WO1991011256A1 - Microgels fonctionnels complexes actifs presentant une cinetique de formation rapide - Google Patents

Microgels fonctionnels complexes actifs presentant une cinetique de formation rapide Download PDF

Info

Publication number
WO1991011256A1
WO1991011256A1 PCT/US1990/001649 US9001649W WO9111256A1 WO 1991011256 A1 WO1991011256 A1 WO 1991011256A1 US 9001649 W US9001649 W US 9001649W WO 9111256 A1 WO9111256 A1 WO 9111256A1
Authority
WO
WIPO (PCT)
Prior art keywords
process according
group
microgels
complex functional
alkali
Prior art date
Application number
PCT/US1990/001649
Other languages
English (en)
Inventor
Adam F. Kaliski
Original Assignee
Industrial Progress, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Industrial Progress, Inc. filed Critical Industrial Progress, Inc.
Priority to AU55461/90A priority Critical patent/AU655753B2/en
Publication of WO1991011256A1 publication Critical patent/WO1991011256A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/24—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
    • C04B28/26—Silicates of the alkali metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0052—Preparation of gels
    • B01J13/0056—Preparation of gels containing inorganic material and water
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0052—Preparation of gels
    • B01J13/0056—Preparation of gels containing inorganic material and water
    • B01J13/006—Preparation of gels containing inorganic material and water by precipitation, coagulation, hydrolyse coacervation
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
    • C04B12/04—Alkali metal or ammonium silicate cements ; Alkyl silicate cements; Silica sol cements; Soluble silicate cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00482—Coating or impregnation materials

Definitions

  • the present invention relates to a process for the synthesis of complex functional microgels with a rapid formation kinetics in aqueous media and the resulting composi ⁇ tions.
  • the present invention relates to in- situ synthesis of such microgels with flocculating, cementing and surface-chemistry modifying functions in aqueous disper- sions of quantitatively predominant particulate matter to be used essentially non-reactive therewith, to affect the properties of this particulate matter in an advantageous manner.
  • the complex functional microgels of the present invention are synthesized from subcolloidal reactive silico-aluminate and similar hydrosols and bivalent and multivalent inorganic salts and/or organic, cationically-active, chemical compounds with at least two reactive groups in each molecule. Discussion of the Relevant Art
  • colloids are the lowest-rank systems known in nature equipped with “memory.” As such, they "remember” their history in chronological detail and react accordingly in terms of their resultant properties and functional behavior. As a conse ⁇ quence, any intentional or accidental deviation from an established synthesis procedure, or reaction conditions, will inescapably cause certain differences, mostly quantitative but sometimes profoundly qualitative, in the constitution and/or functional properties of the resultant colloidal systems.
  • titanium dioxide pigments on the market today are coated with a more or less dense layer of silica or silico-aluminate gels deposited in situ by a controlled inter ⁇ action between relatively highly concentrated solutions of sodium silicate and appropriate gel-setting agents, such as sulfuric or hydrochloric acids, ammonium sulfate, alum or sodium aluminate, in aqueous dispersions of the pigment.
  • appropriate gel-setting agents such as sulfuric or hydrochloric acids, ammonium sulfate, alum or sodium aluminate
  • the surface coatings mentioned represent continuous gels which are fundamentally different from the instantaneously in-situ formed microparticulate gels (microgels) of the present invention.
  • U.S. Patent No. 3,726,000 to Wildt relating to the use of in-situ formed continuous alumino-silicate gels as intrinsic cements toward the preparation of composite pigments, may be considered as typical of the general prior art in this area of technology dating back for over half a century.
  • Many other intrinsic cementing media were also used for the same purpose, e.g., sodium silicate and aluminum chloride in U.S. Patent No. 2,176,876 to Alessandroni, aliphatic acid in U.S. Patent No. 3,453,131 to Fadner, ethylenediamine and citric acid in U.S. Patent No. 4,075,030 to Bundy, urea-formaldehyde in U.S. Patent No. 4,346,178 to Economou, or silicon tetra- chloride in WO 87/00544 to Jones.
  • Hoffmann's so-called "silicomagnesium-aluminate- hydrate” gel is factually a mechanical blend of a separately prepared silico-aluminate gel and a subsequently prepared magnesium-hydroxide gel, hence, fundamentally different from true complex (multicomponent) gels synthesized according to the present invention.
  • Hoffmann's antacid gel was prepared by mixing concentrated solutions of sodium silicate and an aluminum salt under alkaline conditions for extended periods of time, e.g., 30 min., to form a solidified silico- aluminate cogel.
  • this cogel was crushed and homogenized into a flowable pulp into which a concentrated solution of magnesium sulfate was introduced gradually over a period of time lasting 3 hours.
  • the in-situ precipitated magnesium hydroxide hydrate became mechanically, though intimately, dispersed within the previously fluidized pulp of the continuous silico-aluminate cogel.
  • Inorganic anion-exchangers and a process for their synthesis are disclosed by Duwell in U.S. Patent No. 3,002,932.
  • the above anion exchangers were prepared by .... "coprecipi at- ing mixed hydrated oxides of a pair of homolomorphic metals chosen from the group consisting -of aluminum, silicon, titanium, zinc, and zirconium, the lower-valent member of said pair being present in major amount, in an aqueous medium at a pH in the range of about pH 5 to 7, drying the aqueous mixture at a temperature below 150 ⁇ C, and washing the dried mixture with water to remove soluble impurities therefrom.”
  • the above technology, as quoted, is based again on physical mixtures of separately prepared gels.
  • Tu As documented amply in everyday industrial ex ⁇ perience, relatively small differences in the preparation, handling or post-treatment of such gels, the incorporation of various transient or permanent adjuvants notwithstanding, will often result in significant modification of such important product features as abrasion resistance, catalytic activity and selectivity, inhibition resistance or pore-size distribution.
  • Tu also employed a certain specific brand of anionic polyacrylamide (transient adjuvant) to modify the mechanical structure of the catalyst matrix. Accordingly, after a subsequent burnout of the organic substance occluded in the latter matrix, Tu was able to obtain a more favorable pore- size distribution.
  • 3,484,271 describes the formation of functional (release) coatings on moving paper webs by an insitu interaction between consecutively applied separate solutions of organic anionic and cationic compounds with at least two functional groups in each molecule.
  • These release coatings are made in the form of continuous, totally imper ⁇ vious, gel films devoid of any particulate occlusions. As a matter of fact, a particulate matter embedded in such films would more or less completely destroy these films' useful release properties.
  • U.S. Patent No. 2,974,108 to Alexander discloses a method of synthesis of stable alumino-silicate aquasols (hydrosols), with ion-exchange capacities equivalent to those of better zeolites and also very good antisoiling properties.
  • aquasols are synthesized with the aid of intricate thermal regimes and time-consuming procedures, using silicic acid (rather than alkali-metal, or quaternary ammonium, silicate used in practicing the present invention) and sodium aluminate as the principal reagents.
  • silicic acid rather than alkali-metal, or quaternary ammonium, silicate used in practicing the present invention
  • sodium aluminate as the principal reagents.
  • the preferred end product, according to Alexander contains 5% to 20% of substantially spheroidal porous particles, with particle diameters ranging optimally from 10 milimicrons to 50 milimicrons (nanometer) and particle porosity between 10% and 70%, suspended in an aqueous medium with pH between 5 and 10.
  • microgels complex, multicomponent, micro-particulate gels
  • a rapid formation kinetics or conditions under which these microgels can be synthesized and/or utilized.
  • no references whatsoever have been found in the literature with regard to the use of complex microgels toward the manufacture of improved products, or any other application for that matter.
  • the complex functional microgels of the present invention are synthesized by a process comprising the steps of: (a) blending separate aqueous solutions of hydrosol- forming reagents, one of which contains an alkali-metal, or quaternary ammonium, silicate and the other one . of which contains an alkali -metal aluminate and/or alkali-metal zincate, to form a subcolloidal reactive hydrosol;
  • step (b) blending an aqueous solution containing at least one bivalent or multivalent inorganic salt and/or organic, cationi- cally-active, chemical compounds with at least two reactive groups in each molecule with the system obtained from step (a) to crosslink said hydrosol and form in situ a complex function ⁇ al microgel.
  • the ratio of alkali-metal, or quaternary ammonium, silicates to the combined mass of alkali-metal aluminates and/or zincates may range from 1:10 to 10:1, by weight, while the concentrations of said silicates and aluminates (zincates) in the reaction medium should range from 0.1% to 2.0%, by weight.
  • the dosage of crosslinking agents in relation to the com ⁇ bined hydrosol mass may range from less than 0.5:1 to more than 1:1, by weight, for bivalent and multivalent inorganic salts and from 0.1:1 to 1:1, by weight, for organic, cationically- active, chemical compounds with at least two reactive groups in each molecule.
  • complex functional microgels are synthesized in situ in aqueous media to manufacture products which are improved compared with the present ones or which can not be manufactured with the aid of technologies and/or materials of the present art.
  • alkali-metal silicates and quaternary ammonium silicates preferably sodium silicate
  • water-soluble, bi ⁇ valent and multivalent inorganic salts preferably calcium chloride and calcium nitrate, but equally well other similar salts of calcium, magnesium, barium, aluminum, zinc and zircon ⁇ ium, as well as cationically-active organic compounds with at least two reactive groups in each molecule, capable of perform ⁇ ing the same gel-setting functions as bivalent or multivalent inorganic salts.
  • anionic and cationic organic additives used in the process must be compatible with their respective anionic and cationic process streams, as indicated by absence of phase separation, clouding, or premature gelling.
  • a calcium-silico-aluminate microgel was synthesized in water in two chemically and colloidally distinctly different stages.
  • a transient, subcolloidal, reactive sodium-silico- aluminate hydrosol was formed in the first stage and cross- linked in the second stage with a solution of calcium chloride.
  • the synthesis was carried out by injecting simultaneously 40 g of a 5% aqueous solution of sodium silicate (Brand "N"- clear grade, by Philadelphia Quartz Co.) and 40 g of a 5% aqueous solution of sodium aluminate into a beaker containing 250 g of rapidly stirred distilled water, using plastic syringes positioned at diametrically opposite sides of the beaker (the latter precaution was intended to avoid a direct contact of jets of concentrated reagent solutions).
  • 80 g of a 5% aqueous solution of calcium chloride was injected into the beaker while maintaining the stirring at full intensity, causing an "instantaneous" formation of . the microgel. .
  • the freshly formed microgel was extremely fine, but a progressive particle (grain) growth became clearly visible within a few seconds.
  • agitation of the medium was ceased, the entire disperse phase settled to the bottom of the beaker after a couple of minutes in the form of a relatively thin, very fluffy layer under a pool of crystal-clear supernatant. It was very easy to restore the original state of dispersion by agitation; however, the cycle of progressive particle growth and settling set-in again when agitation was discontinued. The above cycle could be repeated countless numbers of times without any noticeable indication of permanent particle enlargement, or other signs of irreversible aging.
  • Example I The unusual colloidal behavior of complex microgels, demonstrated in Example I, is deemed essential to their unique ability to flocculate any particulate matter dispersed in an aqueous medium instantaneously, indiscriminately and complete ⁇ ly, regardless of the particulate matter's physical, chemical or colloidal make-up. This behavior is also essential to the ability of complex microgels to intimately cement the floccu ⁇ lated (aggregated) particulate matter upon subsequent dewater- ing and drying.
  • complex microgels of the present invention can be prepared in less than one-fifth of one second, from three separate drops of dilute reagent solutions aligned in a proper order on a microscopical glass slide.
  • the first drop containing a solution of sodium silicate was combined with the second drop containing a solution of sodium aluminate, to synthesize a sodium-silico- aluminate hydrosol.
  • Example I The quantitative proportions of water and microgel-forming reagents in Example I were selected so as to simulate a reaction medium for synthesizing new types of aggregate pigment products invented by the Applicant and disclosed in the name of Adam F. Kaliski in co-pending U.S. Patent Applications Nos. 07/420,388 and 07/420,472; filed October 12, 1989.
  • the aggregate pigments mentioned have vastly improved optical and other performance properties, compared with those of the pigmentary raw materials from which they were derived.
  • the amount of water and proportions of microgel- forming reagents used in Example I were the same as would be used typically per 100 g of pigmentary raw material in actual plant manufacturing operations.
  • the sodium-silico-aluminate hydrosol in Example I as well as similar hydrosols of sodium-silico-zincate and sodium- silico-alu inate-zincate types, are formed instantly by simply blending separate solutions of sodium silicate and sodium aluminate (and/ or sodium zincate) in water. From a colloid- chemical standpoint, these hydrosols represent transient, low- molecular-weight, highly reactive inorganic, polymers of anionic polyelectrolyte " ype * Prepared and utilized according to the present invention, they remain completely clear to the eye for several hours devoid of a visually perceptible Tyndall effect.
  • the loss of hydrosol reactivity occurs gradually and can be avoided by reducing the time interval between hydrosol formation and its crosslinking by cationic gel-setting agents.
  • the duration of this time interval in laboratory experiments is maintained usually between one and twenty seconds. In large scale batch manufacturing operations the duration of the time interval in question may extend to several minutes, but is considerably shorter (ranging from approximately 20-30 seconds to a couple of minutes) with continuous manufacturing proces ⁇ ses. Since molecular weights of freshly formed hydrosols grow avalanche-like when high concentrations of hydrosol-forming reagents are involved, the concentrations of sodium silicate and sodium aluminate in the reaction medium should not exceed 2% each, by weight.
  • sodium silicate and sodium aluminate (zincate) should be present in reaction media containing particulate matter at concentrations of at least
  • hydrosols are fundamentally different from hydrosol (aquasol) products of the present art.
  • the former are transient intermediate products with a relatively short useful life span, serving exclusively for the purpose of synthesizing the complex functional microgels in question and having no practical use on their own. They belong to the class of "amicrons" (subcolloids) with average particle dimensions smaller than 5 nm, which, according to the nomenclature accepted in many textbooks of colloid chemistry, occupy a boundary position between molecular solutions and conventional colloids.
  • hydrosols of the present invention which lack any visual indication of the existence of a particulate phase, can remain in the amicron category for only a limited period of time.
  • hydrosols Upon a certain maximum permissible period of aging, which, depending on the concentration of hydrosol- forming reagents in the reaction medium, may extend from a couple of minutes to several hours, these hydrosols become intrinsically coarser (acquire excessive molecular weight) and fall out from the category of subcolloids. The consequence of this excessive molecular-weight growth is loss of chemical reactivity, which renders the sodium-silico-aluminate (zincate) hydrosols unsuitable for the . synthesis of complex functional microgels.
  • the freshly formed subcolloidal reactive hydrosols become crosslinked with gel-setting agents, such as bivalent and multivalent inorganic salts and/or organic, cationically- active, chemical compounds with at least two reactive groups in each molecule, to form the complex (multi-component) microgels mentioned previously.
  • gel-setting agents such as bivalent and multivalent inorganic salts and/or organic, cationically- active, chemical compounds with at least two reactive groups in each molecule, to form the complex (multi-component) microgels mentioned previously.
  • gel-setting agents such as bivalent and multivalent inorganic salts and/or organic, cationically- active, chemical compounds with at least two reactive groups in each molecule, to form the complex (multi-component) microgels mentioned previously.
  • simple salts e.g., NaCl, Na2SU , aNU3, and/or similar ammonium compounds, being formed as by ⁇ products.
  • purely inorganic complex microgels of the present invention represent hybrid macromolecules of a polymer- polycondensate type, while the organic/inorganic ones (with organic compounds built intrinsically into the molecular structure) represent hetero-macromolecules of the same polymer- polycondensate type.
  • the complex functional microgels of the present invention are formed in a virtually instantaneous manner. It is estimated that the chemical reaction between low-molecular- weight, subcolloidal, hydrosols (anionic polyelectrolytes) and bivalent or multivalent inorganic salts, or equivalent organic crosslinking agents, resulting in the formation of hybrid, polymer-polycondensate, macromolecules, occurs in less than one microsecond. The rapid growth of these macromolecules into giant formations with a useful molecular weight of many billion units is estimated to take place within an interval of a couple of milliseconds.
  • flocculants have a relatively narrow molecular-weight distribution, hence, are incapable of satisfying widely diversified flocculation requirements inherent to many polydisperse and heterodisperse colloidal systems, encountered routinely in paper, pigment, and many other industries.
  • the formation of the intermediate reactive subcolloidal hydrosols and resultant complex microgels of the present invention are not stoichio- metric. Identical hydrosols and/or microgels are synthesized each time, however, when the reagent concentrations and proportions, as well as reaction conditions maintained during synthesis, are the same. On the other hand, the principal quantitative and qualitative compositions of above hydrosols and microgels may be varied within unusually broad ranges without detriment to these hydrosols', or microgels', intended functional performance.
  • the ratio of sodium silicate to sodium aluminate, sodium silicate to sodium zincate, and sodium silicate to the combined mass of sodium aluminate and sodium zincate, in forming the subcolloidal reactive hydrosols may range from 10:1 to 1:10, by. weight, the preferred ratio for most practical applications being 1:1.
  • the ratio of organic, cationically-active, crosslinking agents to hydrosol mass must be determined empirically for each par- ticular agent and specific application. The reason for this is that the chemical properties of organic crosslinking agents mentioned are vastly more differentiated from the standpoint of their effect upon end-use properties of products obtained by flocculation and cementing with complex functional microgels, than are those of corresponding inorganic crosslinking agents.
  • the need for selective screening is perhaps best exemplified by the fact that even small proportions of certain organic crosslinking agents, e.g., 0.1% to 0.2%, by weight, on the total hydrosol mass, may deprive the resultant complex microgels of adhesive properties or even render them completely hydrophobic, hence, of limited applicability in aqueous media.
  • the relative proportions of properly screened organic crosslinking agents should range, according to present indications, from 0.1% to 5% of the mass of particulate matter.
  • Another uniquely broad latitude with regard to the reaction conditions in general pertains to the pH range, extending from 3.5 to more than 12, under which the complex microgels of the present invention can both be synthesized and perform their intended functions.
  • the solutions of crosslinking reagents must be acidified first, using predetermined amounts of sul"furic acid, alum, or other inorganic or organic acidifying agents.
  • the quantity of acidifying agent needed must be 'assessed independently by titrating beforehand an aliquot sample of a normally prepared, alkaline, microgel.
  • the acidifying agents can also be added to an already formed (alkaline) microgel, such as may be preferred in certain practical applications.
  • the formation of the complex functional microgels mentioned is virtually totally independent from the temperature of the reaction medium.
  • the above microgels can be formed in principle within the entire temperature interval in which water remains fluid, i.e., from above the freezing point to below the .boiling point..
  • the practical temperature limits depend only on the thermal stability of particulate matter present in the system and considerations of process economy and convenience.
  • alkali-compatible organic anionic polyelectro- lytes such as sodium salts of polyacrylic acid or carbox-y- methyl cellulose, or anionically-active monomolecular organic compounds with two or more reactive groups in each molecule, such as sodium salts of N-(l,2-dicarboxyethyl)-N-alkyl sulpho- succinamate (Aerosol 22), can be built chemically into the microgel structure by adding them to the aqueous medium before. or along with, the hydrosol-forming reagents.
  • organic cationic polymers such as polyacrylamides, or cationically-active organic monomolecular compounds with two or more reactive groups in each molecule, such as methyl-dodecyl- benzyl-trimethyl ammonium chlorid-methyldodecylxylene bis(tri- methyl) ammonium chloride (Hyamin 2389), can be built chemical ⁇ ly into the microgel structure by adding them to the solutions of bivalent or multivalent inorganic salts used for crosslink ⁇ ing of the subcolloidal reactive (poly-anionic) hydrosols of the present invention, or using them as independent crosslink ⁇ ing agents.
  • microgel synthesis was carried in essentially the same way as in Example I, except that other materials were also present in the reaction medium.
  • the latter consisted of 249 g distilled water and 1 g polyacrylic-emulsion adhesive with an average particle size of 45 nm and glass-transition temperature of -40° C.
  • the latter .material is representative of a new class of water-borne emulsion adhesives developed by the Applicant and disclosed in the name of Adam F. Kaliski in the co-pending U.S. Patent 'Application Serial No.
  • the principal reaction medium in this example consisted of
  • the freshly synthesized microgel behaved in the same manner as microgels synthesized in the two previous examples, the supernatant being similarly crystal clear.
  • a subsequent filtration yielded a completely uniformly colored residue ("filter cake”) and a crystal clear filtrate, identical results being obtained with numerous other commercial dyes.
  • the papermaking process mentioned above permits one to use simultaneously unlimited numbers of dyes, all of these dyes being retained 100% with the microgel-flocculated furnish. This is especially advantageous in the manufacture of colored papers, the dye-related expenses being always very substantial. It is not unusual for the cost of dyes used in the manufacture of intensely-colored paper products " -, e.g., cocktail napkins, to be two or three times higher than the cost of all other raw materials combined.
  • the instantaneous, indiscriminate and complete flocculat ⁇ ing action of the in-situ formed complex functional microgels of the present invention makes possible to use even most polydisperse and heterodisperse furnishes, such as could not be handled in a practical manner by any of the acidic, or neutral- to-alkaline, papermaking processes of the present art.
  • Virtually no limits to potential furnish diversities are envisaged in that, in the Applicant's extensive experimenta ⁇ tion, a water-based colloidal system able to resist the overpowering instantaneous, indiscriminate and complete flocculating action of the in-situ formed complex functional microgels has not yet been encountered.
  • the complex functional microgels of the present invention may also be applied to the manufacture of wet-laid nonwoven products.
  • the complex functional microgels of the present invention are also uniquely suited for the manufacture of practically unlimited numbers of types of structural aggregate pigments with vastly improved optical properties, also equipped with a- priori designed functional properties.
  • the technology for the synthesis of such pigments was invented by the Applicant and disclosed in the name of Adam F. Kaliski in co-pending U.S. Patent Applications Serial Nos. 07/420,388 and 07/420,472; filed October 12, 1989.
  • microgels of the present invention While the primary purpose of the complex functional, in- situ formed, microgels of the present invention is to induce an instantaneous, indiscriminate and complete flocculation (aggregation) of all particulate components of a slurry, their secondary purpose is to provide an arbitrary level of intrinsic cementation to the aggregated particulates, such as pigments, fibers, dyes, etc., upon subsequent drying or other finishing operations.
  • the desired level of cementation may be obtained by varying the composition, and/or dosage, of the complex microgels, such as to provide the end products, e.g., paper webs or composite pigments, with sufficient mechanical integrity to withstand the customary shearing (loading) and/or comminution regimes to which they may be exposed in practical handling and end-use operations.
  • the adhesive action of above microgels is possible only due to the extremely small particle size, as well as deformability, enabling the microgel particles to orient themselves effectively as discrete ultrathin formations at the interfaces between adjacent particulates (pigment particles, cellulosic fibers) to be cemented.
  • the tertiary purpose of the complex functional microgels of the present invention synthesized in situ in dispersions of particulate matter, to impart directly, by virtue of their inherent physical and surface-chemical properties, certain specific material and functional properties to the aggregated and cemented products, important from the standpoint of these products' end-use applications.
  • the above effects can be realized through a purposeful modification of the chemical composition, and/or physical properties, of the complex functional microgels.
  • a surface-chemical modification providing an enhanced compatibility of the end product (composite pigment, paper web) with organic media may be attained by an intrinsic incorporation of suitable, anionically and/or cationically active organic compounds with at least two reactive groups in each molecule, into the macromolecules making up the complex microgels of the present invention.
  • An indirect surface-chemical modification of the end products can be attained by co-aggregation of such powerful surface-chemical modifiers in their own right as organic dyes or polymer-emulsion adhesives, possible due to the instantaneous, indiscriminate and complete flocculating action of the complex functional microgel . s of the present invention.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Structural Engineering (AREA)
  • Colloid Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Catalysts (AREA)

Abstract

Procédé pour synthétiser des microgels fonctionnels complexes actifs présentant une cinétique de formation rapide, dans un milieu aqueux et compositions résultantes.
PCT/US1990/001649 1990-01-31 1990-03-28 Microgels fonctionnels complexes actifs presentant une cinetique de formation rapide WO1991011256A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU55461/90A AU655753B2 (en) 1990-01-31 1990-03-28 Functional complex microgels with rapid formation kinetics

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US472,763 1983-03-07
US47276390A 1990-01-31 1990-01-31

Publications (1)

Publication Number Publication Date
WO1991011256A1 true WO1991011256A1 (fr) 1991-08-08

Family

ID=23876845

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1990/001649 WO1991011256A1 (fr) 1990-01-31 1990-03-28 Microgels fonctionnels complexes actifs presentant une cinetique de formation rapide

Country Status (9)

Country Link
EP (1) EP0512986A4 (fr)
CN (1) CN1031988C (fr)
AU (1) AU655753B2 (fr)
CA (1) CA2075194A1 (fr)
IL (1) IL94920A (fr)
IN (1) IN171538B (fr)
MX (1) MX173809B (fr)
WO (1) WO1991011256A1 (fr)
ZA (1) ZA905091B (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0600902A1 (fr) * 1991-07-22 1994-06-15 Industrial Progress, Inc. Produits de pigmentation a base de tio 2? en agregat
EP0908228A1 (fr) * 1996-05-01 1999-04-14 Adam Kozan Chuo Kenkyusho Co., Ltd. Procedes de production d'un gel mineral et de fines

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050234136A1 (en) * 2004-04-19 2005-10-20 Holland Brian T Colloidal compositions and methods of preparing same

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2974108A (en) * 1957-01-14 1961-03-07 Du Pont Aluminosilicate aquasols and their preparation
US4026721A (en) * 1976-03-19 1977-05-31 Westvaco Corporation Composite silicate pigment
US4201689A (en) * 1977-06-18 1980-05-06 Henkel Kommanditgesellschaft Auf Aktien Process for the production of tenside-containing cation exchanger aluminosilicates
US4217240A (en) * 1976-09-02 1980-08-12 E. I. Du Pont De Nemours And Company Stable aluminosilicate aquasols having uniform size particles and their preparation
US4247420A (en) * 1979-03-23 1981-01-27 W. R. Grace & Co. Hydrocarbon conversion catalyst preparation
US4606900A (en) * 1984-01-27 1986-08-19 Sud-Chemie Aktiengesellschaft Method of preparing crystalline zeolitic aluminosilicates

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5510539B2 (fr) * 1972-05-22 1980-03-17
FR2277769A1 (fr) * 1974-07-10 1976-02-06 Mirsky Yakov Procede de preparation des zeolithes sous forme de granules spheriques exempts d'agglomerant
US5116418A (en) * 1984-12-03 1992-05-26 Industrial Progress Incorporated Process for making structural aggregate pigments
US4818729A (en) * 1987-10-13 1989-04-04 Aluminum Company Of America Process for preparing stabilized high cristobalite

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2974108A (en) * 1957-01-14 1961-03-07 Du Pont Aluminosilicate aquasols and their preparation
US4026721A (en) * 1976-03-19 1977-05-31 Westvaco Corporation Composite silicate pigment
US4217240A (en) * 1976-09-02 1980-08-12 E. I. Du Pont De Nemours And Company Stable aluminosilicate aquasols having uniform size particles and their preparation
US4201689A (en) * 1977-06-18 1980-05-06 Henkel Kommanditgesellschaft Auf Aktien Process for the production of tenside-containing cation exchanger aluminosilicates
US4247420A (en) * 1979-03-23 1981-01-27 W. R. Grace & Co. Hydrocarbon conversion catalyst preparation
US4606900A (en) * 1984-01-27 1986-08-19 Sud-Chemie Aktiengesellschaft Method of preparing crystalline zeolitic aluminosilicates

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0512986A4 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0600902A1 (fr) * 1991-07-22 1994-06-15 Industrial Progress, Inc. Produits de pigmentation a base de tio 2? en agregat
EP0600902A4 (fr) * 1991-07-22 1994-11-23 Ind Progress Inc Produits de pigmentation a base de tio 2? en agregat.
EP0908228A1 (fr) * 1996-05-01 1999-04-14 Adam Kozan Chuo Kenkyusho Co., Ltd. Procedes de production d'un gel mineral et de fines
EP0908228A4 (fr) * 1996-05-01 2000-01-12 Adam Kozan Chuo Kenkyusho Co L Procedes de production d'un gel mineral et de fines

Also Published As

Publication number Publication date
IL94920A0 (en) 1991-04-15
CN1031988C (zh) 1996-06-12
CA2075194A1 (fr) 1991-08-01
CN1053780A (zh) 1991-08-14
EP0512986A1 (fr) 1992-11-19
AU5546190A (en) 1991-08-21
MX173809B (es) 1994-03-29
IL94920A (en) 1995-06-29
AU655753B2 (en) 1995-01-12
ZA905091B (en) 1991-05-29
EP0512986A4 (en) 1993-04-07
IN171538B (fr) 1992-11-14

Similar Documents

Publication Publication Date Title
US5116418A (en) Process for making structural aggregate pigments
US5312484A (en) TiO2 -containing composite pigment products
US5344487A (en) Layered composite pigments and method of making same
SU692543A3 (ru) Способ получени заполненных микрокапсул
US6063291A (en) Dewatering of aqueous suspensions
JPS5998723A (ja) 炭酸カルシウム分散物およびその製法
JPH07506328A (ja) 高固形分含有量のベントナイトスラリの製造方法
US5378399A (en) Functional complex microgels with rapid formation kinetics
AU655753B2 (en) Functional complex microgels with rapid formation kinetics
JPH06509055A (ja) 集合ＴｉＯ↓２ピグメント製品
JP2000516536A (ja) ゼオライトクリスタロイド凝集剤を用いる水の処理方法
JPH05506179A (ja) 構造アグリゲート顔料
EP2069573A2 (fr) Composition silicieuse et son utilisation dans la fabrication du papier
RU2283390C1 (ru) Способ получения пигмента для изготовления бумаги и картона
JPS5911617B2 (ja) 強化プラスチツクスおよびバインダ−製造用の水性ラテツクス材料
AU703657B2 (en) Dewatering of aqueous suspensions
JP3101903B2 (ja) 釉薬原料及び釉薬
RU2213822C1 (ru) Способ изготовления бумаги для печати
EP1513769A1 (fr) Compositions de silicate de magnesium synthetiques et procede de production de celles-ci
Kaliski et al. TiO 2-containing composite pigment products
SE439653B (sv) Sett att vid papperstillverkning anvenda en sterkelsekomposition bestaende av katjonisk sterkelse och karboxymetylcellulosa eller polyakrylsyra samt medel herfor
MXPA98003360A (es) Suspension de hidroxido de magnesio estable por largo tiempo y proceso para su produccion

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BG BR CA FI HU JP KP KR NO RO SU

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB IT LU NL SE

WWE Wipo information: entry into national phase

Ref document number: 2075194

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 1990908004

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1990908004

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1990908004

Country of ref document: EP