EP0309576A1 - Composition permettant de modifier les proprietes rheologiques - Google Patents

Composition permettant de modifier les proprietes rheologiques

Info

Publication number
EP0309576A1
EP0309576A1 EP19880904749 EP88904749A EP0309576A1 EP 0309576 A1 EP0309576 A1 EP 0309576A1 EP 19880904749 EP19880904749 EP 19880904749 EP 88904749 A EP88904749 A EP 88904749A EP 0309576 A1 EP0309576 A1 EP 0309576A1
Authority
EP
European Patent Office
Prior art keywords
composition
clay
compound
systems
compositions
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP19880904749
Other languages
German (de)
English (en)
Inventor
Donald R. Elliott
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sued Chemie Inc
Original Assignee
United Catalysts 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 United Catalysts Inc filed Critical United Catalysts Inc
Publication of EP0309576A1 publication Critical patent/EP0309576A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
    • C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
    • C01B33/44—Products obtained from layered base-exchange silicates by ion-exchange with organic compounds such as ammonium, phosphonium or sulfonium compounds or by intercalation of organic compounds, e.g. organoclay material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/19—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/04—Thixotropic paints

Definitions

  • the present invention provides compositions related to the improvement in rheological characteristics of systems in which the compositions are incorporated.
  • plastic-type systems or coating systems which will be more specifically defined hereinafter.
  • Representative examples of prior art plastic-type systems include fiberglass or polyester resin/styrene polymers where such plastic-type systems can be in a liquid, semi-solid or gel form.
  • Representative examples of coating systems include paints or laminating systems used in association with plastic-type systems which have become static such as fiberglass.
  • compositions within the scope of the present invention are easily adapted to and can be incorporated into many final end products and systems without the necessity of retooling a manufacturing facility.
  • Fumed Silica which is the most widely used agent in the art to date. Fumed silica is an entirely different chemical composition than those compositions within the scope of the present invention.
  • fumed silica has extremely low bulk density so the volume storage requirements are high. Further, because of such low bulk density it becomes difficult to incorporate the material into many plastic-type systems. Fumed silica is also extremely dusty and requires users to wear protective respiratory masks. Still another disadvantage is that fumed silica is expensive compared to compositions within the scope of the present invention and greater labor costs are associated with incorporating it in plastic-type systems.
  • Another type of rheological agent for plastic-type systems is composed in part of organoclays. These organoclays are also known in the art as organophillic clays.
  • the organophillic clay requires a smectite-type clay base and that rheological agents containing smectite-type clay can be incorporated into aqueous or non-aqueous plastic-type systems.
  • organoclay-rheological agents there are various suppliers of the above-described organoclay-rheological agents, examples of which are, Claytone PSTM available from Southern Clay Products and Polytrope 1131 from N.L. Chemicals.
  • a major problem encountered with commercially available organoclay-rheological agents is that they do not enhance the thixotropic index of plastic-type systems to the level required by many producers of such plastic-type systems into which they are incorporated.
  • the organoclay rheological agents described in the prior-art must first be incorporated into a gel-like carrier before such agents can be incorporated into a plastic-type systems. Of course, this additional step adds additional cost to the use of the organoclay rheological agents already known in the art. Accordingly, in many cases, use of the organoclays provided by the prior art becomes impractical, if not prohibitive. Thus, to date, fumed silica remains the primary rheological agent used in plastic-type systems.
  • compositions within the scope of the present invention are useful for altering the rheological properties of plastic-type systems or coating systems.
  • plastic-type systems are defined as those systems comprised of polymers in a liquid state or a semi-solid state or a gel state which with the passage of time become static, hardened or solid.
  • plastic-type systems can be represented by fiberglass, polyester or polyester/styrene systems.
  • plastic-type systems created by the incorporation of compositions within the scope of the present invention allow greater flexibility in shaping the final static or hardened end product produced by such plastic-type systems.
  • end products include boats, bodies for automobiles, hard hats, casings for telephones, typewriters, computers, etc.
  • Coating systems are those systems comprised of paints and/or laminating systems to provide protective outer coatings to static bases.
  • compositions within the scope of the present invention have been found to be less expensive to incorporate into plastic-type systems than other rheological agents presently known and/or those already commercially available.
  • compositions within the scope of the present invention greatly improve the desired rheological characteristics of the plastic-type systems into which they are incorporated over other types of rheological agents, as will be disclosed more fully hereinafter.
  • compositions of the present invention typically include a smetite clay, a quaternary ammonium compound or mixture of various quaternary ammonium compounds and a compound containing at least one Zirconium atom or a compound containing at least one Silicon atom, in combination.
  • the present invention include processes and materials to promote the interaction of an organophillic clay with either a compound containing the element Zirconium or a compound containing the element Silicon. This combination has heretobefore been unknown in the art for the purposes described hereinafter.
  • the present invention provides compositions useful as rheological agents capable of altering or modifying the rheological characteristics of a system in which they have been incorporated.
  • the compositions are the result of the electromagnetic and/or electrochemical interaction of a clay, a quaternary ammonium compound and a compound containing Zirconium or a compound containing Silicon.
  • the compositions are useful in controlling the rheological properties of plastic-type systems where such plastic-type systems are found in liquid, semi-solid or gel states as well as in coating systems.
  • compositions in accordance with the present invention have been discovered and demonstrated in various experimental methods.
  • compositions in accordance with the present invention are the result of the combinaton of a clay, a quaternary ammonium compound, or mixture of quaternary ammonium compounds, and either a compound containing Zirconium or a compound containing Silicon.
  • the electromagnectic or electrochemical forces responsible for the interaction of the Zirconium or Silicon compounds with the surface of the organophillic clay appear to be covalent banding.
  • compositions within the scope of the present invention unexpectedly and favorably alter the rheological properties of systems into which they have been incorporated.
  • examples of such systems include plastic-type systems and coating systems as hereinbefore defined.
  • compositions within the scope of the present invention are useful as rheological agents when incorporated in plastic-type systems or coating systems and, as such, the compositions provide high viscosity at low sheer rates to enhance the rheological properties of such systems.
  • plastic-type systems will have greater propensity to retain their molded form until the plastic-type system has become static; and coating systems, such as paints are easily applied to surfaces without resultant sagging or slumping.
  • Methods by which organophillic clays are prepared are well known in the art.
  • an organic cationic compound such as a quarternary ammonium will react by ion-exchange with the clay having a negative layer lattice and exchangable cations to form an organophillic clay. Due to this phenomenon the clay becomes activated; therefore, it will electromagnectically or electrochemically interact with either a Zirconium compound or a Silicon compound in accordance with the present invention.
  • Clays within the scope of the present invention are smecite-type clays having a cation exchange capacity of at least 75 milliequivalents per 100 grams of clay. There are many commercially available quarternary ammonium compounds which will activate smecite-type clays.
  • a Zirconium compound or a Silicon compound is introduced to the combination, and it has been found within the scope of the present invention that the activated clay and the Zirconium compound or the Silicon compound interact as hereinbefore described creating compositions in accordance with the present invention.
  • the method of forming inventions within the scope of the present invention can be illustrated in weight to weight percentages as follows. A 3.2% to 3.5% clay slurry in water is made. The clay slurry is then filtered to remove any impurities, such as sand or gravel, thus, the clay is cleaned.
  • a 2.0% to 3.0% slurry of the cleaned clay in water is then made which is then mixed and reacted with a 7.0% to 8.0% water emulsion containing the quatenary ammonium or a mixture of quatenary ammounium compounds.
  • the quaternary ammounium compound or compounds activate the clay causing the clay to become organophillic.
  • the organophillic clay is then mixed and reacted with 1.0% to 2.0% of either a Zirconium or a Silicon compound within the scope of the present invention.
  • the excess water can be removed by filitration and the resultant solids can be dried.
  • castor oil compounds may be incorporated into the dried solids in accordance with the present invention, thus, allowing greater flexibility in the control of the plastic-type or coating systems rheology in which the present invention has been incorporated.
  • R 1 is respresentative of either a carboxylic acid group or an aromatic group containing at least six Carbon atoms or an alkyl group of the general formula (CH 2 ) n CH 3 . More specifically, it has been found that when R 1 represents an alkyl group, the alkyl group contains less than 16 Carbon atoms. Regardless whether R 1 is representive of a carboxyl group including acids, an aromatic group or an alkyl group, it has been found that under laboratory conditions the resultant rheological properties of compositions within the scope of the present invention were generally the same.
  • Silicon compounds can also be used within the scope of the present invention and can be represented by the general formula:
  • R 2 , R 3 or R 4 may be represented by a hydroxyl group or groups represented by the formula -O-R x or any combination thereof.
  • R 5 can be C 6 H 5 .
  • R 2 , R 3 or R 4 represents -O-R x
  • the Oxygen molecule is bonded to a Silicon atom and R x .
  • R x represents an alkyl group including from two to four Carbon atoms.
  • compositions of the present invention can be incorporated into a system without the use of a gel-like carrier as required by the rheological agents presently known.
  • compositions within the scope of the present invention may be incorporated into systems with the use of a gel-like carrier.
  • Zirconium or Silicon compounds are reacted in combination with the previously described clay and quarternary ammonium compound or compounds, the composition is dried.
  • the compositions are thereafter ready to be incorporated into systems such as a plastic-type systems or coating systems as hereinbefore defined. Additionally, in accordance with another feature of the present compositions, it has been discovered that the addition of castor oil compounds in concentrations of up to 25% by weight of the composition will further advantageously alter the rheological properties of the plastic-type system into which the composition is incorporated.
  • compositions of the present invention are compatible with many plastic-type systems and/or coating systems and may be incorporated into such systems in concentrations from 0.10%-2.00% by weight of such systems.
  • rheological agents are generally incorporated into plastic-type systems and/or coating systems by either of two methods. Those methods are known as the "pre-gel” or “direct add” methods.
  • pre-gel can be described as the addition of the rheological agent into a gel-like carrier which is thereafter incorporated into a system.
  • the "direct add” method is self explanatory in that the rheological agent is incorporated directly into the system without the necessity of a gel-like carrier. It has unexpectedly been found that compositions within the scope of the present invention may successfully be incorporated into systems by either the "pre-gel” or
  • organoclay rheological agents can only be incorporated into systems via the "pre-gel” method, otherwise, such organoclay rheological agents separate from such systems and fail to yield meaningful modification to such systems rheology.
  • the “drain out” test is a quantitative measurement of the ability of a system to retain its form or shape until such system has become static. More specifically, “drain out” can be described as the percentage of surface area of a glass matting, such as fiberglass, from which the system has drained becauseof gravity with such percentage being measured as a function of time.
  • the “drain out” tests for compositions within the scope of the present invention were conducted using the following procedure. The various rheological agents of the present invention were incorporated into a system in a ratio of 1.0% by weight of the system.
  • the carrier was 8141 resin manufactured by Cargill, Inc.
  • Percentage figures represent the ratio of settled rheological agent height to total system height, i.e. the amount of rheological agent that has settled out of the carrier do to the force of gravity as a function of time.
  • ZR represents the Zirconium compounds in accordance with the present invention having the following functional portion:
  • SI represents the Silicon Compounds within the scope of the present invention having the following formula:
  • i ZR and SI represent the same compounds as previously identified.
  • CO Claytone PSTM.
  • FS represents Fumed Silica.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Compositions utiles en tant qu'agents rhéologiques et/ou thixotropiques pouvant altérer ou modifier les caractéristiques rhéologiques d'un système dans lequel elles ont été incorporées. Les compositons sont le résultat de l'interaction électromagnétique et/ou électrochimique d'une argile, d'un composé d'ammonium quaternaire et d'un composé contenant du zirconium ou un composé contenant du silicium. Les compositions sont utiles pour modifier et en particulier réguler les propriétés rhéologiques de systèmes de type plastique que l'on trouve à l'état liquide, semi-solide ou de gel, ainsi que dans des systèmes de revêtement.
EP19880904749 1987-03-26 1988-03-28 Composition permettant de modifier les proprietes rheologiques Withdrawn EP0309576A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US5047387A 1987-03-26 1987-03-26
US50473 1987-04-06

Publications (1)

Publication Number Publication Date
EP0309576A1 true EP0309576A1 (fr) 1989-04-05

Family

ID=21965444

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19880904749 Withdrawn EP0309576A1 (fr) 1987-03-26 1988-03-28 Composition permettant de modifier les proprietes rheologiques

Country Status (2)

Country Link
EP (1) EP0309576A1 (fr)
WO (1) WO1988007981A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0640122B1 (fr) * 1991-02-15 1997-07-16 S.C. JOHNSON & SON, INC. Preparation de solutions stables et aqueuses d'organosilane hydrolysable
KR102395678B1 (ko) * 2014-05-16 2022-05-06 베수비우스 유에스에이 코포레이션 내화성 바인더 시스템

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4040974A (en) * 1976-04-26 1977-08-09 N L Industries, Inc. Synthesized gellants containing smectite-type clay and process for producing same
US4105578A (en) * 1976-12-10 1978-08-08 N L Industries, Inc. Organophilic clay having enhanced dispersibility
US4116866A (en) * 1977-07-01 1978-09-26 N L Industries, Inc. Organophilic clay gellant
US4528104A (en) * 1982-08-19 1985-07-09 Nl Industries, Inc. Oil based packer fluids
US4558075A (en) * 1984-03-30 1985-12-10 Ppg Industries, Inc. High-solids coating composition for improved rheology control containing organo-modified clay
TR22515A (tr) * 1984-04-27 1987-09-17 English Clays Lovering Pochin Bir organik vasat icinde kolayca dispersiyon hale getirilebilir bir organo-kilin hazirlanmasi
US4640716A (en) * 1985-06-26 1987-02-03 Engelhard Corporation High bulking pigment and method of making same
US4631091A (en) * 1985-08-13 1986-12-23 English China Clays Lovering Pochin & Co. Ltd. Method for improving the dispersibility of organoclays

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8807981A1 *

Also Published As

Publication number Publication date
WO1988007981A1 (fr) 1988-10-20

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