CA1188017A

CA1188017A - Colloidal size hydrophobic polymer particulate having discrete particles of an inorganic material dispersed therein

Info

Publication number: CA1188017A
Application number: CA000391078A
Authority: CA
Inventors: Jitka Solc
Original assignee: Dow Chemical Co
Current assignee: Dow Chemical Co
Priority date: 1980-12-15
Filing date: 1981-11-27
Publication date: 1985-05-28
Also published as: JPS57125203A; US4421660A; DE3172083D1; JPH0357921B2; EP0054832B1; AU551755B2; BR8108203A; EP0054832A1; AU7817081A

Abstract

ABSTRACT
Colloidal size particles of an inorganic solid such as magnetic iron oxide or titanium dioxide are encapsulated in a hydrophobic addition polymer such as a polymer of styrene by a polymerization process wherein a water-immiscible (hydrophobic) monomer is dispersed in a stabilized aqueous colloidal dispersior.
of the inorganic particles and subjected to conditions of emulsion polymerization. The resulting encapsulated particles are usefully employed as catalysts, toners, pigments, and magnetic diagnostic latexes.

Description

1 ~

A CC)LLOIDAL SIZE HYDROP~[OBIC POLYMER PARTICULATE
HAVING D I SCRE:TE PART I CLES OF AN INORGANI C
MATERIAL DISPERSED THEE~EIN

This invention relates to colloidal size particulates containing particles of an inorganic material and to polymeriæation processes used to prepare such particulates.

Metals, metal oxides, pigments, fillers and other inorganic particulates that tend to agglomerate are often coated with or encapsulated in hydrophobic ~ polymers ~or use in a wide variety of applications such :: as electroconductive additives to plastics, toners in electrophotographic applications and pigmented paints.
Conventionally, such particulates are prepared by (1) treating the inorganic solid with acid, a combina-tion of acid and base, alcohol or a polymer solution;
~ ~2~ dispersing an addition polymerizable monomer in an : 15 aqueous dispersion of a tr~ated inorganic solid and (3) subjecting the resulting dlspersion to emulsion polymerization conditions. Examples of such methods are de~cribed in U.S. Patent Nos. 4,048,136; 3,383,346;
3,935,340; 3,544,500 and 3,884,871. Unfortuna-tely, these methods are deficlent in that they of~en requlre expensive mlllt1-step procedures, anchoring agents, :
27, 950-F -1-.

.

functlonal additives, and s-tabilizing agents. Also, the polymeric particulates often must be employed as viscous pastes or dry powders.

In one aspect, the present invention is a process for preparing a colloidal size particulate comprising the steps of (1) emulsifying at least one hydrophobic, emulsion polymerizable monomer in an aqueous colloidal dispersion of discrete particles of an inorganic solid, said dispersion being maintained in a reasonably stable state with a member selected from the group consisting of a chemical dispersant and surfactant and (2) subjecting the resulting emulsion to emulsion polymerization conditions to form a stable, fluid aqueous colloidal dispersion of the particulate wherein essentially every particle of the inorganic solid is coated with the hydrophobic polymer resulting from said polymexization such tha~ substantially all o the inorganic particles are maintained in a discrete spaced apart relationship to each other by the hydro-phobic polymer.

In another aspect, this invention relates to a stable, fluid aqueous colloidal dispersion comprising a continuous aqueous phase and a polymer/inorganic solid disperse phase wherein a substantial portion of the particles of the disperse phase comprise a hydrophobic polymer matrix haviny dispersed therein colloidal inoryanic solid particles such that sub-stantially all of the inorganic particles are maintained ~ in a discrete spaced apart relationship to each other : 30 by the hydrophobic polymer.

27~950-F -2-In a further aspect, this lnvention resides in a par-ticulate having colloidal-slze particles wherein substantially all of said partlcles comprise a hydrophobic polymer matrix and at least one discrete colloidal particle of an inorganic solid dispersed in said matrix.

The matrix particulates of this invention are particularly useful in applications requiring a colloidal size particulate having magnetic properties. Examples of such applications include (1) the separation of a water-miscible fluid from a water-immiscible fluid as described in U.S. Patent No. 4,108,767; (2) clarification processes as described in U.S. Patent Nos~ 4,089,779 and 4,110,20~; and (3) the absorption of e.l.m. radiation.
Such matrix particulates are also useful in magnetic paints, electrically resistive barriers and moldable magnetic powders, as toners in electrophontographic applications, electroconductive additives for plastics, pigments in paint and ink formulations and pigmentary core latexes. Such particulates are suitably employed as diagnostic materials in human and animal health applications such as described in Nature/ Vol. 270, pp.
259-261 (17 Nov. 1977); Science, Vol. 200, pp. 1074-1076 ~ June 1978) and U.S. Patent No. 4,157,323; and as catalysts such as described in U.S. Patent No. 4,157,323.

Inoryanic solids suitably employed in the practice of this invention are inorganic materials in the form of colloidal particles, i.e., have diameters generally less than about 0.6 micrometer, preferably from 0.005 to ahout 0.4 micrometer, most prèferably from about n. 005 to about 0.1 micrometer, which particles tend to form aggregates if not treated with a dispersant or surface active agent. When dispersed in water, these inorganic particulates tend to aggregate or agglomerate upon standing. Often, as a result of ~i 27,950-F -3-such agglomeration, the lnorganic particles settle to the lower region of the aqueous dispersion. These solids are insoluble in water and hydrocarbon and are incapable of adsorbing more than 5 weight percent of hydrocarbon based on the weight of the solid.

Examples of such inorganic solids are lnorganic pigments such as titanium dioxide, zinc oxide, antimony oxide, magnesium oxide, fly ash, red oxide, yellow oxide, lemon chrome and cobalt blue; powders of metals including titanium, copper, brass, gold and stainless steel; carbonates such as calcium and magnesium carbonates; phosphates such as calcium and l~ad phos-phates; silica and silicates such as clay and glass particles; chromates such as lead chromate; metal salts such as silver chloride; inert filler materials such as titanates and talc; ferrites; and aluminum hydrates.
Of particular interest are powders of metals and metal alloys such as aluminum, cobalt, iron, copper, nickel, chromium, zinc, palladium, silver, ruthenium, platinum, gold, rhodium, lead and alloys of these metals. Also of interest are the oxides of such metals, particularly magnetic oxidès such as iron, nickel, cobalt or alloys thereof, as well as oxides of other elements such as titanium dioxide and silica. Of special interest are titanium dioxide that is preferably in the form of particles having an averag~ diameter in the range from about 002 to about 0.4 micrometer, silica that is preferably in the form of particles having an average diameter from about 0.005 to about 0.2 micrometer, and the magnetic iron oxides of the formula Fe3O4 which are in the form of finely divided magnetic particles or ferrofluids as such are disclosed in U.S. Patent No.
3,981,844, preferably those having an average particle 27,950-F ~4-3~7 diameter in the range from about 0.005 to about 0.1 micrometer.

Typically, such ferrofluids are aqueous dispersions of magnetic particles which are prepared by methods normally employed in comminuting metals and their ores, e.g., grinding and electrolysis or by precipitation methods. In both instances, chemical dispersants and/or surfactants are used to maintain the aqueous dispersions in a reasonably stable state.
Similar aqueous colloidal dispersions of nonmagnetic, inorganic solids are prepared by conventional techniques used in the manufacture of colloidal gold, calcium carbonate, titanium dioxide and silica. Examples of such methods are described by A. King in Inorganic Preparations, Van Nostrand (1936); H. N. Holmes in Manual of Colloid Chemistry, MacMillan (1~22); R. R.
Myers et al. in Pigments, Marcel-Dekker (197$) and Angew. Chem., International Ed., Vol. 19, 190-196 (lg~O) o The hydrophobic monomers employed in the practice of this invention are essentially water-immiscible, i.e., the monomer forms a separate phase when 5 g of monomer i5 mixed with 100 g of water. Such water-immiscible monomer(s) will polymerize under emulsion polymerization conditions to orm a water-insoluble polymer which will exist in the form of a stable aqueous colloidal dispersion, usually with the aid of suita~le surface active agents. Examples of suitable hydrophobic monomers include monovinylidene aromati.c monomers such as styrene, vinyl toluene, t-butyl styrene, chlorostyrene, vinylbenzyl chloride and vinyl pyxidene; alkyl e~ters of a,~-ethylenically 27,950-F 5 3~7 unsaturateA acids such as ethyl acrylatel methyl meth-acrylate, butyl acrylate and 2-ethylhexyl acrylate;
unsaturated esters of saturated carboxyli.c acids such as vinyl acetate, unsaturated halides such as vinyl chloride and vlnylidene chloride; unsaturated nltriles such as acrylonitrile; dienes such as butadiene and isoprene; and the like. Of these monomers, the mono-vinylidene aromatics such as styrene and the alkyl acrylates such as butyl acrylate are preferred.

In addition to such hydrophobic monomer, relatively minor portions, e.g., less than 10, pre-ferably less than 5, weight pexcent based on total monomer component, of a water-soluble monomer such as an ethylenically unsaturated carboxylic acid or iks salt such as acrylic acid or sodium acrylate; meth-acrylic acid, itaconic acid and maleic acid; an ethylenically unsaturated carboxamide such as acryl-amide; vinyl pyrrolidone; hydroxyalkyl acrylates and methacrylates such as hydroxyethyl acrylate, hydroxy-propyl acrylate and hydroxyethyl me-thacrylate; amino-alkyl esters of unsa-turated acids such as 2~aminoethyl methacrylate; epoxy functional monomers such as gly-cidyl methacrylate; sulfoalkyl esters of unsaturated acids such as 2-sulfoethyl methacrylate; ethylenically unsaturated quaternary ammonium compounds such as vinylbenzyl trimethyl ammonium chloride may be employed.

It is critical, however, that such water--soluble monomers not be employed in amounts sufficient to render the resultin~ polymer soluble in water.
Particularly effective monomer recipes for the practice of this invention are those cont~; nl ng from 20 to 90 weight percent of styrene, from 10 to 80 weight percent 27,950-F -6-of alkyl acrylate such as butyl acrylate and from 0.01 to 2 weight percent of the unsaturated carboxylic acids such as acrylic acid, all based on the weigh-t of total monomers.

In the practice of this invention, it is preferred to initially prepare an aqueous colloidal dispersion of the inorganic solid by contacting said solid with an aqueous solution of a water~soluble surfactant or emulsifier thereby forming the dispersion which contains from about 5 to about 70 weight percent of the inorganic solid. Typically, suitable surface active agents or emulsifiers include salts of fatty acids such as po-tassium oleate, metal alkyl sulfates such as sodium lauryl sulfate, salts of alkyl aryl lS sulfonic acids such as sodium dodecylbenzene sulfonate, polysoaps such as sodium polyacrylate and alkali metal salts of methyl methacrylate/2-sulfoethyl methacrylate copolymers and other sulfoa].kyl acrylate copolymers, and other anionic surfactants such as the dihexyl ester of sodium sulfosuccinic acid; nonionic surfactants such as the nonionic condensates of ethylene oxide with propylene oxide, ethylene glycol and/or propylene glycol; and cationic surfactants such as alkylamine-guanidine polyoxyethanols, as well as a wide variety of micelle genera~ing substances described by D. C. Blackley in Emulsion Pol~merization, Wiley and Sons, Chapter 7 (1975) and other surfactants listed in McCutcheon's Detergents and Emulsifiers, 1980 Annual, North American Edition, McCutcheon, Inc., Morristown, NJ. Also included among the suitable surfactants are the surface active polymers (often called polysoaps), e.g., those described in U.S. Patent No. 3~65~032O Of the suitable surfactants, the anionic varieties such as the potassium salts of 27,950-F -7-functionalized oligomers, e.g., Polywet varieties sold by Uniroyal Chemical, are preferred. Such surface active agents or emulsifiers are employed in amounts sufficient to provide a stable dispersion of the inorganic solid in water. Preferably, such surface active agents are employed in concentrations in the range from about 0.2 to about 10, most preferably from about 1 -to a~out 6, weight percent based on the aqueous phase. Particularly desirable processes for forming such aqueous colloidal dispersions of inorganic solids are described in U.S. Patent Nos. 3,826,667; 3,981,844;
3,843,540 and Industrial Engineering Production and Research Development, Vol. 14, 147-151 (1980).

The aqueous dispersion of inorganic solid is then comblned with the water-immiscible monomer to form the desired emulsion by normal mixing procedures, for example, passing both the dispersion and monomer through a high shear mixing device such as a Waring blendor, homogenizer or ultrasonic mixer. Alternatively and preferably, the monomer i5 added continuously to the aqueous dispersion of inorganic solid during the polym~
erization. Advantageously, the monomer is in the form of an aqueous emulsion of the monomer which emulsion is maintained by a water-soluble monomer and/or a water-soluble emulsifier such as described hereinbefore. Asanother alternative, the a~ueous emulsion of inorganic solid and water~immiscible monomer can be prepared by adding colloidal size inorganic particles to an exist-ing aqueous emulsion of monomer. In such instances, it 3Q is often desirable to add additional emulsifier to the emulsion prior to or simultaneous with the addition of the inorganic solid.

27,95Q~F -8-In the emulsion of inorganic solld and water-~immiscible monomer, the aqueous phase is present in a proportion sufficient to be the continuous phase of the emulsion. The inorganic solid is present in proportions sufficient to provide the matrix particulate, with the desired characteristics, e.g., magnetic properties, pigmentation, etc. The water-immiscible monomer is present in proportion sufficient to enclose or encap-sulate the inorganic solid when polymerized, and suf-ficient emulsifier and/or surface active agent ispresent to provide an aqueous colloidal emulsion which is sufficiently stable to be subjected to emulsion polymerization conditions. Preferably, the emulsion contains from about 0.1 to 25 weight percent of inorganic solid, from about 1 to 30 weight percenk of monomer and a remai ni ng amount of the agueous phase including emulsifier (surfactant), catalyst and the like.

The emulsion polymerization conditions employ~d in the practice of this invention are generally conven-tional free-radical type polymeriæations carried out in the presence of a radical initiator such as a peroxygen compound, an azo catalyst or ultraviolet light.
Preferably, such polymeri2ation is carried out in the presence of a water-soluble peroxygen compound at temperatures in the range from about 50 to 90C. The emulsion is generally agitated during the polymerization period to maintain adequate feed transfer. The con-centratlon is normally in the range from about 0.005 -to 8, preferably from about 0.01 ~o 5, weight percent based on total monomer.

E~amples of suitable catalysts include inor-ganic persulfate compounds such as sodium persulfate, 27,950-F -9-potassium persulfate, ammonium persulfate; peroxides such as hydrogen peroxide, t-butyl hydroperoxide, dibenzoyl peroxide and dilauroyl peroxide; azo cata-lysts such as azobisisobutyronitrile, and other common free-radical generating compounds. Also suitable are various forms of free-radical generating radiation means such as ultraviolet radiation, elec-tron beam radiation and gamma radiation. Alternatively, a redox catalyst compositio~ can be employed wherein the polym-erization temperature ranges from about 25 to 80C.Exemplary redox catalyst compositions include a per-oxygen compound as described hereinbefore, preferably potassium persulate or t-butyl hydroperoxide and a reducing component such as sodium metabisulfite and sodium formaldehyde hydrosulfite. It is also suitable to employ various chain transfer agents such as mercap-tans, e.g., dodecyl mercaptan; dialkyl xanthogen disul fides; diaryl disulfides and others listed in Blackley, supra, Chapter 8 in concentrations as described therein.

~0 Following emulsion polymerization, the emul-sion polymerizate can be withdrawn from the polymeriza tion vessel and (1) the emulsion is employed as is or

(2) the unreacted monomer and other volatiles are removed to form a concentrated emulsion and then used or (3) the matrix particulate can be separated from the aqueous continuous phase of the dispersion by conven-tional means such as drylng under vacuum. The dried matrix particulate preferably contains from 1 to 70 weight percent of inorganic solid and from 99 to 30 weight percent of polymer matrix.

The following examples are given to illustrate the invention and should not be construed as limi-ting 27,950-F -10-8(~7 its scope. Unless otherwise indicated, all parts and percentages are by weight.

Example 1 An aqueous dispersion of iron oxide (Fe3O4) is prepared by the procedure described in Table I, footnote (2).

To a 3-neck flask equipped with a stlrrer, two addition funnels and a condenser is added a mixture of 507 g of the 28.3 percent solids dispersion of Fe3O4 ~200 gauss and average particle size less -than 0.5 micrometer) and 20~ g`of deionized water. The mixture is then heated under nitrogen atmosphere to 90C while stirring the mixture. At this temperature of 90C, a monomer stream and an agueous surfactant stream are separately introduced via the two addition funnels into the flask, each stream being introduced at the rate of 5.5~6.0 ml/min over a period of 90 minutes. The monomer stream consists of 64 g of styrene, 16 g of butyl acrylate and 3.0 g of t-butyl hydroperoxide. The aqueous stream consists of 80 g of deionized water, 1.25 g of a potassium salt of a func-tionalized oligomer sold by Uniroyal Chemical under the trade name "Polywet KX~4" and 2.0 g of sodium formaldehyde hydrosulfite.
The resulting reaction mixture is stirred and maintained 2S under nitrogen at 90C for an additional half hour.
The resulting 24.6 percent solids latex is concentrated by distilla-tion under vacuum to a 29.7 percent solids latex having dispersed particles with a polymeric as well as magnetic charact~ristic. The particles have a narrow particle size distribution and an average particle diameter o 0.107 micrometer as determined by hydrodynamic chromatography. The latex remains stable in an applied * Trade Mar3c 27,950-F

magnetic field of 60 grams and exhiblts propertles common to magnetic colloids. For example, such magnetic colloids are magnetizable liquids that are instantly demagnitized upon removal of a magnetic field and levitate an object upon application of a magnetic field. Magnetization of the latex by a Collpits oscil-lator circuit technique, described by E. A. Peterson et al. in the Journal of Colloidal and Interfacial Science, 70, 3 (1977), is estimated to be 135 gauss.

Example 2 A mixture of 7 g of Ferrofluid A-05 (200 gauss, 25.7 percent solids) sold by Ferrofluidics Corporation, Burlington, MA; 1 g of a 10 percent a~ueous solution of the dihexyl ester of sodium sulfosuccinic acid and 140 g of water are converted to an aqueous dispersion with an ultrasonic probe operating at 90 percent capacity for 2 minutes. The resulting disper-sion is added to 15 g of styrene contai nl ng O .1855 g of t-butyl peroxide. The dispersion is heated with agita-tion under a nitrogen atmosphere to 93C. A 0.05-g portion of sodium formaldehyde hydrosulfite dissolved in 2 ml of water is introduced illtO the dispersion.
The polymerization reaction is continued for 2 hours to form an aqueous colloidal dispersion containing 10.3 percent solids. The resulting matrix particulate is recovered in the form of an aqueous dispersion which is responsive to a magnetic field. Electrornicrographs of individual matrix particles show them to have a polymer matrix enclosing discrete particles of the Ferrofluid.
Many matrix particles are observed to contain more than one discrete particle of magnetic iron oxide. The average particle diameter of the matrix particulate is about 0.085 micrometer.
* Trade ~lark 27,950-F ~12-Example 3 A 40-g portion of Ferrofluid A-01 (50 gauss~
containing 7.2 percent solids is cenkrifuged on a high speed laboratory centrifuge for 6 hours at 17,000 rpm.
A 3.8-g portion of sediment (60 percent solids) is recovered from the centrifugation and redispersed in 15 g of an aqueous solution cont~ining 5 percent of potassium oleate and 3.2 g of an aqueous solution con-t~i ni ng 4 percent of the dihexyl ester of sodium sulfo-succinic acid. The resulting dispersion is combinedwith 230 g of deionized water and then agitated using an ultrasonic probe. To the resulting dispersion is added 25 g of styrene and 0.2 g of t-butyl peroxide.
The dispersion is heated under nitrogen with agitation to a temperature of 90C. The dispersion contalns 0.88 percent of Fe304, 0.3 percent of potassium oleate, 0.04 percent of the dihexyl ester, 9.1 percent of styrene and 0.76 percent o t-butyl peroxide. At this point, 0.05 g of sodium formaldehyde hydrosulfite dissolved in 2 ml of water is introduced into the dispersion and the polymerization reaction is allowed to proceed for 30 minutes. Following this time, a 9.4 percent solids polymer matrix latex of polymer matrix ixon particles is recovered wherein the average particle diamete.r of the matrix particles is 0. oa micrometer.

Example 4 A 3.8-g sample of the sediment as prepared in Example 2 is dispersed in 15 g of an aqueous solution of 5 percent of potassium oleate. This dispexsion is co~bined with 220 g of deionized water and agitated with an ultrasonic probe. To this dispersion is added 25 g of styrene and 0.196 g of t-butyl hydroperoxide.
This dispersion contains 0.9 percent of F304, 0.28 27,950-F -].3~

percent of oleate, 9.47 percent of styrene and 0.07 percent of t-butyl peroxide. The resulting dispersion is heated under nitrogen with agitation to 90C and 0.05 g of sodium formaldehyde hydrosulfite is added to the dispersion. The reaction is allowed to proceed for 30 minutes. The resulting latex of encapsulated iron particles contains 7.4 percent solids.

Similar results are achieved with the fore-going procedure when sodium lauryl sulfate, sodium dihexyl sulfosuccinate, methyl methacrylate/2-sulfoethyl methacrylate/acrylic acid ~67/6/27~ terpolymer, methyl methacrylate (30/20) copolymer, methyl methacrylate/-2-sulfoethyl methacrylate (85/15) copolymer or mixture of two or more of same is substituted for the potassium lS oleate. In these polymers, the numbers in parenthesis represent mole percentages of the individual monomers.

Example 5 I. Dispersion of Inorganic Solid Except for the magnetic iron oxide of Sample No. 11 of the ollowing table, several pigment disper sions are prepared by dispersing the pigment specified in Table I in an aqueous solution of a potassium salt of a functionalized oligomer sold by Uniroyal Chemical under the trade name "Polywet KX-4." The dispersion of magnetic iron oxide is prepared according to footnote (2) of the following table. Dispersion is achieved by using an ultrasonic probe 3 times operating at 90 percent capacity for 5 minutes each time. The disper-sion is allowed to stand overnight and the top layer cont~l nl ng the colloidal dispersed pigment is decanted and retained for the subsequent polymerization.

27,950-F -14-II. Polymerizatlon Each of the aforementioned pigment dispersions is subjected to the following emulsion polymerization procedure.

A mixture of 14.5 g of one of the pigment dispersions specified in Table I, 150 g of deionized water and 1.7 g of lN NaOH is prepared by using an ultrasonic probe operating at 90 percent capacity for 4 minutes. This mixture is charged to a one-liter,

3-neck flask e~uipped with a stirrer, condenser and 2 addition funnels. The mixture is heated with agitation under nitrogen to 90C. A monomeric stream consisting of 20 g of styrene and 20 g of butyl acrylate and an aqueous stream consistiny of 45 g of deionized water, 1~5 g of a 40 parcent solution of Polywet KX-4 in water, 1 g of lN NaOH and 0.75 g of sodium persulfate are eacn added at the rate of about 2 ml/minute. After addition of the monomer and aqueous stream is comple~ed, the resulking reaction mixture is maintained under nitrogen and with agitation at 90C for 40 minutes.
The xesulting latex is placed under vacuum with agita~
tion to remove unreacted monomer and water thereby providing a latex, herein called "a dlspersion of a matrix particulate."

The several aqueous dispersions of matrix particulates are described in Table I.

27,g50-F -15-TABLE I
Pi~ment Dispersion Pigment~1) Dispersant~2) Monomer(3~ Emulsifier{4) Sample Avg Part Amst Amt Wt Ratio Amt Amt No.Type Size, ~m Wt % ~ Wt % ~Ye~ of Monomer Wt % Type Wt %
1 Ti2 <045 2.3 KX-4 0.6 S/BA 1:115.7 KX-4 0.43 2 ~io2 'f 5-5 " 2.0 S/BA 1:118.4 " 0.20 3 Tio2 " 10.2 " 0.25 S/BA 1 117.0 ~' 0.78

4 Tio2 " 11.7 " 0.36 S/BA 1:1 7.8 " 0.58 C~CO3< 0 091.3 " 0.036 S/BA1:1 12.7 " 0.30 6 ZnO< 0.115.6 " 0.50 S/BA 9:118~7 " 0.48 ~ ~
7 ZnO " 13.6 " Q.64 S/BA 9:113.5 " 0.35 ~3 8 Clay< 0.386.5 " 0.70 S/BA 1:119.2 " 0.23 9 Silica < 0.045 5.6 " 1.0 S/BA1:1 18.7 " 0.20 Silica " 6.5 " 1.2 S/BA 1:112.9 " 0.06 ll Magnetic Iron Oxide< 0.035 7.3 " 4 5 S/BA4:1 8.l 1! 0.

~ TABLE I ~Con'd) ui Average Initiator~53 % Particle .Sample Amt Solids Di~meter No. Type Wt % (6) ~m(7) 1 Na2S28 0.29 17.8 0.53 (0.114 2 " 0,13 24.3 0.~5 ~0.15~
3 " 0.16 28.1 0.74 (0.12) 4 " 0.20 20.2 0.68 ~0.118) " 0.20 14.0 0.42 6 " 0.16 23.8 0.38 7 " 3.11 27.2 0.31 8 " G.12 25.0 0.85 ~~
9 i' 0.07 23.5 0.12 " 0.05 1~.5 0.116 11 TBHP 0.18 19.6 0.09 ~ TABL~ I (Co~'d) ~, (1~ Average particle size in micrometers ~m3 as measured by electron microscopy. Weight percent of pigment based on weight of aqueous dispersion of matrix particulate.
(2) KX~4 = Pol~wet KX-4 sold by Uniroyal Chemical. Weight percent of dispersant based on weight of aqueous dispersion of matrix particulate.
In the ~reparation of the iron oxide dispersion of Sample No. 11, an ~queous solutio~30f ~rric and f~rrous salts are mixed in amounts to maintain the Fe /Fe molar ratio at ~2:1. Magnetic iron oxide is then precipitated at 0-10C by rapid addition of lN NH OH and vigorous agitation until pH of 9-10 is reached. Immediately the~eafter, the dispersant is introduced with agitation to the aqueous medium containing the precipitated iron oxide and the mixture is heated at 90C for one hour. During this period, hydrochloric acid is added until the pH of the mixture reaches 7.5. The particles of precipitated iron oxide are washed with deionized water and redispersed in deionized water containing ~ Ç~
additional dispersant by using an ulirasonic probe. Magnetization of ' 0 the dispersed iron oxide is measured by a Collpits oscillator circuit -~
technique.
(3) S = styrene, BA = butyl acrylate. Weight percent of monomer based on weight of aqueous dispersion of matrix particulate.
(4~ KX-4 = ame as in (2) of this Table. Weight percent of emulsifier based on weight of aqueous dispersion of matrix particulate.
~5) TB~P = tert-butyl hydroperoxide. Weight percent of initiator b~sed on weight of agueous dispersion of matrix particulate.

~ TABLE I (Con'd) (6) % 501ids determined by freezing agueous dispersion of matrix particulate in methylene chloride/dry ice bath and drying the dispersion at 1 mm Hg for 36 hours. The solids ~matrix particulate) are then weighed and converted to % solids by dividing weighed solids by weight of the aqueous dispersion of matrix particulate. The dr}ed matrix particulate is compression molded at ~25C to form a disk (2.54 cm diameter and 1.27 cm thick).
(7) Average particle diameter determined by hydrodynamic chromatography.
Sarnple Nos. 1-4 represent bimodal systems with the diameter for each mode being shown separately.

.

Example 6 Using a Waring blendor, a 150-g portion of titanium dioxide ha~ing an average particle size in the range of 0.2-0.4 micrometer is dispersed in 350 g of deionized water containing 0.3 g of an ethanolated alkylguanidine amine complex sold by American Cyanamld under the trade name Aerosol C-61. The resulting dis-persion is then combined with mixing with 240 g of deionized water containing 15 g of a 40 percent solu-tion of Polywet KX-4 in water.

rhis dispersion (471 g) is combined with 248 g of deionized water, 4 g of a 40 percent solution of Polywet KX 4 in water, 3 g of lN NaOH and 0.8 g of a 1 percent solution of the pentasodium salt of (carboxy-methylimino) bis~ethylenenitrilo)tetraacetic acid inwater. The resulting mixture is charged to a 3-neck flask equipped with a stirrer, two addition funnels and a condenser. The mixture is stirred and heated under nitrogen to 90C. At this temperature, (1) a monomer stream consisting of 40 g of styrene and 40 g of butyl acrylate and (2) an aqueous stream consisting of 80 g of deionized water, 10 g of a 40 percent solution of Polywet KX-4 in water, 2.2 g of Na2S20~ and 9 g of lN
NaO~ are introduced into the flask with each stream being introduced at the rate of ~2 ml/min. Af~er the addition of the monomer and aqueous streams is com-pleted, the resulting mixture is maintained at 90C
under nitrogen and agitation for an additional 30 minutes. The resulting latex which contains 19.4 percent solids is concentrated via evacuation to a 55 percent solids dispersion which is a bimodal dispersion wherein one mode has an average partlcle diameter of 0.65 micrometer and ~he other mode has an average particle diameter of 0.11 micrometer.

27,950-F -20-¢) IL7 ~ coating is prepared from the latex that exhiblts excellent opacity.

27,950~F -21-

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process for preparing a colloidal size particulate comprising the steps of (1) emulsifying at least one hydrophobic, emulsion polymerizable monomer in an aqueous colloidal dispersion of discrete particles of an inorganic solid, said dispersion being maintained in a reasonably stable state with a member selected from the group consisting of a chemical dispersant and surfactant and (2) subjecting the resulting emulsion to emulsion polymerization conditions to form a stable, fluid aqueous colloidal dispersion of the particulate wherein essentially every particle of the inorganic solid is coated with the hydrophobic polymer resulting from said polymerization such that substantially all of the inorganic particles are maintained in a discrete spaced apart relationship to each other by the hydrophobic polymer.

2. The process of Claim 1 wherein the particles of the inorganic solid have an average diameter less than 0.6 micrometer.

3. The process of Claim 1 wherein the aqueous dispersion of the inorganic solid is prepared by contacting said solid with an aqueous solution of a water-soluble surfactant and the same surfactant is used to emulsify the monomer in the aqueous dispersion of inorganic solid.

4. The method of Claim 1 wherein the inor-ganic solid is iron oxide, titanium dioxide, calcium carbonate, silica, zinc oxide or clay.

5. The method of Claim 1 wherein a water-soluble surfactant is used to emulsify the hydrophobic monomer, said surfactant being a potassium salt of a functionalized oligomer or a salt of a fatty acid.

6. The method of Claim 1 wherein the monomer is a monovinylidene aromatic monomer, an alkyl ester of an ethylenically unsaturated carboxylic acid or a mixture thereof.

7. A stable, fluid aqueous colloidal dis-persion comprising a continuous aqueous phase and a polymer/inorganic solid disperse phase wherein a sub-stantial portion of the particles of the disperse phase comprise a hydrophobic polymer matrix having dispersed therein the colloidal inorganic solid particles such that substantially all of the inorganic particles are maintained in a discrete spaced apart relationship to each other by the hydrophobic polymer.

8. The dispersion of Claim 7 wherein the inorganic solid is magnetic and the dispersion exhibits the characteristics of a magnetic colloid.

9. A particulate having colloidal-size particles wherein substantially all of said particles comprise a hydrophobic polymer matrix and at least one discrete colloidal particle of an inorganic solid dispersed in said matrix. ~

10. The particulate of Claim 9 wherein the inorganic solid is iron oxide, titanium dioxide, cal-cium carbonate, silica, zinc oxide or clay, and the particulate contains from 1 to 70 weight percent of inorganic solid, from 30 to 99 weight percent of matrix polymer.

11. The particulate of Claim 9 wherein the inorganic solid is titanium dioxide and the particulate is a bimodal one with one mode having an average particle size in the range from 0.1 to 0.15 micrometer and the other mode having an average particle diameter in the range from 0.6 to 0.75 micrometer.