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
  • C04B24/2688—Copolymers containing at least three different monomers
  • C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
• • 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
  • C04B24/16—Sulfur-containing compounds
  • C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
  • C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
• • 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
  • 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
  • C04B24/2652—Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles
  • C04B24/2658—Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles containing polyether side chains
• • 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
  • C04B24/2664—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers
  • C04B24/267—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers containing polyether side chains
• • 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
  • C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C04B24/283—Polyesters
• • 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
  • C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
• • 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
  • C04B28/02—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 hydraulic cements other than calcium sulfates
• • 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
  • C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
  • C04B2103/302—Water reducers
• • 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
  • C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
  • C04B2103/308—Slump-loss preventing 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
  • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
  • C04B2111/00034—Physico-chemical characteristics of the mixtures
  • C04B2111/00068—Mortar or concrete mixtures with an unusual water/cement ratio

Definitions

• the present invention relates to modification of hydratable cementitious compositions; and, more particularly, to water-reducing plasticization of concrete or mortar having a specific water/cement ratio range using a polycarboxylate-containing comb type polymer comprising two different but specific size ranges within polyoxyalkylene-containing pendant groups to permit effective modification in low-to-mid- range water reduction applications.
• PC polycarboxylate
• HRWR high range water reduction
• EP 0 850 894 B1 of Hirata et al. disclosed PC copolymers which functioned as HRWR dispersants and which were made from polyalkylene glycol ether-based monomers and maleic acid based monomers. Similar to Tanaka et al., Hirata et al. disclosed molecular size ranges extending upwards to 100,000 and expressed a strong preference for using a large number of alkylene oxide groups.
• Lorenz et al. disclosed a PC copolymer comprising four components of an unsaturated dicarboxylic acid, an unsaturated alkenyl ether having 1 to 25 oxyalkylene units, an unsaturated alkenyl ether having 26 to 300 oxyalkylene units, and an unsaturated monomer comprising a hydrolysable moiety.
• This reference indicates that the copolymer demonstrated a lower binding affinity with cement particles initially and could be overdosed into the cementitious composition initially to obtain workability. Over time, the hydrolysable moieties become saponified, resulting the retention of the workability in the cementitious composition.
• Yamashita et al. disclosed a PC copolymer comprising an alkenyl ether having 1 to 100 oxyalkylene groups, an alkenyl ether having 1 1 to 300 oxyalkylene groups, and an unsaturated carboxylic acid. Again, one reads that Yamashita et al.
• PC copolymers have not been sufficiently explored for low-to-mid-range plasticization, because the concrete industry has become accustomed to using the more expensive polycarboxylate (PC) type copolymers for HRWR applications, while using non-PC cement dispersants, such as lignin type plasticizers, primarily for low-to-mid-range applications. It appears that in the concrete industry, therefore, PC type copolymers are reserved customarily for high range water reduction (HRWR) applications, i.e., for achieving the 12 to 30 percent reduction in hydration water.
• HRWR high range water reduction
• Kuo et al. disclosed a method for achieving low-to-mid-range water reduction in hydratable cementitious compositions having a water/cement ratio of 0.40-0.80, wherein the method involves using one or more PC copolymers made from a polyoxyalkylene monomer, an unsaturated carboxylic acid monomer, and, optionally, an unsaturated water-soluble hydrophilic monomer.
• HRWR high range water reduction
• PC polycarboxylate
• HRWR high range water reduction
• the present inventor believes that using a PC copolymer having two different but specific size ranges within its polyoxyalkylene-containing pendant groups, despite achieving inferior HRWR performance as compared to conventional superplasticizers which are otherwise used in low water-to-cement (w/c) compositions, provides superior performance surprisingly and unpredictably when W/C is increased; such that the present invention provides a satisfactory alternative to lignin and other non- PC type dispersants when used in low-to-mid range water reduction applications (LRWR, MRWR).
• LRWR low-to-mid range water reduction applications
• the present invention describes a method for achieving low-to-mid-range reduction of water in concrete or mortar mixes using specifically sized PC copolymer constituents.
• the present invention also reflects an unexpected and surprising improvement, in terms of admixture dosage efficiency at certain high water-cement (w/c) ratios, when PC copolymers taught by the present invention were compared to commercial reference PC polymers used in conventional HRWR applications.
• an exemplary method of the present for achieving low-to-mid-range water- reducing of a hydratable cementitious composition using a comb-type carboxylate copolymer comprises: combining with water and hydratable cement, to form a hydratable mixture having a water/cement (w/c) ratio of at least 0.44 and more preferably at least 0.51 , and wherein the w/c ratio is no greater than 0.80 and more preferably no greater than 0.75, at least one comb-type carboxylate copolymer formed from the following monomer components (A), (B), (C), and optionally (D):
• R 3 (CH 2 ) m (CO>hO ⁇ CH2)oiAO)pR if wherein R 1 and R 2 individually represent hydrogen atom or methyl group; R 3 represents hydrogen or -COOM group wherein M represents a hydrogen atom or an alkali metal; AO represents oxyalkylene group having 2 to 4 carbon atoms (preferably 2 carbon atoms) or mixtures thereof; "m” represents an integer of 0 to 2; “n” represents an integer of 0 or 1 ; “o” represents an integer of 0 to 4; "p” represents an average number of oxyalkylene groups and is an integer from 5 to 35; and R 4 represents a hydrogen atom or Ci to C 4 alkyl group;
• R 3 (CH 2 ) m (CO) (3 ⁇ 4 0(CH2 & (AO q R ⁇
• R 1 and R 2 individually represent hydrogen atom or methyl group
• R 3 represents hydrogen or -COOM group wherein M represents a hydrogen atom or an alkali metal
• AO represents an oxyalkylene group having 2 to 4 carbon atoms (preferably 2 carbon atoms) or mixtures thereof
• "m” represents an integer of 0 to 2
• n represents an integer of 0 or 1
• "o” represents an integer of 0 to 4
• "q” represents an average number of oxyalkylene groups and is an integer from 20 to 200
• R 4 represents a hydrogen atom or Ci to C 4 alkyl group
• R 5 and R 6 individually represent hydrogen atom or methyl group
• R 7 represents hydrogen atom, C(0)OR 8 , or C(0)NH R 8 wherein R 8 represents a Ci to C 4 alkyl group, and M represents a hydrogen atom or an alkali metal
• R 11 X wherein R 9 , R 10 , and R 1 1 each independently represent a hydrogen atom, methyl group or C(0)OH; X represents C(0)NH 2 , C(0)NHR 12 , C(0)NR 13 R 14 , O-R 15 , S0 3 H, C 6 H 4 S0 3 H, or C(0)NHC(CH 3 )2CH 2 S0 3 H, or mixture thereof, wherein R 12 , R 13 , R 14 , and R 15 each independently represent a Ci to C5 alkyl group; and wherein the molar ratio of component (A) to component (B) is from 15:85 to 85: 15, and further wherein the molar ratio of component (C) to the sum of component (A) and component (B) is 90: 10 to 50:50.
• the copolymer formed from components (A), (B), (C), and optionally (D) has a weight-average molecular weight of 8,000 - 50,000, more preferably 10,000 - 40,000, and most preferably 12,000 - 30,000, as measured by gel permeation chromatography (using polyethylene glycol as standards and with conditions described in further detail hereinafter).
• the present invention also relates to cementitious compositions, including concrete and mortar, made according to the exemplary method described above.
• the present invention provides a method and cementitious compositions whereby low-to-mid range water reduction is achieved using specific structures and sizing within the comb-type carboxylate polymer structure.
• cementitious refers to materials that comprise Portland cement or which otherwise function as a binder to hold together fine aggregates (e.g., sand), coarse aggregates (e.g., crushed gravel), or mixtures thereof.
• cement refers to hydraulic binder material such as Portland cement which is produced by pulverizing clinker consisting of hydraulic calcium silicates and one or more forms of calcium sulfate (e.g., gypsum) as an interground additive.
• Portland cement is combined with one or more supplemental cementitious materials, such as fly ash, granulated blast furnace slag, limestone, natural pozzolans, or mixtures thereof, and provided as a blend.
• hydratable refers to cement and/or cementitious materials that are hardened by chemical interaction with water.
• Portland cement clinker is a partially fused mass primarily composed of hydratable calcium silicates.
• the calcium silicates are essentially a mixture of tricalcium silicate (3CaO-Si02 "C3S” in cement chemists notation) and dicalcium silicate (2CaO-Si02, "C2S") in which the former is the dominant form, with lesser amounts of tricalcium aluminate (SCaO-A Cb, "C3A") and tetracalcium aluminoferrite (4CaO-Al203-Fe203, "C 4 AF").
• CaO-Si02 tricalcium silicate
• C2S dicalcium silicate
• crete refers generally to a hydratable cementitious mixture comprising water, cement, sand, a coarse aggregate such as crushed gravel or stone, and one or more optional chemical admixtures.
• copolymer refers to compounds containing constituents derived or formed from the use of three different monomer components (designated as components “A”, “B”, and “C”) and optionally from the use of four different monomer components (i.e., further including at least one optional monomer designated as "D"), as described in exemplary methods of the invention and cementitious compositions made by the methods of the invention.
• an exemplary method of the present invention comprises: combining with water and hydratable cement, to form a hydratable mixture having a water/cement (w/c) ratio of at least 0.44 and more preferably at least 0.51 , and wherein the w/c ratio is no greater than 0.80 and more preferably no greater than 0.75, at least one comb-type carboxylate copolymer having the following monomeric constituents:
• R 3 (CH 2 , :CG) r ⁇ 0 ⁇ CH 2 MAQ1 ⁇ 4>R 4
• R 1 and R 2 individually represent hydrogen atom or methyl group
• R 3 represents hydrogen or -COOM group wherein M is a hydrogen atom or an alkali metal
• AO represents oxyalkylene group having 2 to 4 carbon atoms (preferably 2 carbon atoms) or mixtures thereof
• "m” represents an integer of 0 to 2
• n represents an integer of 0 or 1
• "o” represents an integer of 0 to 4
• "p” represents an average number of oxyalkylene groups and is an integer from 5 to 35
• R 4 represents a hydrogen atom or Ci to C 4 alkyl group
• R 3 (CH 2 ) ra (CO) !1 0 ⁇ CH 2 & (AO)qR
• R 1 and R 2 individually represent hydrogen atom or methyl group
• R 3 represents hydrogen or -COOM group wherein M is a hydrogen atom or an alkali metal
• AO represents oxyalkylene group having 2 to 4 carbon atoms (preferably 2 carbon atoms) or mixtures thereof
• "m” represents an integer of 0 to 2
• n represents an integer of 0 or 1
• "o” represents an integer of 0 to 4
• "q” represents an average number of oxyalkylene groups and is an integer from 20 to 200
• R 4 represents a hydrogen atom or Ci to C 4 alkyl group
• R 5 and R 6 individually represent hydrogen atom or methyl group
• R 7 represents hydrogen atom, C(0)OR 8 , or C(0)NHR 8 wherein R 8 is Ci to C 4 alkyl group, and M is a hydrogen atom or an alkali metal
• R 9 , R 10 , and R 11 each independently represent a hydrogen atom, methyl group or C(0)OH;
• X represents C(0)NH 2 , C(0)NHR 12 , C(0)NR 3 R 14 , O-R 15 , S0 3 H, C 6 H 4 S0 3 H, or C(0)NHC(CH 3 )2CH 2 S0 3 H, or mixture thereof, wherein R 12 , R 13 , R 14 , and R 15 each independently represent a Ci to Cs alkyl group; and wherein the molar ratio of component (A) to component (B) is from 15:85 to 85: 15, and further wherein the molar ratio of component (C) to the sum of component (A) and component (B) is 90: 10 to 50:50.
• the hydratable cementitious mixture is a concrete (which typically contains both a fine aggregate such as sand, and a coarse aggregate such as stones or crushed gravel) designed for low-to-mid range water reduction applications, wherein the cement-to-concrete ratio is 240 to 340 kg/m 3 .
• a concrete typically contains both a fine aggregate such as sand, and a coarse aggregate such as stones or crushed gravel
• the cement-to-concrete ratio is 240 to 340 kg/m 3
• R 3 (CH 2 ) ra (CO ⁇ !1 0 ⁇ CH2) 0 (AO) q R 4
• R 1 and R 2 individually represent hydrogen atom or methyl group
• R 3 represents hydrogen or -COOM group wherein M represents a hydrogen atom or an alkali metal
• AO represents an oxyalkylene group having 2 to 4 carbon atoms (preferably 2 carbon atoms) or mixtures thereof
• "m” represents an integer of 0 to 2
• n represents an integer of 0 or 1
• "o” represents an integer of 0 to 4
• "q” represents an average number of oxyalkylene groups and is an integer from 20 to 200
• R 4 represents a hydrogen atom or Ci to C 4 alkyl group
• R 5 and R 6 individually represent hydrogen atom or methyl group
• R 7 represents hydrogen atom, C(0)OR 8 , or C(0)NH R 8 wherein R 8 represents a Ci to C 4 alkyl group, and M represents a hydrogen atom or an alkali metal
• R11 x wherein R 9 , R 10 , and R 1 1 each independently represent a hydrogen atom, methyl group or C(0)OH;
• X represents C(0)NH 2 , C(0)NHR 12 , C(0)NR 13 R 14 , O-R 15 , S0 3 H, C 6 H 4 S0 3 H, or C(0)NHC(CH 3 )2CH 2 S0 3 H, or mixture thereof, wherein R 12 , R 13 , R 14 , and R 15 each independently represent a Ci to C5 alkyl group; and wherein the molar ratio of component (A) to component (B) is from 15:85 to 85: 15, and further wherein the molar ratio of component (C) to the sum of component (A) and component (B) is 90: 10 to 50:50.
• the molar ratio of component (A) to component (B) is, preferably, from 15:85 to 85: 15; more preferably, from 20:80 to 75:25; and, most preferably, from 25:75 to 65:35.
• the letters "m,” “n,” and “0" in monomer components (A) or (B) are integers of 0, 1 , and 0, respectively.
• the molar ratio of component (C) to the sum of component (A) and component (B) ranges from 90: 10 to 50:50, more preferably from 80:20 to 60:40, and most preferably from 75:25 to 65:35.
• the molar ratio of component (D) to the sum of component (A), component (B), and component (C) ranges from 1 :99 to 20:80 and is more preferably from 3:97 to 10:90.
• the sum of the number of oxyalkylene repeating unit "p" in component (A) and the number of oxyalkylene repeating unit “q" in component (B) is not more than 120, preferably not more than 80.
• the number of oxyalkylene repeating unit "q" in component (B) minus the number of oxyalkylene repeating unit "p" in component (A) is 8, preferably 10 or higher.
• the weight-average molecular weight of the polycarboxylate copolymer is 8,000 - 50,000 as measured by gel permeation chromatography (GCP) using polyethylene glycol (PEG) as standards and in accordance with the GPC conditions described in Example 1 below. More preferably, the weight-average molecular weight of the polycarboxylate copolymer polymer is 10,000 - 40,000, and, most preferably, is 12,000 - 30,000. The molecular weight may be determined using Gel Permeation Chromatography (GPC) under the conditions described in Example 1 below.
• GCP gel permeation chromatography
• the term "comprises" when used to describe the monomer components means that the comb-type carboxylate copolymer is formed from monomer components (A), (B), (C), and optionally (D) and may be formed from additional monomers (i.e., in addition to) having different structure or groups apart from what has been described for monomers (A), (B), (C), and optional (D); whereas “consists essentially of” means, depending upon context, that constituents of the polycarboxylate copolymer are formed from using monomer components (A), (B), and (C) only or from using monomer components (A), (B), (C), and (D) only.
• the comb- type carboxylate copolymer may be formed using monomer components (A), (B), and (C) only.
• Examples of monomers for component (A) include, but are not limited to, poly(ethylene glycol) methyl ether acrylate, poly(ethylene glycol) methyl ether methacrylate, poly(ethylene glycol) methyl ether maleate monoester, poly(ethylene glycol) methyl ether fumarate monoester, N-poly(ethylene glycol) acrylamide, N- poly(ethylene glycol) methacrylamide, poly(ethylene glycol) vinyl ether, poly(ethylene glycol) allyl ether, poly(ethylene glycol) methallyl ether, poly(ethylene glycol) isoprenyl ether, poly(ethylene glycol) vinyloxybutylene ether, wherein the number of oxyalkylene repeating units is in the range of 5 to 35, more preferably in the range of 8 to 30, and most preferably in the range of 10 to 25.
• Examples of monomers for component (B) include, but are not limited to, poly(ethylene glycol) methyl ether acrylate, poly(ethylene glycol) methyl ether methacrylate, poly(ethylene glycol) methyl ether maleate monoester, poly(ethylene glycol) methyl ether fumarate monoester, N-poly(ethylene glycol) acrylamide, N- poly(ethylene glycol) methacrylamide, poly(ethylene glycol) vinyl ether, poly(ethylene glycol) allyl ether, poly(ethylene glycol) methallyl ether, poly(ethylene glycol) isoprenyl ether, poly(ethylene glycol) vinyloxybutylene ether, wherein the number of oxyalkylene repeating units is in the range of 20 to 200, more preferably in the range of 25 to 150, and most preferably in the range of 30 to 100.
• the number of oxyalkylene repeating units in component (B) is at least 10 more than the number of oxyalkylene repeating units in component (A).
• monomer component (C) include, but not are limited to, acrylic acid, methacrylic acid, Ci-C 4 alkyl maleic monoester, N-(Ci-C 4 ) alkyl maleic monoamide, Ci- C 4 alkyl fumaric monoester, N-(Ci-C 4 ) alkyl fumaric monoamide, or mixtures thereof.
• unsaturated, water-soluble monomer of optional monomer component (D) include, but not limited to, acrylamide, methacrylamide, N-alkyl acrylamide, N-alkyl methacrylamide, ⁇ , ⁇ -dialkyl acrylamide, N,N-dialkyl methacrylamide, vinyl alkyl ether, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, 3-acrylamido-2-methylpropane sulfonic acid, styrene sulfonic acid, salts of these acids, or mixtures thereof.
• the active amount of the comb-type carboxylate copolymer which is constituted from monomer components (A), (B), (C), and optionally (D), is combined with cement in the amount of from 0.04 to 0.14 percent by weight of the cement, and more preferably from 0.05 to 0.1 1 percent by weight (wt%) based on cement weight.
• at least one additional admixture may be added to the water and cement in addition to the comb-type carboxylate copolymer.
• Such admixture can be selected from the group consisting of gluconic acid or salt thereof, an alkanolamine, an air detraining agent, an air-entraining agent, and mixtures thereof.
• the said at least one additional admixture is mixed with the carboxylate copolymer prior to combining with the cement and water.
• a conventional air detraining (defoaming) agent may be used in combination with the polycarboxylate copolymer as contemplated within the present invention, and used in an amount as deemed necessary or desired by the admixture formulator or applicator.
• EP 0 415 799 B1 of Gartner taught air-detraining nonionic surfactants which included phosphates (e.g., tributylphosphate), phthalates (e.g. , diisodecylphthalate), and polyoxypropylene-polyoxyethylene block copolymers (which are not deemed to be superplasticizers) (See EP 0 415 799 B1 at page 6, II. 40-53).
• phosphates e.g., tributylphosphate
• phthalates e.g. , diisodecylphthalate
• polyoxypropylene-polyoxyethylene block copolymers which are not deemed to be superplasticizers
• US 5, 156,679 of Gartner taught use of alkylate alkanolamine salts (e.g., N-alkylalkanolamine) and dibutylamino-w-butanol as defoamer.
• US 6, 139,623 of Darwin et al. disclosed antifoaming agents selected from phosphate esters (e.g., dibutylphosphate, tributylphosphate), borate esters, silicone derivatives (e.g., polyalkyl siloxanes), and polyoxyalkylenes having defoaming properties.
• US 6,545,067 of Buchner et al. disclosed butoxylated polyalkylene polyamine for reducing air pore content of cement mixes.
• US 6,803,396 of Gopolkrishnan et al. disclosed low molecular weight block polyether polymers described as containing ethylene oxide and propylene oxide units as detrainers.
• US 6,569,924 of Shendy et al. disclosed the use of solubilizing agents for solubilizing water-insoluble defoamers.
• the conventional air detraining (defoamer) compositions may be employed with the comb-type PC polymer described herein, and thus further exemplary methods and compositions of the invention further comprise one or more air detraining agents.
• compositions and methods of the invention may further comprise or include the use of at least one other agent selected from the group consisting of (i) a non- high range water reducer (non-HRWR) such as gluconic acid and its salts; (ii) an alkanolamine such as triethanolamine, triisopropanolamine, diethylisopropanolamine, or mixture thereof; (ii) a second defoamer which is different in terms of chemical structure from the first defoamer employed, (iv) an air-entraining agent such as a higher trialkanolamine such as triisopropanolamine or diethylisopropanolamine, a lignosulfonate, a naphthalene sulfonate, a melamine sulfonate, an oxyalkylene- containing non-HRWR plasticizer, an oxyalkylene-containing shrinkage reducing agent (which does not function as a HRWR additive), or a mixture
• the present invention also relates to hydratable cementitious compositions which are made by combining the comb-type carboxylate polymer (made from components A, B, C, and optionally D), and optional additional chemical admixtures, as just described above. While the invention is described herein using a limited number of embodiments, these specific embodiments are not intended to limit the scope of the invention as otherwise described and claimed herein. Modification and variations from the described embodiments exist. More specifically, the following examples are given as a specific illustration of embodiments of the claimed invention. It should be understood that the invention is not limited to the specific details set forth in the examples. All parts and percentages in the examples, as well as in the remainder of the specification, are based on weight or percentage by weight unless otherwise specified.
• any range of numbers recited in the specification or claims, such as that representing a particular set of properties, units of measure, conditions, physical states or percentages, is intended to literally incorporate expressly herein by reference or otherwise, any number falling within such range, including any subset of numbers within any range so recited.
• any number R falling within the range is specifically disclosed.
• any numerical range represented by any two values of R, as calculated above, is also specifically disclosed.
• This section describes an exemplary process for making a comb-type carboxylate copolymer for low-to-mid-range water reduction use in accordance with the present invention.
• a three-neck round bottom flask was fitted with a mantle heater, a thermocouple connected to temperature controller and a mechanical stirrer.
• the reactor was charged with a prescribed amount of de-ionized water, purged with argon gas and then heated to 65°C.
• a solution containing prescribed amounts of two poly(ethylene glycol)methyl ether methacrylate (MPEGMA) having different molecular weights, acrylic acid (AA), 3-mercaptopropionic acid and de-ionized water was prepared in advance.
• GPC Gel Permeation Chromatograph
• the weight-average molecular weights of the resulting polymers can be measured by employing gel permeation chromatography (GPC), using polyethylene glycol (PEG) as standards and the following separation columns: ULTRAHYDROGELTM 1000, ULTRAHYDROGELTM 250 and ULTRAHYDROGELTM 120 columns.
• the GPC processing conditions are as follows: 1 % aqueous potassium nitrate as elution solvent, flow rate of 0.6 mL/min., injection volume of 80 ⁇ , column temperature at 35°C, and refractive index detection.
• Table 1 summarizes the results of the carboxylate polymer samples of this invention as well as of the reference samples.
• Reference 1 was synthesized via the same process and contains poly(ethylene glycol)methyl ether methacrylate while Reference 2 is a commercial polycarboxylate containing isoprenyl poly(ethylene glycol) ether and acrylic acid.
• This example illustrates the water-reducing effect of the comb-type carboxylic copolymers of the present invention by measuring the slump of concrete.
• Concrete mixes were fabricated using three different mix proportions as shown in Table 2. The amount of water varied depending on the type and amount of cement and depending on the weight ratios of water to cement (w/c). The results shown in Table 3 below are based on cement sourced from Holcim Theodore plant (Alabama, US), slump was measured as a function of percentage of active polymer dosage to cement [% s/c]. Table 2
• This example compares the slump retaining performance of the comb-type copolymers against the reference polymers.
• the test protocol described in Example 2 was employed, except that the slump was measured at 10-minute, 30-minute, and 45- minute or 50-minute marks.
• the results are shown in Tables 6, 7, and 8 for three different cements mentioned above (e.g., sourced from Holcim's Theodore, Holcim's Ste. Genevieve; and LaFarge's Ravena, respectively).

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