EP1153071A1 - Particles attached to first and second polymers having mutual non-covalently associative groups - Google Patents
Particles attached to first and second polymers having mutual non-covalently associative groupsInfo
- Publication number
- EP1153071A1 EP1153071A1 EP99972656A EP99972656A EP1153071A1 EP 1153071 A1 EP1153071 A1 EP 1153071A1 EP 99972656 A EP99972656 A EP 99972656A EP 99972656 A EP99972656 A EP 99972656A EP 1153071 A1 EP1153071 A1 EP 1153071A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- group
- polymer
- composition
- covalently
- particles
- 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- Withdrawn
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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2641—Polyacrylates; Polymethacrylates
- C04B24/2647—Polyacrylates; Polymethacrylates containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
-
- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0045—Polymers chosen for their physico-chemical characteristics
- C04B2103/0059—Graft (co-)polymers
- C04B2103/006—Comb polymers
-
- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0068—Ingredients with a function or property not provided for elsewhere in C04B2103/00
- C04B2103/0079—Rheology influencing agents
-
- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0068—Ingredients with a function or property not provided for elsewhere in C04B2103/00
- C04B2103/0086—Chelating or complexing agents
Definitions
- the present invention relates to a polymeric system for modifying the rheology or fluidity of an aqueous particle-containing environment, such as a cementitious composition.
- the present invention relates to a novel multi-component system of polymeric materials that operate to modify or control the rheology or flow properties of aqueous slurries or dispersed particulates.
- aqueous slurries or dispersions of particles such as the paint, water treatment, ceramics, and electromagnetic recording materials industries. It is particularly appropriate for use in the cement and concrete industries and other industries in which the control of rheological or flowability properties and the stability of the particle slurry or dispersion are critical issues.
- a novel composition and method for modifying the rheology or flow characteristics of aqueous slurries or particulate dispersions are therefore needed.
- the present invention provides a non-covalently-associated, in-situ rheology modifier complex for use in modifying the rheology (or flowability properties) of an aqueous particle-containing environment.
- the modification or enhancement of the flowability of an aqueous slurry or dispersion of particles in an aqueous is achieved by the formation of an in situ molecular complex formed by polymers or constituents that become non-covalently-associated or complexed with each other near or at the surface of the particle which is intended to be dispersed in the aqueous environment.
- non-covalently-associative complexes of the invention may be achieved, for example, by the use of fatty acid moeities located on components which, through mutual "hydrophobicity" in the aqueous environment, form an association or complex much in the way that micelles are formed by electrically charged colloidal particles.
- the term "in situ” is used to describe the formation of the dispersing complex outside of the factory, either in the mix water, in the slurry or dispersion (e.g., concrete), or in a storage tank.
- the present invention therefore represents a fundamental and startling departure from prior art "comb-type" superplasticizers, in which a polymer “backbone” or main chain (containing carboxylic acid or hydroxyl groups for surface attachment to cement particles) is grafted by covalent bonding to pendant "teeth” groups (containing poly(oxyalkylene) repeating units which function to disperse the calcium particles within the slurry).
- a polymer “backbone” or main chain containing carboxylic acid or hydroxyl groups for surface attachment to cement particles
- pendant “teeth” groups containing poly(oxyalkylene) repeating units which function to disperse the calcium particles within the slurry.
- the present invention provides greater “tunability” in that it is easier to select and combine the particle-attaching component/function with the particle- dispersing component/function, using a minimum number of components or process steps.
- non-covalently-associative polymers or constituents to provide rheology-modifier complexes "in situ," the present inventors think it easier to design, test, evaluate, optimize, and implement different rheology modifier systems. This is done simply by adjusting the type and/or ratio of the polymer or constituent components and “zippering" the different components together.
- An exemplary composition of the invention thus comprises a first polymer having components represented by the formula X' m Y' n wherein component X' represents a particle-attaching group operative to attach to the surface of the particle to be dispersed within the aqueous environment.
- X' is a component, preferably a repeating unit, comprising at least one carbonyl group, carboxylate, carboxylic acid, hydroxyl group, hydroxylate or oxide, sulfonyl group, sulfate, sulfonate, phosphonyl group, phosphonate group, boronic acid or its derivatives, or an amine.
- Y' represents a first non-covalently-associative group that is covalently bonded to component X'; and "m” and “n” separately represent integers at least equal to 1.
- the invention further comprises a second polymer represented by the formula Y"Z' (or Y"Z'Y") wherein Y" is a second non-covalently-associative group which is complementary to the first non-covalently-associative group; and component Z' is a group operative to disperse the particle (when attached by X'Y') within the aqueous environment.
- the first and second polymer components when incorporated into an aqueous particle-containing environment, form a non-covalent association or complex by mutual operation of the complementary first and second non-covalently-associative groups within the aqueous environment.
- This allows the resultant complex to attach to, as well as to disperse, particles within the slurry or dispersion.
- the particle-attaching and particle-dispersing functionalities become combined in a non-covalent manner.
- the first and second non-covalently-associative groups comprise hydrophobic groups which are complementary to each other.
- Fig. 1 is a conceptual illustration of a prior art "comb-type" graft chain polymer molecule attached at the surface of a particle (e.g., cement) dispersed within an aqueous environment (e.g., cementitious slurry); and
- a particle e.g., cement
- aqueous environment e.g., cementitious slurry
- Fig. 2 is a conceptual illustration of a rheology modifier of the present invention, which can be formed in situ through the use of non-covalently-associative groups attached to a particle-attaching group and a particle-dispersing group, at the surface of a particle (e.g., cement) dispersed within an aqueous environment (e.g., cementitious slurry).
- a particle e.g., cement
- aqueous environment e.g., cementitious slurry
- aqueous particle-containing environment means and refers to particles or particulate matter that is dispersed, suspended, or dispersible or suspendible in, or otherwise contained in, water-based systems, such as are used for making paint formulations, priming compositions, surface coatings, or other surface treatment compositions, water treatment compositions (e.g., scaling control materials), ceramic materials, electromagnetic recording materials, patching compounds, crack and joint filler materials, and the like.
- the phrase includes aqueous slurries as well as dispersions of particulate matter.
- cement composition refers to pastes, mortars, grouts such as oil well cementing grouts, and concrete compositions comprising a hydraulic cement binder.
- pastes are mixtures composed of a hydraulic cement binder (usually, but not exclusively, Portland cement. Masonry cement, or Mortar cement and may also include limestone, hydrated lime, fly ash, blast furnace slag, and silica fume or other materials commonly included in such cements) and water; mortars are pastes additionally including fine aggregate, and concretes are mortars additionally including coarse aggregate.
- the cement compositions tested in this invention are formed by mixing required amounts of certain materials, e.g., a hydraulic cement, water, and fine or coarse aggregate, as may be applicable to make the particular cement composition being formed.
- non-covalently-associated refers to groups or moieties on components which operate, when placed in the aqueous environment wherein particles are intended to be dispersed, to draw or bring the rheology-modifier components together to form a molecular complex wherein the functionality of particle-attachment and the functionality of particle-dispersing- ability are combined.
- non-covalently-associated are used in contradistinction to prior art "comb-type" superplasticizers which are formed by covalently bonding one molecule onto another to form covalent bonds, such as through copolymerization or grafting reactions.
- hydrophobic association An exemplary manner of achieving a non-covalent association is through the use of hydrophobic groups which cluster together, similar to the formation of micelles from charged colloidal particles, so as to form a molecular complex within the aqueous environment. While it is not intended that the present invention be confined by the theoretical concepts and illustrations herein, the present inventors believe that the concept of "hydrophobic association" is helpful for illustrating an exemplary mode of achieving and understanding the features, advantages, and performance of the invention.
- Fig. 1 is a conceptual illustration, similar to that contained in the above- mentioned article of K. Yoshioka et al., J. Am. Ceram. Soc, Vol. 80 (10), 2667 - 2671 (1997), of prior art comb-type superplasticizers, such as poly-(carboxylic acid) type polymers with graft chains of ethylene oxide maleic acid or ethylene oxide acrylic acid copolymers.
- the resultant molecular structure is said to be "comb- like” in that its main “backbone” polymer is grafted (covalently) to "teeth-like" pendant hydrophilic groups.
- Fig. 2 is a conceptual illustration of an exemplary non-covalently-associated rheology modifier of the present invention.
- the polymer components of the invention may be understood conceptually to be non-covalently-associative in that the particle attachment group and particle dispersing group each are attached to non- covalently-associative groups, such as (for example) mutually hydrophobic groups, that tend to make them associate with each other or otherwise form a complex or interaction near or at the surface of the particle.
- non-covalently- associative groups such as hydrophobic groups
- the resultant complex therefore, yokes together the particle-attaching aspect with the panicle-dispersing aspect without employing covalent bonds.
- an exemplary composition of the present invention comprises a first polymer having components represented by the formula X' m Y' n .
- X' represents a component, preferably a repeating unit, that functions to attach to the particle to be dispersed. This component preferably has repeating units having at least one carbonyl group, carboxylate, carboxylic acid, hydroxyl group, hydroxylate or oxide, sulfonyl group, sulfate, sulfonate, phosphonyl group, phosphonate group, boronic acid or its derivatives, or an amine.
- X' may comprise a quaternary ammonium salt if the particles to be suspended are clay particles.
- Y' represents a component, preferably a repeating unit, comprising a first non-covalently-associative group.
- the first polymer components X' and Y' are covalently bonded together and may be arranged in block order (e.g., -( X'X'X') - ( Y'Y'Y')-), or, more preferably, in random order (e.g., -X ⁇ 'X'X'Y'Y'-, - X'Y'X'Y'X'Y'-, etc.).
- the number of repeating units of X' and Y' are represented by "m" and "n,” respectively, which separately are integers of at least 1.
- m is preferably an integer of 2-2000; while “n” is preferably an integer of 1-1000.
- the first polymer is conceptually illustrated in Fig. 2 and is illustrated as being attached at points to the surface of a particle (cement), while its non-covalently-associative components are illustrated as being in a non-covalent-association with the corresponding non-covalently-associative group of the second polymer, which has components represented by the formula Y"Z' (or it may be represented by the formula Y"Z'Y”).
- Y" represents a second non-covalently-associative group which is complementary to the first non-covalently-associative group (Y 1 ) of the first polymer mentioned above.
- the complementary non-covalently-associative groups Y' and Y" are preferably identical or chemically-similar to each other, although they do not necessarily need to be. Preferably, both are comprised of repeating units.
- Z' represents a particle dispersing group that is covalently bonded to the second non-covalently-associative group Y" and is operative to disperse the attached particle within the aqueous environment.
- the Z' group is conceptually illustrated as being disposed away from the attached (cement) particle and outward into the aqueous surrounding environment (in the manner of micelle formation).
- the first and second polymers of the present invention form a non-covalently-associated complex within the aqueous environment, such as in a hydraulic cementitious composition, thereby combining a particle-attaching ability with a particle-dispersing ability.
- the first and second non-covalently-associative groups on the first and second polymers comprise hydrophobic groups such as fatty acids, which tend to cluster together in situ (e.g., forming a complex in the aqueous environment similar to soap micelles in water) to form the non-covalently bonded rheology modifier complexes of the present invention.
- the particle- attaching properties of the first polymer may be altered, for example, with respect to the nature of the particles to be dispersed (e.g., surface characteristics, particle size and morphology, type and density of ions or attachment points on the surface, etc.).
- the particle-dispersing properties of the second polymer may be altered, for example, with respect to the nature of the aqueous environment in which the particles are to be dispersed (e.g., quality of water, softness or hardness, presence or absence of surfactants or surface-active agents, etc.).
- a preferred first polymer X' m Y' n has the formula
- R 1 hydrogen or -CH 3 .
- R 2 -I'-(OA) j -R 3 wherein - I'- represents - COO-, -CONH-, -CH 2 O-, -O-, or mixture thereof;
- M hydrogen, an alkali or alkaline earth metal, or ammonium ion;
- "m” 1 - 2000; and
- "n” 1 - 2000.
- the ratio of "m" to "n” (m:n) is 100:1 to 3: 1.
- the second polymer has the formula R 3 -(AO) p -R'.
- Exemplary Y' and Y" (hydrophobic) groups may comprise C ⁇ -C 20 alkyl groups, alkylaryl groups, or mixtures or derivatives thereof. Such groups, when bonded to respective X' and Z' groups are believed to provide suitable hydrophobicity when employed in aqueous environments such as cementitious slurries.
- Another type of hydrophobic group which is also believed suitable for use as Y' and Y" (hydrophobic) groups is represented by the formula R 3 SiO(SiR 2 O) n - SiR 3 wherein R 3 represents an alkyl group or alkylphenyl group, and "n" is an integer of 1-1000.
- Exemplary Z' groups which function to disperse the particles in the aqueous environment, preferably include oxyalkylene groups such as ethylene oxide groups (“EO”), polyethylene oxide groups (“PO”), or mixtures thereof (referred to as "EO/PO” groups). Among these, EO groups are preferred. If EO/PO mixtures are used, preferably the EO:PO ratio is at least 3:1.
- the Z' groups may preferably comprise hydrophilic groups, although it has been found that in some cases they may not necessarily be classified as “hydrophilic” (water-loving) in a technical sense, so long as they operate to disperse the particle within the aqueous matrix.
- these polymer components may be derived from known cement-attaching groups, hydrophobic groups, and cement dispersing groups as may be known in the art.
- the ratio of the first polymer to second polymer is 0.05 to 2.0 wt % (s/s cement), and more preferably 0.1 to 0.5 wt % (s/s cem).
- An exemplary method of the invention for modifying the rheology of an aqueous particle-containing environment comprises combining the above-described exemplary dispersing composition with particles and mix water.
- the dispersing composition may be incorporated first into the aqueous environment before addition of the particles, or combined first with particles before they are introduced into the aqueous environment.
- the particles, dispersing composition, and water may also be mixed together simultaneously.
- Further exemplary methods include, for example, incorporating one of the components (X'Y') first with the particles to be dispersed, and then incorporating the other component (Y"Z') into the mix water, such that non-covalently-associated complex X'Y'*Y"Z' is formed when the particles and mix water are combined.
- the first polymer component X'Y' may be introduced to cement particles during the manufacture of the cement, such as before and/or during the grinding stage; and then the second polymer component Y"Z' (or Y"Z'Y") may be introduced at a subsequent stage, when the cement particles (coated and/or intermixed with the polymer component X'Y') are combined with mix water to obtain a mortar or concrete.
- the second polymer Y"Z' may therefore be subsequently introduced during, after, or just before the mix water is to be combined with the cement particles.
- an exemplary method for modifying the rheology of a cementitious composition comprises introducing, during cement particle manufacture, said first component X'Y', and, at a subsequent time, introducing said second polymer component Y"Z' to the mix water during the formation of mortar or concrete.
- compositions comprising particles (to be dispersed) and either one or both of the above-described X'Y' or Y"Z' components; as well as aqueous compositions comprising particles (to be dispersed) and either one or both of said X'Y' and Y"Z' components.
- a 10 g (0.14 mol) of acrylic acid was weighed into a 250 mL round-bottom flask that was then fitted with a mechanical stirrer, a reflux condenser, and a mtrogen supply.
- a sample, 4.2 g (0.0093 mol), of polyethylene glycol) 4- nonylphenyl ether acrylate was weighed in air and added to the reaction flask along with 50 mL of 2-propanol.
- a 0.73 g (0.007 mol) sample of mercaptopropionic acid was added, and the mixture was sparged (deoxygenated by displacement) with nitrogen. After 10 minutes of sparging, the mixture was put under a positive pressure of nitrogen and then heated to 60 °C with stirring.
- a mortar mix containing 760 g of ordinary Portland cement with 1575 g of sand and 334 g of water was formulated.
- the admixture was pre-dissolved in the mixing water, 5 minutes before the test.
- 0.5g of defoamer, tri-butylphosphate (TBP) was added to all mixes.
- TBP tri-butylphosphate
- the mortar was mixed for 5 minutes with a Hobart mixer, then slump was measured by placing the mortar mix into a cone and inverting the cone onto a table to cast a cone-shaped sample, and then measuring the drop in height of the cone.
- slump-flow (diameter of spread) was measured.
- Air content was measured by ASTM C185 (1995). After the test, the mortar mix was used for the measurement of setting time.
- the first polymer is the one derived from Example 1 and comprises acrylic acid (as " X' " component having cement particle-attaching functionality) copolymerized to a polyethylene glycol group terminated with nonylphenyl pendant groups (as " Y' " hydrophobic group having non-covalently-associative functionality).
- the second polymer used comprised polyethylene oxide (as " Z' " particle-dispersing group) terminated with nonylphenyl pendant groups (as " Y” " hydrophobic group having non-covalently- associative functionality).
- the second polymer was commercially available from BASF under the tradename ICONOL.
- the ICONOL polymers are designated as NP- 40, NP-50, NP-70, and NP-100 to identify the number of nonylphenyl repeating units (e.g., NP-40 signifies that the polymer has 40 repeating NP units).
- the mortar testing results are shown in Table 1.
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10970098P | 1998-11-24 | 1998-11-24 | |
US109700P | 1998-11-24 | ||
PCT/US1999/027025 WO2000031172A1 (en) | 1998-11-24 | 1999-11-15 | Particles attached to first and second polymers having mutual non-covalently associative groups |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1153071A1 true EP1153071A1 (en) | 2001-11-14 |
EP1153071A4 EP1153071A4 (en) | 2003-05-02 |
Family
ID=22329071
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99972656A Withdrawn EP1153071A4 (en) | 1998-11-24 | 1999-11-15 | Particles attached to first and second polymers having mutual non-covalently associative groups |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1153071A4 (en) |
JP (1) | JP2002530498A (en) |
AU (1) | AU1478400A (en) |
WO (1) | WO2000031172A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102007020523A1 (en) | 2007-05-02 | 2008-11-06 | Helling, Günter, Dr. | Metal salt nanogel-containing polymers |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4808641A (en) * | 1986-07-31 | 1989-02-28 | Fujisawa Pharmaceutical Co., Ltd. | Concrete admixture |
WO1997011132A1 (en) * | 1995-09-18 | 1997-03-27 | W.R. Grace & Co.-Conn. | Improved drying shrinkage cement admixture |
US5661206A (en) * | 1993-06-11 | 1997-08-26 | Mbt Holding Ag | Fluidity control of cementitious compositions |
WO1997035814A1 (en) * | 1996-03-26 | 1997-10-02 | Arco Chemical Technology, L.P. | Cement additives |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA829843A (en) * | 1969-12-16 | W. J. Osmond Desmond | Polymer coated particles | |
JPS58138764A (en) * | 1982-02-10 | 1983-08-17 | Asahi Chem Ind Co Ltd | Mixed solution for mortar for tiling |
JP2746332B2 (en) * | 1989-09-05 | 1998-05-06 | 株式会社竹中工務店 | Method for producing high-strength cellular mortar and lightweight concrete |
US5714538A (en) * | 1995-12-26 | 1998-02-03 | Lexmark International, Inc. | Polymeric dispersants for pigmented inks |
-
1999
- 1999-11-15 AU AU14784/00A patent/AU1478400A/en not_active Abandoned
- 1999-11-15 WO PCT/US1999/027025 patent/WO2000031172A1/en not_active Application Discontinuation
- 1999-11-15 EP EP99972656A patent/EP1153071A4/en not_active Withdrawn
- 1999-11-15 JP JP2000583994A patent/JP2002530498A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4808641A (en) * | 1986-07-31 | 1989-02-28 | Fujisawa Pharmaceutical Co., Ltd. | Concrete admixture |
US5661206A (en) * | 1993-06-11 | 1997-08-26 | Mbt Holding Ag | Fluidity control of cementitious compositions |
WO1997011132A1 (en) * | 1995-09-18 | 1997-03-27 | W.R. Grace & Co.-Conn. | Improved drying shrinkage cement admixture |
WO1997035814A1 (en) * | 1996-03-26 | 1997-10-02 | Arco Chemical Technology, L.P. | Cement additives |
Non-Patent Citations (1)
Title |
---|
See also references of WO0031172A1 * |
Also Published As
Publication number | Publication date |
---|---|
EP1153071A4 (en) | 2003-05-02 |
AU1478400A (en) | 2000-06-13 |
JP2002530498A (en) | 2002-09-17 |
WO2000031172A1 (en) | 2000-06-02 |
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