Title of Invention

CEMENT ADDITIVE

Abstract

A cement additive comprising a polycarboxylic acid type copolymer and/or a salt thereof and a polyalkylene glycol derivative, wherein said polycarboxylic acid type copolymer contains one or more species of copolymers composed of at least an unsaturated polyalkylene glycol type monomer and an unsaturated mono-or dicarboxylic acid type monomer as their monomer components. Concretes in which the additive is used have excellent flow, without significant retarding effect, and a low air entrainment. When used with concrete for steam curing, it allows earlier removal of form work.

Full Text

FORM 2 THE PATENTS ACT 1970 [39 OF 1970] COMPLETE SPECIFICATION [See Section 10] "CEMENT ADDITIVE" MBT HOLDING AG, of Vulkanstrasse 110, CH-8048 Zurich, Switzerland, The following specification particularly describes and ascertain the nature of the invention and the manner in which it is to be performed :- This invention relates to a cement additive and more particularly, to a cement additive used to improve the fluidity and appearance of strength of cement slurry, cement paste, mortar and concrete. Various cement additives comprising polycarboxylic acid type copolymers. have been proposed for enhancing the fluidity and flowability of concrete. While this works well for ordinary concretes, it is not so effective when high strength and high durability are required, as such copolymers tend to entrain an excess of air and retard setting. In relation to pre-formed concrete products, it is strongly desired to decrease the total time spent in a form and to prevent defects when the form is removed. For such products, good appearance is also highly desirable, when the form is removed after steam curing. Various polycarboxylate materials to achieve this have been proposed, but none have been entirely satisfactory, causing such problems as retarded setting and low fluidity. It has now been found that a cement additive containing apolycarboxylic acid type copolymer and a polyalkylene glycol derivative having a specific molecular structure can alleviate and sometimes completely remove all the above-mentioned problems, by having a high dispersing ability for various concretes, improving and retaining the fluidity of concrete, and also making it possible to increase the strength of pre-formed concrete, such that form removal after stetan curing can be carried out relatively early, giving a product with low aeration. The invention therefore provides a cement additive containing a polycarboxylic acid type copolymer and/or the salts thereof and a polyalkylene glycol derivative, said polycarboxylic acid type copolymer contains at least one species of copolymer, the monomers of which copolymer comprise at least an unsaturated polyalkylene glycol type monomer (A) and an unsatur-ated mono- or dicarboxylic acid type monomer (B). The invention also relates to a cement additive, wherein the polycarboxylic acid type copolymers are copolymers which additionally include as monomer components an unsaturated polyalkylene glycol ester type monomer (C) and/or a monomer (D) polymerizable with the above-mentioned monomers (A) and (B), or with the monomers (A), (B) and (C). The invention further relates to the above-mentioned cement additive, wherein the monomer (A) is a compound according to the general formula (1): wherein R1, R2 and R3 are each independently hydrogen or methyl, provided that not all are methyl; R4 is -CH20-5 -(CH2)20-, -C(CH3)20- or -0-; the total carbon number of R1, R2, R3 and R4 is 3; R50 is one or more species of C2-C4 oxyalkylene groups, and in the case of two or more species may be block or random; R6 is hydrogen or a C1-C22 alkyl, phenyl or C1-C:8 alkylphenyl group; p is an integer from on average 1 to 100; the monomer (B) is a compound according to the general formula (2): wherein R7 and R8 are each independently hydrogen or methyl; R9 is hydrogen, methyl or ? (CH2)qCOOM2; R10 is -(CH2)r-; q and r are each independently an integer from 0 to 2; M1 and M2 are a monovalent metal, a divalent metal, ammonium or an organic amine; the monomer (C) is a compound according to the general formula (3): wherein R11and R12 are each independently hydrogen, methyl or (CH2)uCOOM3, u is an integer from 0 to 2, M3 is a monovalent metal, a divalent metal, ammonium or an organic amine; R130 is one or more species of C1-C4 oxyalkylene groups, and in the case of two or more species may be block or random; R14 is hydrogen or a C1-C22 alkyl, phenyl or C1-C22 alkylphenyl group; s is an integer from 0 to 2; t is an integer an average from 1 to 300; and the monomer (D) is a compound according to the general formula (4): wherein RI5,R16,R18 and R19 are each independently hydrogen or methyl, provided that not all are methyl; R170 is one or more species of C2-C4 oxyalkylene groups, and in the case of two or more species may be block or random; w is an integer an average from 1 to 300; v and x are each independently an integer from 0 to 2, The invention also relates to the abovementioned cement additive, wherein the composition ratios of the monomers (A) and (B) in the polycarboxylic acid-type copolymers are 30-100 mole % based on the total mole amount of the monomers, and the average molecular weight of said polycarboxylic acid-type copolymer is from 3,000- 100,000 (all molecular weights (MW) referred to herein were measured by gel permeation chromatography with polyethylene glycol as standard). The invention also relates to the abovementioned cement additive, wherein the average molecular weight of the polyalkylene glycol derivatives is from 1,000-100,000, in which the alkylene is one or more C2-C4 species, and the terminal groups of the polyalkylene glycol is hydrogen or a C1-C18 alkyl or phenyl group. Further, the invention relates to the abovementioned cement additive containing 100 weight parts of the polycarboxylic acid type copolymers and 10-50 weight parts of the polyalkylene glycol derivatives. Also, the invention relates to the abovementioned cement additive, wherein the amount of the polycarboxylic acid type copolymers added to cement is 0.05-1.0 % by weight based on the weight of cement, and the amount of the polyalkylene glycol derivatives added to cement is 0.005-0.5 % by weight based on the weight of cement. Further, the invention relates to use of the abovementioned cement additive in high strength concrete. The invention also relates to the use of the abovementioned cement additive in the formation of pre-formed concrete articles by steam curing. The invention further provides a method of preparation of a high-strength concrete mix, comprising the incorporation in the mix of a cement additive as hereinabove described. The invention further provides a method of preparation of a concrete mix adapted to be used for the manufacture of articles by steam curing, comprising the incorporation in the mix of a cement additive as hereinabove described. In a cement additive according to the invention, the monomers (A) are typically compounds according to the abovementioned general formula (1), more specifically, the compounds in which 1-100 mole of an alkylene oxide is added to an unsaturated alcohol such as 3-methyl-2-buten-l-ol, 3-methyl-3-buten-l-ol, 2-methyl-3-buten-2-ol. One or more species of unsaturated alcohol may be used. Examples of monomers (B) include compounds according to general formula (2), more specifically, for example, acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and citraconic acid. One or more species of these may be used. Monomers (C) are typically compounds according to general formula (3). Specific examples include unsaturated polyalkylene glycol monoester type monomers such as polyethylene glycol monoesters, polypropylene oxide monoesters, monoesters of polyethylene glycol/polypropylene oxide copolymers, derivatives in which a terminal hydrogen, of these glycols is etherified, and the like, such as triethylene glycol monoacrylate, polyethylene glycol (MW 200) monoacrylate, polyethylene glycol (MW 400) monoacrylate, polyethylene glycol (MW 600) monoacrylate, polyethylene glycol (MW 1000) monoacrylate, polyethylene glycol (MW 2000) monoacrylate, polyethylene glycol (MW 4000) monoacrylate, polyethylene glycol (MW 6000) monoacrylate, triethylene glycol monomethacrylate, polyethylene glycol (MW 200) monomethacrylate, polyethylene glycol (MW 400) monomethacrylate, polyethylene glycol (MW 600) monomethacrylate, polyethylene glycol (MW 1000) monomethacrylate, polyethylene glycol (MW 2000) monomethacrylate, polyethylene glycol (MW 4000) monomethacrylate and polyethylene glycol (MW 6000) monomethacrylate, and one or more species of these may be used. The monomers (D) are typically compounds according to general formula (4), specific examples including unsaturated polyalkylene glycol diester type monomers and/or styrene, styrenesulfonic acid and/or the salts thereof, acrylic acid alkyl esters (alkyl of C22 maximum), methacrylic acid alkyl ester (alkyl of C22 maximum), maleic anhydride, maleic acid monoesters (alkyl of C22 maximum), and/or alkylene glycol of C3 maximum and 1-300 alkylene glycol units, maleic acid diester (alkyl of C22 maximum and /or alkylene glycol of C3 maximum and 1-300 alkylene glycol units, vinyl acetate, acrylamide and acrylamide methylpropansulfonic acid and/or the salts thereof. Specific examples include styrene, styrenesulfonic acid and/or the salts thereof, acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid butyl ester, methacrylic acid methyl ester, methacrylic acid ethyl ester, methacrylic acid butyl ester, maleic anhydride, maleic acid methyl monoester, maleic acid ethyl monoester, maleic acid methyl diester, maleic acid ethyl diester, vinyl acetate, acrylamide, acrylamide methylpropansulfonic acid and/or the salts thereof, methallyl sulfonic acid and/or the salts thereof. One or more species of these may be used. Specific non-limiting examples of polycarboxylic acid type copolymers are those described in JP, A, H5-306152, JP, A, H6-211949, JP, A, H9-286647 and JP, A, HI 0-236858. The composition ratio of the monomers (A) and (B) in the polycarboxylic acid type copolymers in the invention to total amount of the monomers is preferably 30-100 mole %, and the average molecular weight is preferably 3,000-100,000. In the polyalkylene glycol derivatives of the invention, the average molecular weight is 1,000-150,000, preferably 1,000-100,000, more preferably 4,000-50,000, the alkylene is one or more C2-C4 species, and it may be block or random in the case of 2 or more species, the terminal groups of polyalkylene glycol are hydrogen, C18 maximum alkyl or phenyl groups. In a cement additive of the invention, the preferred proportions are 100 weight parts of polycarboxylic acid type copolymers and 10-50 weight parts of polyalkylene glycol derivatives. A cement additive of the invention is preferably used in such a quantity that polycarboxylic acid type copolymers are present in the proportion 0,05-1.0 % by weight based on cement weight and polyalkylene glycol derivatives are present in the proportion 0.005-0.5 % by weight based on cement weight. However, the amount of the cement additive according to the invention to be used can be appropriately determined according to a cement composition used, it basically being the amount which is necessary to attain the desired strength development and improved time to form removal after steam curing, and it is possible that suitable proportions outside these limits may be found. A cement additive according to the invention may be used for stiff consistency concrete, plastic concrete, high fluidity concrete, high strength concrete, cement paste as generally used, mortar, grout, concrete and the like, although the beneficial effects of the invention are most noticeable in high strength concrete in which the water/cement ratio is low. A cement additive according to the invention may be mixed, if desired, with other additives to expand its versatility. Typical examples of other additives are conventional water-reducing agents (lignosulfonate, oxycarboxylate, polyalkylsulfonate, polycarboxylate), air content-regulating agents, drying shrinkage reducing agents, accelerators, retarders, foaming agents, anti-foaming agents, anti-rust agents, set acceleration agents, high early-strengthening agents, efflorescence-inhibiting agents, bleeding inhibitors, pumping aids, and water-soluble polymers. A cement additive according to the invention exhibits a high dispersing ability of a degree never obtained by use only of polycarboxylic acid-type copolymers to various concretes such as ordinary concrete, high strength concrete and steam curing concrete. Without restricting the scope of the invention in any way, it is believed that this is the result of a synergistic effec+ of the polycarboxylic acid type copolymers and the polyalkylene glycol derivatives. It both enhances the fluidity of concrete and maintains this fluidity, thereby making it possible to increase the strength development and decrease the time for form removal after steam curing. The latter is particularly valuable in that it permits economies such as the reduction of time spent in a form used and the reduction of defects in concrete products manufactured in a concrete factory. The invention is now further illustrated by the following non-limiting examples wherein are used the cement additives containing polycarboxylic acid type copolymers and polyalkylene glycol derivatives according to the invention. Examples The compositions of the polycarboxylic acid type copolymers in the cement additives used in the examples and in the comparative examples are shown in Table 1. Said polycarboxylic acid type copolymers can be obtained by known polymerization methods described in, for example, JP, A, H5-306152, JP, A, H6-211949, JP, A, H9-286647 and JP, A, H10-236858. The polyalkylene glycol derivatives in the cement additives used in the examples and in the comparative examples are also shown in Table 2. In order to illustrate the effect of these cement additives, the concrete compositions (shown in Table 3) are designed to have slump of 18.5±1 cm and air content 4.5%. The total quantity of materials in each case is 80 litres, and all the materials are added to a 100 litre pan-type forced mixing mixer, and mixed for 120 sec. to give the concrete compositions. The concrete compositions thus obtained are measured for slump , air content, setting time and compressive strength. Further, the compressive strength in the case of accelerating the appearance of strength by steam curing was measured. 1) Slump: measured according to JIS A 1101, 2) Air content: measured according to JIS A 1128, 3) Setting time: measured according to JIS A 6204 Supplement 1, 4) Compressive strength Ordinary curing: measured according to JIS A 1108, Steam curing: the sample is pre-cured at 20°C for 2 hr, then warmed to 65°C in 2 hrs 30 min, kept at 65°C for 4 hrs. After allowing to cool to 20°C over 4 hrs, the testing is carried out according to JIS A 1108. (Materials used) Mixing water: tap water, Cement: ordinary portland cement (density 3.16 g/cm3), Fine aggregate: Oi River pit sand (specific gravity 2.59, FM=2.74), Coarse aggregate: Oume crushed stone (specific gravity 2.65, MS [median size?]=20mm). The results of the above measurement are shown in Table 4. In the Table, the examples 1-13 and the comparative examples 1-4 are for the results obtained from the ordinary cement, and the examples 14,15 and the comparative examples 5, 6 are those obtained from the high strength concrete. The examples 1-7 show the cases in which the type of the polycarboxylic acid type copolymers is changed, and the examples 1 and 8-13 are the cases in which the type of the polyalkylene glycol derivatives is changed. The comparative examples 1 and 5 show the cases in which a polyalkylene glycol derivative is not used, and the comparative examples 2-4 and 6 are the cases in which compounds other than the polycarboxylic acid type copolymers in the invention are used. As is evident from the comparison between the comparative example 1 and the examples 1-13, and from the comparison between the comparative example 5 and the examples 14 and 15, the ordinary concrete and the high strength concrete, in which the cement additives together with the polyalkylene glycol derivatives of the invention are used, both show a tendency to accelerate setting, whereby the slump values are large (fluidity) and their slump lowering over 60 min is small (high flowability), demonstrating a preferable compressive strength both for ordinary curing and steam curing. The comparative examples 2-4 and 6 are those in which compounds other than the polycarboxylic acid type copolymers in the invention are used, though in these examples the development of compressive strength is not sufficient, because there is demonstrated a retardation of setting. Table 1 Typeof Pohycar-boxylic Acid-type copolymer Type of monomer and composition ratio Average Molecular Weight Monomer (A) Monomer (B) Monomer (C) Monomer (D) Mole ratio (%) Type AGhio. Mole ratio Type Mole ratio (%) Type AGNo. Mole ratio (%) Type PCA-1 15 Polyethylene glycol mono-vinyl ether 50 Maleicacid - - - - - 20000 PCA-2 15 2-Melhyl2-piopen-1-olaflsylene oxide adduct 50 Maleicacid 30000 PCA-3 15 Polyethylene glycol rnctto-vinyi ether 50 Maleicacid 02 Polyethylene glycol maleicacid ester 75 - - 35000 PCA-4 15 Polyethylene glycol poryprapyiene glycol alM ether 50 Maleicacid 03 Poryeflryleneglycol maleicacid ester 25 0.1 Mafeic anhydride 24000 PCA-5 15 Polyethylene glycol ally! ether 12 Maleicacid - - - 02 Styrene 32000 PCA-6 15 2-Methyl2-propen-l-olalkykne oxide adduct 25 Acrylic acid 02 Acrylarrride mdhylpiopan sulfonic acid 27000 PCA-7 15 2-Meftyl2-propen-l-olalkyiene oxide adduct 75 Acrylic acid 02 Polyethylene glycol dirnethacrylicackl ester 75000 P-1 1 2-Methyl 2-propen-1-olalkylene oxide adduct 50 Maleicacid 2 Polyethylene glycol maleicacid ester 25 30000 P-2 1 Polyalkylene glycol rnorovinyl ether 50 Maleicacid 2 Polyethylene glycol mefhacrylic acid ester 25 - - 28000 P-3 - - - Acrylic acid 2 Polyethylene glycol methacrylic acid ester 100 - - 28000 Table 2 Sample mark Component name of polyalkylene glycol Average molecular weight PAG-1 Polyethylene glycol 4000 PAG-2 Polyethylene glycol 6000 PAG-3 Polyethylene glycol 10000 PAG-4 Polyethylene glycol 20000 PAG-5 Polyethylene glycol 50000 PAG-6 Polyethylene glycol-polypropylene glycol block polymer 4000 PAG-7 Polyethylene glycol oleic acid ester 5000 Table 3 (Blend) Type of Concrete W/C (%) s/a (%) Unit amount (Kg/m3) W C S G Ordinary Concrete 50 46 160 320 823 993 High-strength concrete 35.6 44 160 450 741 968 Table 4 (Concrete test) Type of blend No. Polycaibo type capol xylic acid ymer PAG Slump (cm) Air content (%) Setting time (min) Compressive strength (N/mm2) Type Amount added (wt%) Type Amount added (Wf/o) Just after 60 min later Justafer 60 min later Start End Standard curing age3days steam curing age7hrs Example Ordinary Concrete 1 PCA-1 0.2 PAG-4 0.03 19.0 15.0 4.5 4.5 355 450 25.0 27.6 2 PCA-2 0.2 PAG-4 0.03 18.5 16.0 4.4 4.4 350 450 25.4 27.9 3 PCA-3 0.2 PAG-4 0.03 18.0 15.5 4.6 4.5 355 450 25.2 27.6 4 PCA-4 0.2 PAG-4 0.03 18.5 19.0 4.4 4.5 355 460 24.5 27.1 5 PCA-5 0.2 PAG-4 0.03 18.0 15.0 4.4 4.3 355 450 25.6 28.3 6 PCA-6 0.2 PAG-4 0.03 18.0 15.0 4.6 4.5 355 450 25.2 27.4 7 PCA-7 0.2 PAG-4 0.03 18.5 18.5 4.3 4.4 355 450 24.1 29.2 8 PCA-1 0.2 PAG-1 0.05 18.0 15.0 4.2 4.3 355 450 25.2 28.4 9 PCA-1 0.2 PAG-2 0.05 18.0 15.0 4.4 4.5 355 450 25.6 28.3 10 PCA-1 0.2 PAG-3 0.05 18.5 15.0 4.5 4.6 355 450 25.4 28.3 11 PCA-1 0.2 PAG-5 0.05 18.0 15.0 4.5 4.3 355 450 25.3 28.3 12 PCA-1 0.2 PAG-6 0.03 18.5 15.0 4.6 4.4 355 450 26.7 28.4 13 PCA-1 0.2 PAG-7 0.03 18.5 15.0 4.6 4.5 355 450 26.7 27.1 High Strength Concrete 14 PCA-1 0.2 PAG-4 0.03 19.0 15.0 4.5 4.5 300 395 36.4 39.1 15 PCA-2 0.2 PAG-4 0.03 18.5 16.0 4.4 4.4 305 390 36.2 39.0 Ordinary Concrete 1 PCA-1 0.3 - - 17.5 6.0 4.4 4.0 380 485 20.4 23.4 2 P-l 0.2 PAG-4 0.05 18.5 14.5 4.3 5.7 355 450 22.4 23.5 3 P-2 0.2 PAG-4 0.05 19.0 13.5 4.5 5.9 355 455 22.6 23.8 Gomparaltve Example 4 P-3 0.2 PAG-4 0.05 18.5 14.0 4.5 5.9 380 470 22.7 23.5 High strength concrete 5 PCA-1 0.3 13.0 6.0 4.4 4.0 340 495 31.0 35.2 6 P-3 0.3 PAG-4 0.05 18.5 14.0 4.5 5.9 350 445 31.5 36.0 We Claim: 1. A cement additive comprising: (a) a polycarboxylic acid copolymer and/or a salt thereof and a polyalkylene glycol compound, wherein said polycarboxylic acid copolymer contains at least one species of copolymer derived from at least an unsaturated polyalkylene glycol ether monomer (A) and an unsaturated mono- or dicarboxylic acid monomer (B) as its monomer component; or (b) a polycarboxylic acid copolymer and/or a salt thereof and a polyalkylene glycol compound, wherein said polycarhoxylic acid copolymer contains at least one species of copolymer derived from at least an unsaturated polyalkylene glycol ether monomer (A) and an unsaturated mono- or, dicarboxylic acid monomer (B) as its monomer component and said polycarboxylic acid copolymer is additionally derived from an unsaturated polyalkylene glycol ester monomer (C) and/or monomer (D), which is copolymerizable with monomers (A) and (B), or with monomers (A), (B) and (C); wherein for (a) and (b), the monomer (A) is a compound according to general formula (1) wherein R1, R2 and R3 are each independently hydrogen or methyl, provided that not all are methyl; R4 is -CH2O-, -(CH2) 2O-, -C(CH3) 2O- or -0-; the total carbon number of R1, R2, R3 and R4 is 3, R50 is one or more species of C2-C4 oxyalkylene groups, and, in the case of two or more species, is optionally block or random; R6 is hydrogen or a C1-C22 alkyl, phenyl or Ci-Cis alkylphenyl group; p is an integer from on average 1 to 100, the monomer (B) is a compound according to general formula (2): R7 R8 R9 R10OOM1 wherein R7 and R8 are each independently hydrogen or methyl; R9 is hydrogen, methyl or -(CH2)qCOOM2; R10 is -(CH2)r-; q and r are each independently an integer from 0 to 2; M1 and M2 are a monovalent metal, a divalent metal, ammonium or an organic amine. the monomer (C) is a compound according to general formula (3): HC=C (3 R11 (CH2)sCOO(R130)tR14 wherein R11 and R12 are each independently hydrogen, methyl or (CH2)uCOOM3, u is an integer from 0 to 2, M3 is a monovalent metal, a divalent metal, ammonium or an organic amine; R130 is one or more species of C2-C4 oxyalkylene groups, and, in the case of two or more species, is optionally block or random; R14 is a C1-C22 hydrogen or an alkyl, phenyl or C1-C22 alkylphe/ryl group; s is an integer from 0 to 2; t is an integer an average from 1 to 300; and the monomer (D) is a compound according to the following general formula (4): R15 R16 R18 R19 HC=C C=CH (4 (CH2)vCOO(R170)wOC(CH2)>( ?#>? wherein R15, R16, R18 and R19 are each independently hydrogen or methyl, provided that not all are methyl; R170 is one -or more species of C2-C4 oxyalkylene groups, and in the case of two or more species, is optionally block or random; w is an integer an average from 1 to 300; v and x are each independently an integer from 0 to 2; which contains 100 weight parts of polycarboxylic acid copolymer and 10-50 weight parts of polyalkylene glycol in mixing proportion. 2. A high strength concrete mix, comprising a cement mix and a cement additive as claimed in claim 1. 3. . The high strength concrete mix as claimed in claim 2, wherein the amount of cement additive is such that the amount of polycarboxylic acid copolymer to cement is 0.05-1.0% by weight based on the weight of cement, and the amount of the polyalkylene glycol to cement is 0.005-0.5% by weight based on the weight of cement. 4. A method of preparation of a high-strength concrete mix, comprising the incorporation into a concrete mix a cement additive as claimed in claim 1. 5. The method as claimed in claim 4, wherein the amount of cement additive is such that the amount of polycarboxylic acid copolymer to cement is 0.05-1.0% by weight based on the weight of cement, and the amount of the polyalkylene glycol to cement is 0.005-0.5% by weight based on the weight of cement. Dated this 10th day of August, 2001. (JAYANTA PAL) OF RENFRY & SAGAR ATTORNEY FOR THE APPLICANTS

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