating steps of the process. The cements of emulsifiable viscosities in the preferred range of 7.000 to 10,000 centipoises generally comprise by weight at least 25% and preferably over 50% of solvent, depending on the polymer to which the invention is applied.  
 BRIEF DESCRIPTION OF THE DRAWING In the accompanying drawings:  
  FIGS. 1A and 3A are respectively a flow sheet or diagram of aportion of a complete process, and a diagrammatic plan view of a portion of an apparatus, embracing the present improvement; and FIGS. l-l6 illustrate more generally the process steps and apparatus features which cooperate with said specific improvements and to the embodiment thereof in a complete process and apparatus for producing latex from an emulsion of solvent polymer cement; and in FIGS. l-l6:  
  FIG. 1 is a flow sheet or diagram illustrating the sequences of steps and flow of material in typical embodiments of process.  
  FIG. 2 is a diagram of a preferred form of equipment for preparing the emulsion, corresponding to portions 7-13 of FIG. 1, the corresponding elements having the same numerals raised by 100, and respective parts thereof being designated by modifying letters.  
  FIG. 3 is a similar diagram of a preferred form of device for dispersing the emulsion of solvent/polymer cement into the steam flow, and segregating and separating the latex phase from the vapor phase, and further 7 treating the latex phase. corresponding to portions 14 and following of FIG. 1.  
  FIG. 4 is a more or less diagrammatic elevation partly cut away of a preferred embodiment of the portion 14 of FIG. 1.  
  FIG. is a more or less diagrammatic elevation, partly cut away. of a preferred form of separator corresponding to portion 16 of FIG. 1.  
  FIG. 6 is a more or less diagrammatic horizontal cross-section taken on line VI-VI of FIG. 5.  
  FIG. 7 is a more less diagrammatic elevation partly cut away of a preferred arrangement comprising a solvent-cement aqueous emulsion homogenizer delivering its output directly to an aerosol generator.  
  FIGS. 8 to II are diagrammatic flow sheets indicating modes of admixing partially concentrated latex. with or without water vapor evolved therefrom. with the gaseous and liquid phase from the aerosol generator. for aiding in the segregation and separation thereof.  
  FIGS. 12 to are vertical elevations partly cut away of types of mixer nozzles or in line mixers employable as aerosol generators and/or mixers in the practice of the invention, e.g. in FIGS. 8 to 11.  
  FIG. I6 is a more or less diagrammatic elevation of another embodiment.  
 DESCRIPTION OF PREFERRED EMBODIMENTS a. In General The particular improvements hereinafter described in connection with FIGS. 1A and 3A pertain to improvements in overall processes and apparatus for producing latices. and are particularly cooperative with preferred embodiments thereof.  
  In such preferred embodiments as illustrated in FIG. I, the high polymer 1, e.g. elastomer and/or plastomer material as hereinafter described. is prepared as a high polymer composition 4 for conversion to a cement, as by working in appropriate masticating. comminuting. or attenuating equipment 2, such as a rubber mill, Banbury. comminutor. extruder, or the like. In accordance with the aforesaid applications provision may be made for incorporating one or more known polymer compounding ingredients 3, e.g. rubber reinforcing filler. into the said polymer composition in such a way that the ingredients 3 are thereafter contained within the polymer particles of the latex being formed, for which purpose the said ingredient or ingredients 3 may be worked into the high polymer 1 by working therewith in the masticating equipment 2, providing such polymer composition will. when dispersed in a suitable solvent for the polymer and with the aid of an emulsifying agent and adequate emulsifying equipment. produce an aqueous dispersion that is essentially of precursor latex particle size. By such procedure the said polymer ingredients may become fixed to the compounding ingredient. i.e. the polymer particles can become reinforced by the fillers. and in effect become so intimately attached thereto, or embrasive thereof. as to retain the same when dispersed as a cement. In the case of compounding ingredients desired to be incorporated in the latex particles. but not requiring working with the polymer itself, such ingredients 3 may be fed into the cement forming equipment or dissolver 5 independently of the said polymer composition 4, as is also indicated in FIG. 1.  
  In the cement forming equipment or mixer or dissolver 5 which may also comprise a disperser, the high polymer composition 4 is combined and preferably stirred or otherwise worked with solvent 6 appropriate for the high polymer and for the process, as further described herein. to form a solvent cement 7 of the high polymer composition 4 and of any extraneously added compounding ingredients 3, the adequate dispersion of which in the cement may require vigorous working. which may even be accomplished by the passage of the cement through a suitable dispersing equipment 7a.  
  The solvent/polymer cement 7 is then combined with emulsifier 8 appropriate for the high polymer and the process. and with water 9 in a course emulsion mixing equipment 10 where the ingredients are mixed, preferably with the aid of heat, to form a course cement in water emulsion 11, which is then passed one or more times through an ultradispersing equipment l2, preferably of the type hereinafter described. which breaks up the relatively large particles of solvent-cement forming the discontinuous phase in the course emulsion 11 into particles principally of precursor latex size, i.e. which will be of latex particle size when relieved of their solvent content, and preferably in the upper portion of the colloidal size range.  
  As in my aforesaid applications the course cementin-water emulsion 11 may be passed one or more times. usually 6 to l2 times, through one or more so-called ultradispersers 12 e.g. the Moulds type more fully described hereinafter, in order to accomplish a sufficient reduction of latex particle size. The resulting fine emulsions have rather wide ranges of cement droplet size distribution and adjusted if necessary to an appropriate temperature, as by the cooler 13A, by-pass 138 and/or heater 13C, may be fed by suitable positive displacement, e.g. plunger, pump means 13D, to a homogenizer 13E, preferably of the vibrating blade type operating at 300 p.s.i. inlet and 30 p.s.i. outlet or of the resiliently restricted orifice type operating at pressures in the range of l .000 to 10,000 p.s.i., for reducing the particle I size distribution of the fine emulsion. The resulting emulsion 13 of reduced particle size distribution or without cooling by a cooler 13F is preferably delivered directly to a steam mixer or aerosol generator 14 where it is dispersed into a flow of steam as hereinafter de scribed. As indicated in FIG. 1 the emulsifier material 8 may be formed into an aqueous emulsifier solution 8&#39; with water 9&#39; saturated with solvent or with water 9&#34; from an extraneous source.  
  The resulting fine cement-in-water emulsion 13, in accordance with my aforesaid applications may be an unstable emulsion of only temporarily precursor latex size particles, and may be either stabilized as by adding further treatment or may be immediately converted into an aerosol, of which the dispersed phase may comprise colloidal and larger sized droplets in a steam/solvent vapor continuum, thus minimizing agglomeration of polymer-solvent particles into greater than precursor latex particle size, and is therein stripped of its solvent content. In such aerosol form the stripping is accomplished without excessive foaming and while avoiding or minimizing formation of coagulum, desiderata which cannot be attained when any substantial proportion of solvent is attempted to be removed from an aqueous emulsion of high polymer solvent cement in other than an aerosol condition. As in the aforesaid applications. the formation of the aerosol is preferably accomplished by providing a flow of steam 14a as an initial continuous phase and introducing the aqueous emulsion of at least temporarily precursor latex sized particles 13 as a discontinuous phase into the flow of steam as the initial continuous phase in a mixer or aerosol generator 14, whereby volatile solvent 6 is vaporized to become the continuous phase or the principal part thereof. and a corresponding amount of steam is condensed to supply the heat of vaporization for the solvent and become added as water to the discontinuous phase. As explained in connection with FIGS. 3 and 4, in certain embodiments of the process a part only of the steam may be supplied at a first station where the emulsion of polymer/solvent solution is introduced, and&#39;the remainder of the steam may be introduced at one or more stations down-stream from said first station. As the phase transition is accomplished the resulting gaseous and nongaseous phases are usually in a form resembling an aerosol and the aerosol droplets are then coalesced to form a latex separable from the vapor phase. Even when the emulsion has been prepared with only a limited quantity of emulsifier and has its dispersed phase only temporarily of precursor latex particle size, the latex produced by the phase transition in the aerosol may be sufficiently stable for coalescence or even for concentration. When these conditions do not pertain liquid emulsifier or liquid emulsifier solution may be added to the aerosol produced in the aerosol generator l4, as at 8A2.  
  The coalescing step may be practiced by passing the gaseous and non-gaseous phases through a coalescing means 15 in the form of a segregator or coalescer while maintaining the temperatures of the flows within the limited range for stability of the latex, and the coalesced droplets. now definitely of greater than aerosol size. are collected in the form of a bulk latex from the gaseous continuous phase. As is more fully described in connection with FIG. 3, in certain embodiments of the present invention, the coalescing is accomplished by subjecting the aerosol, on its way to a reduced pressure separator 16, to the action of centrifugal force for effecting segregation or coalescence of the nongaseous phase. as by passing the gas and latex phases of the aerosol through a centrifugal pump, and preferably a centrifugal pump having the type of pump rotor, pump chamber and inlet and outlet means illustrated in U.S. Pat. No. 3,324,798. As is also more fully described in connection with FIG. 3, in lieu of the centrifugal segregator, other types may be employed, e.g. a plate-type tortuous path segregator or an axial impact phase segregator. The final separation or collection may be attained by delivering the flows from the segregator 15 into a separator or collector 16, from the lower part of which the latex is drawn, and from an upper parat of which the continuous phase is passed to condensing equipment 17 maintained under vacuum, preferably a vacuum of the order of 28 to 29 inches of mercury, by withdrawal of uncondensed gases therefrom by vacuum pumping equipment 18, e.g. a steam jet, and the separator or collector 16 may be of various forms and may even be incorporated with a segregator 15 as is described in said copending application Ser. No. 691,823,  
  Still referring to FIG. 1, the high polymer composition latex l9 withdrawn from the separator 16 may be in part delivered as product 24, and is recycled as indicated at 21, that is it may be cycled through a different or the same heater and separator 21 and 16 for concentrating the latex, in which event the latex is heated to evaporate water therefrom under sub-atmospheric pressure at temperatures within the limited temperature range for its stability, and in accordance with the present improvements (FlGS. 1A and 3A) said circulation of latex may be passed in contact with a surface heated in the range of 212 to 260 F. for a sufficient time to destabilize and coagulate of greater than colloidal size. but not so long as to coagulate and remove any substantial proportion of the latex sized particles. by heating fluid passing externally to its flow path in 21 from the valved heat sources shown connected to 21. When such concentrating step has been employed, the product 24 resulting therefrom will be a latex of increased solids content.  
  As in my application Ser. No. 784,596 (now U.S. Pat. No. 3.622.127). various provisions may be employed for modifying the latex 20. These provisions are illustrated at 24 and following in FIG. 1 herein. Thus. in these embodiments of the process, the latex of intermediate solids content maybe mixed in a hold tank. mixer. or proportionate feeder 24 with polymerization catalyst 24a and monomer material 24b, and after appropriate adjustment of its temperature. as by a heat exchanger means 25, may be passed to polymerization reaction means 27. The modified polymer latex delivered by the reactor with or without added emulsifier 84A may be delivered to storage 29, preferably through a cooler 28, pending delivery as by a pump 30 for further treatment in heating and separating apparatus 31 and 32, which may be of the type shown at I220 and l2l6F in FIG. 3, hereinafter described, In this further treatment residual solvent. odors. and unreacted monomers. if any. may be removed, and if desired the latex may be further concentrated. The modified latex from separator 32, which in each event will have, along with other modifications, 21 higher solids content than the latex 20, may be passed by a pump 34 to product storage 36, preferably through a cooler 35.  
  In certain embodiments of the process, the operations up to point 24 may be conducted to form latex of low molecular weight polymer, which enables a latex of higher solids content to be employed without having to deal with excessively high viscosity, and monomer 24b and catalyst 24a, and temperature in the apparatus 27 may be employed in such quantities and degree as to materially augment the molecular weight of the polymer. and especially when it is desired to highly augment such molecular weight, polymer cross-linking agent 240 may be added in the mixer 24, for intimate association and reaction in the apparatus 27.  
  The final stripping. deodorizing, and/or concentrating in separator 32 is preferably effected as shown with the aid of condensing equipment 37 and vacuum pumping apparatus 38, and when such equipment produces a yield of recoverable fluid, e.g. pure water. such may be returned for reuse, e.g. to the water supply 9, as shown. Where prolonged shelf life is deisred, additional emulsifier may be added to the latex from SAS, preferably ahead of the pump 34.  
  In a still further embodiment of the invention, exemplified in FIG. 3, the stripped latex 324 having been substantially freed of particles of greater than colloidal size but still containing residual solvent, is subjected to concentration. deodorizing, and stripping of residual solvent in a heating apparatus 1220 and separator 1216, and is then, as a finished high solids latex, subjected to heating to an appropriate temperature at 1225, and further treatment with polymerization catalyst 1224a and monomer material 1224b and/or cross linking agent 1224: for effecting grafting or crosslinking of the polymer molecules contained in the particles of the finished latex. When necessary after this treatment. the grafted or cross-linked latex may be stripped of residual volatiles and odor, as by passing it through a stripper-deodorizer-concentrator circuit. which may be the same circuit 1220-1216 isolated for this purpose as by opening valves 1227a and 1229 and closing valves 1228 and 1231. Delivery of the treated latex to storage 1233 is preferably effected after cooling in a heat-exchanger 1232, by appropriate adjustment of the valves 122721-1231.  
 b. The Polymer Material 1 The new process is applicable to the preparation of latices from solvent solutions or dispersions of polymer materials which are essentially solvent soluble or dispersable and essentially water insoluble, including natural rubber and polymers of one or more ethylenically unsaturated monomers containing from 2 to 20 carbon atoms, preferably from 2 to carbon atoms. It is especially applicable to those elastomers and plastomers which, with or without plasticiser, have the foregoing properties and properties adapting their latices for use as adhesives, binders, film forming materials, coating materials, etc. Examples of such elastomers and plastomers. illustrative but not restrictive of those to which the invention can be applied, are as follows: butyl rubber, chlorinated butyl rubber, polyisobutylene, polybutadiene, polyisoprene, polyethylene, polypropylene (including both amorphous and/or crystalline polypropylene), ethylene-propylene polymer, ethylenepropylene-diene terpolymer, ethylene-vinylidene monomer interpolymers (including ethylene-vinyl acetate copolymers), butadiene-ethylene copolymers, propylene-butene-I copolymers, butadiene-styrene co polymer, nitrile rubber (including butadieneacrylonitrile and butadiene-methacrylonitrile copolymers), natural rubber, hydrocarbon resins, any of the foregoing polymers grafted with polar or other polymer grafts, as for example, those set forth in British Pat. No. 878,150 to Burke, published Sept. 27, 1961, and solvent soluble mixed plastomers and elastomers, e. g. butadiene-styrene-terpolymers with styrene copolymer resins including graft polymers thereof, as for example, those set forth in Hayes US. Pat. No. 2,802,808. Particularly included are those polymers which are pre pared in essentially water immiscible organic liquid, or under essentially anhydrous conditions, from unsaturated monomers having 2 to carbon atoms. Thus, polymer material includes graft polymer material, and said polymer material may be grafted, per se, or as a solvent solution or dispersion with monomer material including the monomer material set forth under (e) hereinafter, with the aid of a catalyst including the free radical generating catalysts set forth under (f) hereinafter.  
 c. Compounding Ingredients 3, 3a, 1223a.  
  The compounding ingredients which are especially contemplated in the present invention are the solid, particulate, compounding ingredients which are insoluble in the solvents 6, namely: fillers, including rubber reinforcing fillers, pigments, etc., which by the present invention may be incorporated into the polymer composition particles of the latices, rather than merely in the water phases thereof. The solid particulate compounding ingredients of this class comprise those set forth on pages 278 to 345 of Compounding Ingredients for Rubber&#34; 3rd Edition (1961) published by Rubber World, New York, N. Y., herein incorporated by reference, and on pages 146 to 217 of British Compounding Ingredients for Rubber&#34; by Brian J. Wilson (I958) published by W. Heffer &amp; Sons, Ltd., Cambridge, England, herein incorporated by reference. These ingredients thus include but are not limited to carbon black, talc, mica, lithopone, aluminum silicate, calcium silicate, silica, calcium carbonate, calcium sul fate, asbestos, organic pigments, inorganic pigments, and insoluble organic fillers including vinylic fillers and vinylic pigments. The insoluble organic fillers are described in British Pat. No. 799,043 to Burke published July 30, 1958 and in chapter 15 entitled Reinforcement of Rubber by Organic Fillers in the treatise Reinforcement of Elastomers&#34; edited by Gerard Kraus (1965) published by International Publishers, New York, N.Y., herein incorporated by reference.  
 d. The Emulsifiers 8 The invention in its broader aspects is not dependent on the use of any particular emulsifier or combination of emulsifiers, and may be practiced with any selected emulsifier or emulsifier combination suitable for aqueously emulsifying the non-aqueous solvent solutions or dispersions of the polymer materials concerned, for which purpose the emulsifier or combination of emulsifiers must be water soluble or water dispersible. Emulsifiers capable of forming stable aqueous emulsions with polymers may be selected from the following subgroups:  
 a. One or more anionic emulsifiers.  
 b. One or more cationic emulsifiers.  
 c. One or more nonionic emulsifiers.  
 d. Combinations of anionic and nonionic emulsifiers.  
 e. Combinations of cationic and nonionic emulsifiers.  
  The anionic, cationic and nonionic emulsifiers which are water soluble usually contain from 8 to 22 carbon atoms, when non-polymeric, but such limitation does not apply to those which are polymeric, where water solubility or dispersability is the criterion. The polymeric emulsifiers are best employed in conjunction with non-polymeric emulsifiers.  
  Emulsifiers of the anionic, cationic, and nonionic types including in some instances those in polymeric forms are set forth in Detergents and Emulsifiers 1967 Annual by John W. McCutcheon, published by John W. McCutcheon, Inc., Morristown, N. J., and especially those listed therein under the headings of emulsifiers suitable for emulsion polymerization or suitable for the emulsification of polymer material, or suitable for the emulsification of hydrocarbons including hydrocarbon waxes, may be used in practicing the present invention. The use of about 5-20 percent by weight of emulsifier material based on the polymer composition content of the polymer-solvent cement in practically all instances suffices and in most instances 5 to 6 or less percent by weight of emulsifier based on polymer composition content of the cement is sufficient, because the present process minimizes the amount of emulsifier required.  
  The anionic emulsifiers include but are not limited to emulsifiers which are alkali metal salts of fatty acids. partially hydrogenated fatty acids. rosin acids. disproportionated rosin acids. alkyl sulfates. aryl and alkaryl sulfonates. and water soluble and dispersable emulsifiers having the general formula; R(OCH-:CH- ),,OSO X wherein R is an aliphatic. aryl. alkaryl or cyclic radical. n is l to 9, and X is a monovalent alkali metal or ammonium radical.  
 Typical anionic emulsifiers are set forth in Table A.  
 TABLE A Typical Anionic Emulsiflers Acid or Salt Acid Radical Trade Name 1 Potassium hydroabietic and Dresinate 731 dehydroahietic 2 Potassium disproportionated lndusoil JC-l lB tall oil resin 3 Sodium hydrogenated Armeen HT tallow fatty acids 4 Sodium lauryl sulfate Sipex UB Dupanol WAQ 5 Sodium tallow sulfate Conco Sulfate T 6 Ammonium mononaphthalene Lomar PWA sulfonic acid 7 Sodium dodecylhenzene Santomerse 85B sulfate 8 Sodium polymerized alkyl Daxad l5 naphthalene Daxad 23 sulfonic acid 9 Sodium alkyl aryl Nacconol 90F sulfonate Suframin OBS l Sodium alkylnaphthalene Nekal ISA-75 sulfonate I 1 Sodium N-cyclohexyl-N- lgepon (N-42 palmitoyl-taurate 12 Sodium lauryl ether Sipon ES sulfate l3 Sodium alkylaryl Triton W3() polyether sulfate 14 Sodium sulfate ester of Alipal C0433 nonylphenosypoly lethyleneoxy) ethanol l Ammonium sulfate ester of Alipal C0436 nonylphenoxypoly (ethyleneoxy) ethanol [6 Sodium naphthalene Nacconol NRSF sulfonic acid I? Sodium dioctyl ester of Aerosol OT sulfosuccinic acid [8 Sodium saponified Gantex AN-l39 polyt methylvinylether/ maleic anhydride) 19 Sodium saponified poly- Lytron (styrene/maleic SMA-3000A anhydride) TABLE B Typical Cationic Emulsifiers Emulsifier Base Trade Name 1 C ocoamine Armeen C 2 Stearylamine Armeen T 3 N-alkyl trimethylene diamines Duomeen C (alkyl groups derived from Duomeen T cocoanut. soya. and tallow fatty acids) 4 Primary fatty amine ethyelen Priminox T-ZS TABLE B-Continued Typical Cationic Emulsifiers Non-ionic emulsifiers can be selected from the class of emulsifiers which are alkyl polyoxyethylene ethers and alcohols. or polyethylene ethers and alcohols. Other non-ionic emulsifiers include those which are polyoxyalkenated alkyl phenols or alcohols having the formula R(OCHR CHR ),,OH where R is an alkyl, aryl or alkaryl group. R is an alkyl group or hydrogen and n is an integer of 4 to 10 or even higher. Compounds of this type are prepared by condensing an alkyl phenol or an alcohol with ethylene oxide or propylene oxide. Typical nonionic emulsifiers are set forth in Table C.  
 TABLE C Typical nonionic Emulsifiers Chemical Name Trade Name 1. Nonylphenoxypolytethyleneoxy)- lgepal CO-970 ethanol 2. nonylphenyl polyethylene glycol Tergitol TP-J ether 3. poly hyleneglycol fatty ester Modecol L.  
 4. coconut alkanolamide Monamine AA-IOO 5. polyethyleneglycol 400 Pegmol-5942 monolaurate 6. propylenglycol monolaurate 7. castordiethanolamide Emid-6547 8. ethylene oxide condensate Ethomids with primary fatty amides 9. fatty alcohol polyglycolether Lorox l0. sorbitolsesquioleate Nonion OP-83 l l. polyoxyethylene lauryl ether Brij-35 l2. polyoxyethylene lauryl alcohol lgepal-43O l3. polyetherated fatty alcohols Emulphor-CN EmulphorCN-870 l4. polyoxyethylated octyl phenol Triton X400 having 8 to l0 ethylene oxide units The Polymeric Emulsifiers include the water dispersible polyelectrolytes set forth in Hedrick and Mowry&#39;s US. Pat. No. 2.625.529 relating to Methods of Conditioning Soils.&#34; In said patent are listed a number of water-soluble polyelectrolytes and these materials are defined as synthetic water soluble polyelectrolytes having a weight average molecular weight of at least 10.000 and having a structure derived by the polymerization of at least one monoolefinic compound through the aliphatic unsaturated group and substantially free of cross-linking. The present invention has shown that these synthetic water soluble polyelectrolytes can be employed as emulsifiers for the preparation of latices as herein set forth. The disclosed polyelectrolytes of this patent are therefor incorporated herein by reference. it being noted however that the lower limit of molecular weight prescribed by the patentee does not apply. the applicable criterion being that the materials are water soluble or water dispersible emulsifiers.  
  Combinations of emulsifiers. The present invention has disclosed that by using Certain combinations of emulsifiers, it becomes possible to prepare a stable latex from aliphatic hydrocarbon polymers dissolved in hydrocarbon solvents and even in aromatic solvents. as is desirable under certain processing conditions. An effective emulsifier combination for aqueously emulsifying 100 parts by weight of a hydrocarbon rubber dissolved in from about 300 to 600 parts of an aromatic hydrocarbon solvent such as toluene, may comprise parts by weight ofa nonionic emulsifier. e. g. polyoxyethylated octyl phenol such as Triton X-l00. a trade mark product and l part by weight of an anionic emulsifier. e.g. sodium lauryl sulfate.  
  Another effective emulsifier combination for 100 parts by weight of hydrocarbon rubber dissolved in about 400 parts of aromatic solvent such as toluene combines 3 parts by weight of the aryl anionic emulsifier. sodium salt of an alkaryl polyether sulfate e. g. Triton W- (a trade mark product) and 3 parts by weight of the non-aryl anionic emulsifier sodium lauryl sulfate e. g. Dupanol WAQ (a trade mark product).  
  it has for some time been a desideratum in the art to have a stable hydrocarbon rubber latex suitable for combination with asphalt or asphalt emulsions. for road surfacing and roofing purposes, for example. Application Ser. No. 691,823 replaced by application Ser. No. 70.949 now U.S. Pat. No. 3,652,482, has disclosed that latices of hydrocarbon rubber such as butyl rubber. polyisobutylene, ethylene-propylene rubber or rubbery amorphous polypropylene, which are suitable for such use. can be prepared by employing as emulsifier for the hydrocarbon solvent solution of the rubber a combination of emulsifiers in which one or more quaternary ammonium emulsifiers (e. g. the quaternary ammonium compounds supplied under the Redicote trade mark are combined with one or more fatty acid amine or diamine type emulsifiers in the ratio of quaternary ammonium to fatty acid amine in the range of from 1:5 to 5:1. notwithstanding that the quaternary ammonium emulsifiers alone, for the most part, will not form stable aqueous emulsions with the above types of hydrocarbon polymers.  
  For example a stable aqueous latex is obtained from hydrocarbon rubber e. g. butyl rubber or ethylenepropylene rubber, dissolved in an aliphatic or even an aromatic solvent. e.g. hexane, benzene, toluene and/or the zylenes, with the aid of a mixture of the emulsifiers selected from subgroups (a) and (b) in the ratio of 0.5:5 to 5:05 parts by weight, said mixture being employed in the amount of 2 to 10 parts by weight based on the polymer, and said sub-groups (a) and (b) being represented by formulae l and ll respectively:  
  CH CH 3 l 3 I. [R-1&#39;\I-(CH2)3-11\I-CH3] [x] CH3 CH3 II, R&#39;-  
 [ Na (CH2)3 NH3] 2[x] wherein R and R are selected from the alkyl radicals having from 8 to 22 carbon atoms and X is an acid anion. preferably the alkyl radicals being those derived from cocoanut oil and/or tallow fatty acids.  
  The quantity of emulsifier employed in this invention is in the range of 2% to 20% by weight and preferrably 4% to 12% by weight based on the high polymer composition; and if desired. small additions of electrolyte may be made to the latex or in preparing the course or fine emulsion, as. for example, in accordance with the practices referred to in U.S. Pat Nos. 2,955,094 issued Oct. 4, l960 and 3,222,311, issued Dec. 4, 1965, to Esso Research and Engineering Company, as assignee of R. S. Brodkey et al.. and A. L. Miller et al. Alkali metal acid phosphate salts are suitable for this purpose, and are also useful in connection with the use of the addituent 24d (FIG. 1) as above described, for reducing the quantity of said addituent required.  
 e. Monomer Materials 24b, 1224b The ethylenically unsaturated monomer material employable herein is selected from the class consisting of:  
 i. the mono-ethylenically unsaturated aromatic hydrocarbon monomers containing from 8 to 18 car bon atoms,  
 ii. the conjugated diene hydrocarbon monomers containing not more than 12 carbon atoms,  
 iii. the non-conjugated diene hydrocarbon monomers containing not more than 18 carbon atoms,  
 iv. the mono-ethylenically unsaturated monomers containing polar groups and having not more than 18 carbon atoms, and  
 v. the non-conjugated diene and triene monomers containing polar groups and having not more than 22 carbon atoms,  
 the polar groups of iv and v being selected from the class consisting of carboxyl, hydroxyl, carbonyl, ester. ether, nitrile. amine, quaternary ammonium, amide. triazine, halogen, and sulfur or phosphorous containing groups.  
  Examples of the respective groups of monomers comprised in the above class are set forth in my aforesaid applications, particularly application Ser. No. 784,596, filed Dec. 18, 1968, (now U.S. Pat. No. 3,644,263) and are herein incorporated by reference.  
 f. Free-Radical Generating Polymerization Catalysts The free-radical generating catalysts and catalyst systems useful in the range of 0.8 to 20 parts per parts of added monomer materials employed in certain embodiments of the present invention constitute a wellknown class which includes: the inorganic peroxides such as hydrogen peroxide and the like; the various organic peroxy catalysts, such as the dialkyl peroxides, e. g. diethyl peroxide, diisopropyl peroxide, dilauryl peroxide, dioleyl peroxide, distearyl peroxide, di-(tertiarybutyl) peroxide; di-(tertiary amyl) peroxide. dicumyl peroxide and the like; the alkyl hydrogen peroxides such as tertiary butyl hydroperoxide, tertiary amyl hydroperoxide, cumene hydroperoxide, tetralin hydroperoxide, and diisopropyl benzene hydroperoxide and the like; the symmetrical diacyl peroxides, for instance acetyl peroxide, propionyl peroxide, lauroyl peroxide, stearoyl peroxide, malonyl peroxide, succinoyl peroxide. phthaloyl peroxide, benzoyl peroxide; ketone peroxide such as methylethyl ketone peroxide. cyclohexanone peroxide, and the like; the fatty oil acid peroxides, such as cocoanut oil acid peroxides and the like; the  
 unsymmetrical or mixed diacyl peroxides. such as acetyl benzoyl peroxide, propionyl benzoyl peroxide and the like; the azo compounds such as Z-azobis (isobutyronitrile), &#39;l-azobis (2-methylbutyronitrilel. l-azobis (l-cyclohexancarbonitrile) and the like. and other free radical generating catalysts employable in emulsion polymerization, such as peroxy-catalyst compounds in combination with a reducing compound such as an amine. e. g. triethylene tetramine or tetraethylene pentamine. with or without metallic ion combination. e. g.. ferrous ions. which systems are referred to as redox free-radical generating catalyst systems. which latter are further exemplified in the treatise Emulsion Polymerization by F. A. Bovey. et al.. 1955 Interscience Publishers. lnc.. New York. N. Y. at pages 71-93. herein incorporated by reference.  
 g. Cross-linking Agents 24c. 12240 The cross-linking agents useful. in the range of 0.1 to 20 parts per 100 parts of polymer content of the latex by weight, for effecting the cross-linking employed in particular embodiments of the present invention, also form a well-known class of materials which includes: elemental sulfur. selenium and tellurium. and compounds containing these elements. usually in their lower valence states or covalance states. and other polyfunctional free radical generating catalysts. Compounds which liberate sulfur. selenium or tellurium during irradiation or during heat aging (l0() to 200 C.) are useful. Polymers containing sulfur, selenium or tellurium and/or monomers capable of forming such polymers are also useful. Conventional rubber vulcanizing agents and vulcanizing accelerators are particularly adapted to this application. Specific compounds of the class are: The mercapto thiazoles. such as 2-mercaptobenzothiozole and its salts. for example its zinc salt, thiuram sulfides, such as tetraethylthiuram monosulfide and tetrabutylthiuram monosulfide; guanidines, thiourea. substituted thioureas. thiocarbanilides, substituted thiocarbanilides such as o-dimethylthiocarbanilide and its isomers and alkyl homologs; zinc dialkyl dithiocarbamates such as zinc dimethyl dithiocarbamate. zinc diethyldithiocarbamate. zinc dibutyl dithiocarbamate, and zinc dibenzyl dithiocarbamate or accelerators containing these materials. thiurams such as tetramethylthiuram disulfide, tetraethylthiuram disulfide. and other tetra substituted thiuram disulfides; selenium dialkyl dithiocarbamates such as selenium diethyldithiocarbamate; Z-benzothiazyl-N,N-diethylthiocarbamyl sulfide; sodium or potassium dimethyldithiocarbamate; xanthates such as dibutyl zanthogen disulfide and Naugatuck Chemicals CPB and ZBX; alkyl phenol sulfides; bis(dimethylthiocarbamyl) disulfide, dipentamethylene tetrasulfide; and sulfur containing polymers such as Thiokol VA-3. 4.4-dithiomorpholine and disulfides such as benzothiazyl disulfide. In fact. any compound in which sulfur. selenium or tellurium is attached only to an atom of carbon. hydrogen. nitrogen or to another sulfur, selenium or tellurium atom. as the case may be, may be suitable.  
  Also included in the class are the sulfonyl hydrazides and disulfonyl hydrazides. The latter are particularly useful since they contain two widely separated sulfurbearing moieties capable of forming sulfur cross-links or free radical derived cross-linkages (as a result of thermal loss of nitrogen). Blowing agents such as p,p&#39;- oxybis (benzene sulfonyl hydride), p,p&#39;-diphenyl bis(- sulfonyl hydrazide) and m-benzene-bis(sulfonyl hydrazide) are examples of additives which can also be employed as cross-linking agents.  
  Included in the class are the cross-linking azo compounds, e.g. di-cyano-azo-butane; and the like.  
  Included in the class are also the peroxy compounds such as bis(a-, a-dimethyl-dicumy.) peroxide (dicumyl peroxide). l.3-bis(a-, t.butylperoxypropyl) benzene. 2.5-bis(t.butylperoxy)-2.5-dimethylhexane. 2.5- dimethyl-Z.5-di(t.-butylperoxy)hexyne-3. di(a-. a-dimethyl-p-chlorobenzyl)peroxide, di(a-. a-dimethyl-2.4- dichlorobenzyl) peroxide. di(0z-. oz-dimethylnaphthyl)peroxide and the like.  
  Further included in the class are combinations of the above said peroxy compounds and the above said sulfur. selenium and tellurium compounds.  
 h. Ionizing Radiation The ionizing radiation employed in certain embodiments of the present invention is of a type known to those skilled in the art. viz: it is radiation with sufficient energy to remove an electron from an atom. forming an ion pair; this requires an energy of about 32 electron volts (ev.) for each ion pair formed. This radiation has sufficient energy to non-selectively break chemical bonds; thus. in round numbers radiation with energy of 50 electron volts (ev.) and above may be used in lieu of polymerization catalyst. Such ionizing radiation is generally classed in two types; high energy particle radiation. and ionizing electromagnetic radiation. The effect produced by these two types of radiation is similar. the essential requisite being that the incident photons have sufficient energy to break chemical bonds and generate free radicals.  
  The preferred radiation for the practice of the said embodiments of this invention is high energy ionizing radiation, and has an energy equivalent to at least 0.] million electron volt (mev.). Higher energies are even more effective; there is no known upper limit, except that imposed by available equipment and the product stability.  
  When irradiation is employed in the present invention. it is preferably effected at about atmospheric pressure and at temperatures between about 5 and 95 C.. a temperature of about 25-65 C. being preferred.  
  As is well known in the irradiation grafting of solid substrates, the optimum dose of irradiation varies with the particular materials concerned, a dose of about 5.000 rads (0.005 mrad) being required for significant grafting. Dosages and dosage rates may be selected between the limits which with given latices and under the conditions concerned are sufficient to not require excessive time of treatment and those not so high as to cause excessive rise of temperature. e.g. above 95 C., or excessive decomposition of materials concerned. Such limits are well understood by those skilled in the irradiation art. and are readily determined for particular materials by simple tests as above indicated.  
 i. Equipment Homogenizers While the invention in its broader aspect is not limited to any particular homogenizer, the applicant has disclosed that certain types of homogenizer described in Mould. Jr. US. Pat. No. 3,195,867* and Hager US. Pat. No. 3,194,540* as suitable for low viscosity materials such as milk, oil, fruit slurries, etc.. can be employed effectively as an ultradisperser of aqueous emulsions of higher viscous solutions of polymer compositions. especially when connected in tandem. and/or for recycle, and in particular that a combination of such Mould type homogenizers followed by a resiliently restricted orifice type high pressure homogenizer (1,000 to 10,000 p.s.i.) e.g. of the Gaulin type (see Gaulin U.S. Pat. Nos. 753,792* and 756,953* as available from Manton-Gaulin Mfg. Co., Inc., as model K24-3BS but provided with a 75 horsepower motor, provides an aqueous emulsion of solvent/polymer cement yielding a latex having latex particles of an average diameter near the upper end of the colloidal size range suitable for high solids polymer latices, and of relatively narrow particle size distribution, when processed according to the invention. Herein incorporated by reference.  
  In FIG. 2 there is shown an arrangement of such Mould type and Gaulin type homogenizers to constitute a preferred cement emulsifying equipment. This arrangement is provided with optional facilities selectively employable by means of valves for continuous or batch operation, for single unit or tandem unit operation, and for selective complete or partial recycle in each mode of operation, and it will of course be understood that where certain of these optional facilities are not desired they may be omitted without departing from the invention.  
  In this FIG. 2 arrangement the solvent and polymer dispersion I07 and the water and emulsifier solution 108 are adjusted in temperature by heat exchangers llA and passed to the course emulsion mixer equipment. For batch operation, as shown, this equipment may be in the form ofa hold tank I provided with an agitator. For continuous operation. as shown, it may be in the form of in-line mixing equipment 1108. The inline mixer equipment 1108 may also be employed to premix the materials being delivered to tank 110 for batch operation. The coarse emulsion in batch operation is passed from tank 110 under gravity head and/or pressure head contributed by pump 110C to the ultradispersing equipment 112 and/or 112A and/or 1128, or for continuous operation may be passed to the latter directly from the in-line mixer equipment 110B, and under the head developed thereby augmented, if desired, by the heat developed by pump 110C. The coarse emulsion under pressure as aforesaid may be passed through any one of more of the ultradispersing equipments 112-1138 and may be recycled therethrough either directly, or by way of the coarse emulsion tank 110. When the preparation of the emulsion of precursor latex sized particles has been completed this intermediate product may be delivered to storage ll3j, preferably being cooled by means of a cooler 113F to assure maintenance of the emulsion even with minimum quantities of emulsifying agent present. As is indicated in FIG. 2, effective results have been attained by repeatedly passing the coarse emulsion through an equipment 112 of the perforated stator type shown in Mould, Jr. U.S. Pat. No. 3,195,867, and then through one or more equipments 112A and/or 1128 in tandem with, and similar to. equipment 112 but provided with a slotted stator of the type illustrated in FIGS. 5 and 7 of Hager U.S. Pat. No. 3,194,540, with recycling from equipment 112A to the tank 110 and then by gravity head through equipments 112 and 112A, about a half dozen to a dozen times before delivery of theresulting product to the storage tank 113. During recycling. especially with sensitive emulsion prepared with a minimum of emulsifying agent, it is desirable to cool the emulsion which has been heated by working in the ultradispersing apparatus, by means of a heat exchanger in the recycle line, as at 112C.  
  After the emulsion has been reduced to unstable emulsion of precursor latex particle size, when this feature of the process is employed, a further amount of emulsifier may be combined therewith as shown at 113g in FIG. 2 by simple mixing as in mixer M in the lines leading to 113F, without further homogenizing action that would further reduce the particle size of the dispersed phase. The emulsion of at least temporarily precursor latex particle size in the desired range may be fed, when stable or stabilized, to storage 113 or ll3j, or, when only temporarily stable may be fed directly to the mixer or aerosol generator of FIG. 3 via valved line 11311 or valved line 1131&#39;.  
  As is further shown in FIG. 2, various types of homogenizer can be employed for forming the fine emulsion of cement at least temporarily of precursor latex particle size, e.g. a homogenizer of the colloid mill type 213, a homogenizer 313 of the vibrating blade type such as the liquid whistle or Rapisonic (trademark) types (presently preferred when used as in FIG. 7), or an emulsifier of the high pressure resiliently restricted orifice type 113D. 113E to which the emulsion effluent from the ultradispersers 112-112B is fed after heating, e.g. to temperatures of l40l60 F by the heat of 113A. The Gaulin type homogenizer comprises the pump 113D which is a plunger pump that develops from 1,000 to 10,000 p.s.i. depending on the resilient load applied to the valve head means resiliently restricting the emulsifying orifice or valve-opening means of the device. This load can be adjusted in the commercial devices by means ofa hand wheel, shown at the entrance end of the homogenizer 113E. The output from the unit 113E may be delivered to cooler 113F and thence to storage ll3j, or via 11311, or may be stored in tank 113 when recycling through the homogenizer circuit l13D-1I3F is desired.  
 Stripping Mixer The stripping mixer 14 (FIG. 1) which disperses the aqueous emulsion of precursor latex sized solventlpolymer droplets into the gaseous stream of steam is preferably of the type illustrated in FIG. 4, consisting of a conduit section 114, which may be transparent, which has supported centrally thereofa torpedo shaped or fid-shaped member 114A for producing a restricted or venturi-effect passage 114B thereabout. The initial continuous phase of steam is admitted as at 114C to flow through the passage 1148 and produce an area of high velocity and low static head thereat. The aqueous emulsion of solvent-polymer solution is introduced into the central body 114A as by way of the tube 114D upon which it is supported, and issues into the gas stream via a narrow slot 114E extending peripherally of the body 114A at the region of greatest pressure reduced in the space 1148. Auxiliary steam and/or emulsifler may be introduced at 114F and 1146. When a downstream inlet, as IMO, is employed for admission of the auxiliary steam for practicing step (7) of the first embodiment of the invention summarized above, it is desirable to have the quantity of steam admitted upstream thereof, as at 114C, or at 114C and IMF, sufficient in heat content to vaporize substantially all the.