USH493H - Alkylsulfonated polysaccharides and mortar and concrete mixes containing them - Google Patents

Alkylsulfonated polysaccharides and mortar and concrete mixes containing them Download PDF

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Publication number
USH493H
USH493H US06/575,733 US57573384A USH493H US H493 H USH493 H US H493H US 57573384 A US57573384 A US 57573384A US H493 H USH493 H US H493H
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US
United States
Prior art keywords
degree
alkylsulfonated
sulfonation
starch
mortar
Prior art date
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Abandoned
Application number
US06/575,733
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English (en)
Inventor
Fabio Tegiacchi
Benito Casu
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GRACE ITALIANA AN ITALIAN Co
Grace Italiana SpA
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Grace Italiana SpA
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Assigned to GRACE ITALIANA, AN ITALIAN COMPANY reassignment GRACE ITALIANA, AN ITALIAN COMPANY ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: CASU, BENITO, TEGIACCHI, FABIO
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C08B31/08—Ethers
    • C08B31/12—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch
    • 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
    • C04B24/168—Polysaccharide derivatives, e.g. starch sulfate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B11/00—Preparation of cellulose ethers
    • C08B11/02—Alkyl or cycloalkyl ethers
    • C08B11/04—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
    • C08B11/10—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals

Definitions

  • the instant invention concerns improvements in mortar and concrete mixes.
  • the improvement of the instant invention consists of admixing mortar or concrete with a small amount of a fluidizing agent, viz. alkylsulfonated polysaccharides.
  • the instant invention consists in improving the workability of mortar and concrete mixes so as to allow very low water/cement ratios.
  • Mortar and concrete mixes are those mixtures of cementitous material and aggregates defined in ASTM specifications C270 and C125 respectively.
  • the amount of water required for a convenient workability is much greater than that which would be necessary for the full hydration of the hydraulic binder employed for making the mix.
  • the water excess may cause serious handicaps both to the fresh mix (excessive bleeding, segregation, etc.) as well as to the hardened mix (excessive shrinkage, high porosity, lower resistance, etc.).
  • fluidizing agents are designated as fluidizing agents. More particularly, according to the Italian Standards for Testing Materials (UNI), these materials are grouped into two classes, i.e. fluidizing agents and superfluidizing agents. If the agent allows, in standard plastic mortars, a water reduction of not less than 6% (i.e. ##EQU1## wherein V R is the water volume of the reference mix and V A is the water volume, inclusive of the fluidizing agent, of the fluidizing-agent-containing mix), then according to UNI Standard 7102-72 the material is defined as a fluidizing agent. If, on the other hand, said material allows a water reduction of not less than 10%, (i.e.
  • V R is the water volume of the reference mix and V A is the water volume, inclusive of the fluidizing agent, of the fluidizing-agent-containing-mix), then according to UNI Standard 8145 the material is defined as a superfluidizing agent.
  • Fluidizing and superfluidizing agents as above defined meet requirements for type A and type F concrete mixes specified in ASTM C 494-80.
  • lignine-sulfonates lignine-sulfonates
  • gluconates lignine-sulfonates
  • tannates lignine-sulfonates
  • Some known industrial carbohydrates such as, e.g. glucose syrups (v. U.S. Pat. No. 3,432,317) and modified starch hydrolizates (v. Applicant's IT patent application No. 21080 A/80 filed on Apr. 28, 1980) are commonly used in cement mixes both for improving the rheologic properties of the mixes as well as for improving their mechanical strength. Their water reducing capability, though, is very limited and much inferior to that of the superfluidizers.
  • Known superfluidizers are made of polynaphthalene sulfonates (v. e.g. U.S. Pat. No. 2,141,569; DE-AS No. 1,238,831; CA Pat. No. 993,901) and of sulfonated melamine resins (v.e.g. IT Pat. No. 801,078).
  • the alkyl sulfonated polysaccharide superfluidizing agents of the invention are characterized by a degree of polymerization (D.P.) of up to 100, a degree of sulfonation (D.S.) as hereinafter defined and determined, of from 0.2 to 3.0. They can be further characterized by their fluidizing activity, in as much as the addition of 0.4% of the inventive fluidizer is capable of imparting to the mortar to which it is added a flow increase of from 6.5% to 130% whenever the D.S. value is in the range of from 0.20, inclusive, to 1.50, inclusive.
  • D.P. degree of polymerization
  • D.S. degree of sulfonation
  • Illustrative examples of useful polysaccharides for making the inventive superfluidizers are e.g. cellulose, hemicellulose, starches and hydrolizates thereof.
  • Illustrative examples of sulfonating agents for making the inventive superfluidizers are, e.g. chloromethylsulfonic acid, chloroethane sulfonic acid, chloropropane sulfonic acid and 1,3 propane-sultone.
  • the preferred inventive superfluidizers are those made of hydrolized cellulose sulfonated with chloromethane or chloroethane sulfonic acid.
  • Superfluidizers made of wood molasses sulfonated with chloropropanesulfonic acid as well as hydrolized starches sulfonated with chloroethane or chloropropane sulfonic acid are even more preferred.
  • the most preferred inventive superfluidizers are those obtained from water soluble starch hydrolizates having a polymerization degree equal or lower than 100 and chloroethanesulfonic acid, as the sulfonating agent.
  • the sulfonate groups of the inventive fluidizing agents can either be in the free acid form or can be salified with a Group IA and IIA metal cation preferably sodium, potassium or calcium.
  • a Group IA and IIA metal cation preferably sodium, potassium or calcium.
  • Other useful cations can be chosen from ammonium or the organic amines.
  • the amine may be any suitable primary, secondary or tertiary amine, such as, e.g. amines containing an hydroxyl group. Primary, secondary and tertiary alkanolamines are preferred.
  • the inventive superfluidizers are readily prepared by per se known methods.
  • the yield is 80% of the theory.
  • the substitution degree is 0.9.
  • reaction mixture is then allowed to stand for 48 hrs. at ambient temperature and the pH is adjusted to 4 with 2 N NaOH. Finally, the title product is separated from the reaction mixture by precipitation with a 2.5:1.5 methanol/acetone mixture; then said product is dissolved in water and dialyzed through a 3500 Dalton cellulose acetate membrane.
  • the yield is 45% of the theory.
  • the substitution degree is 1.1.
  • the water phase is dialyzed through a 3500 Dalton cellulose acetate membrane.
  • the yield is 80% of the theory.
  • the substitution degree is 0.6.
  • the fluidizing activity of the inventive agents appears to be a function of the starting polysaccharides and of the sulfonating agent used.
  • the sulfonation degree (also referred to herein as D.S.) of the tested inventive sulfoalkyl polysaccharides has been determined by means of the nuclear magnetic resonance spectroscopy ( 1 H - NMR).
  • the NMR spectra shown in FIG. 1 correspond to a typical water soluble starch (a) and to its sulfoethyl derivative (b) (D.S. ⁇ 0.5) as well as to its sulfopropyl derivative (c) (D.S. ⁇ 1.1).
  • the asterisks identify signals corresponding to the --CH 2 --groups of the sulfoethyl and sulfopropyl substituents. These signals permit one to determine the sulfonation degree by relating their area to that of the anomeric signals (H-1).
  • Table 2 shows the dependence of the fluidizing activity on the degree of sulfonation.
  • the sulfonated derivatives in Table 2 have been prepared by subjecting a commercial water soluble starch having a polymerization degree of 80 by sulfonation with the sodium salt of chloroethylsulfonic acid, according to the method described in Example 3.
  • the flow tests are performed with plastic mortars according to UNI Standard 8020 and using a Pt 325 cement; the amount of the fluidizer added being 0.4% of the weight of the cement.
  • the fluidizing effect becomes noticeable after addition of a 0.4 % amount of an inventive superfluidizer having a D.S. value of 0.20.
  • the resulting effect is of little interest from an industrial point of view.
  • a fluidizing effect in the range of those obtainable with known fluidizing agents is achieved by adding 0.4% of an inventive superfluidizer, having a D.S. value of 0.80.
  • the fluidizing effect attained is in the range of those obtainable with an equal amount of commercial superfluidizers.
  • the possibility of fluidizing the mortar and concrete mix depends not only on the sulfonation degree but also on the amount of fluidizing agent added thereto and is all the lower the higher is the sulfonation degree.
  • the dosage of the fluidizer shall be in the range of from 0.2% to 0.6%.
  • the quantity of fluidizer added to the mix is the same for all the samples, i.e. 0.40% (referred to the weight of hydraulic binder).
  • Table 5 shows data obtained with concrete tests carried out according to Italian Standards (UNI 7163), using Pt425 cement of the commerce.
  • inventive alkylsulfonated polysaccharides are useful for making mortar and concrete mixes containing any type of hydraulic binder such as Portland cement and blended cements (Portland blast-furnace slag cement, Portland-Pozzolan or fly ash cement, slag cement).
  • the inventive mortar or concrete mix may contain other additives, such as hardening agents, air-entraining agents, plasticizers, accelerators and retarders known in the art.
  • hydraulic binders used for making mortar and concrete mixes of the invention may already contain additives used in the clinker-grinding process and/or in the hydraulic binder manufacturing process.
  • inventive superfluidizers can be incorporated into the mortar and concrete mix by any convenient method. Thus, they can be added directly to the mix, advantageously as a water solution.
  • inventive fluidizers can be pre-mixed with one or more of the ingredients of the mix. If it is pre-mixed with cement, the fluidizer must necessarily be in the dry state.
  • the inventive fluidizers can also be added to the clinker during grinding.
  • it can be mixed with known grinding aids such as, e.g. alkanolamines and glycols.
  • this invention is advantageously applicable to the production of any kind of mortar and concrete
  • this invention is particularly directed to the field of the additives which improve the workability of the concrete used in civil buildings or massive buildings (as bridges or roads), as well as for pre-cast concrete manufacturing.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Biochemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Structural Engineering (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
US06/575,733 1983-03-03 1984-02-01 Alkylsulfonated polysaccharides and mortar and concrete mixes containing them Abandoned USH493H (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT19879/83A IT1161592B (it) 1983-03-03 1983-03-03 Polisaccaridi alchilsolfonati ad attivita' fluidificante e matle e calcestruzzi contenenti detti polisaccaridi
IT19879A/83 1983-03-03

Publications (1)

Publication Number Publication Date
USH493H true USH493H (en) 1988-07-05

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US06/575,733 Abandoned USH493H (en) 1983-03-03 1984-02-01 Alkylsulfonated polysaccharides and mortar and concrete mixes containing them

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US (1) USH493H ( )
BE (1) BE899046A ( )
CA (1) CA1217482A ( )
CH (1) CH659241A5 ( )
DE (1) DE3406745A1 ( )
FR (1) FR2541990A1 ( )
GB (1) GB2138014B ( )
IT (1) IT1161592B ( )
NL (1) NL8400642A ( )
SE (1) SE8401151L ( )

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5573589A (en) * 1993-03-10 1996-11-12 Sandoz Ltd. Cement compositions containing a sulfated polysaccharide and method
US5986087A (en) * 1995-05-24 1999-11-16 Dystar Textilfarben Gmbh & Co. Deutschland Kg Sulfonation of regenerated cellulose with sulfonated polymers and use of the thus modified fibres
US6068697A (en) * 1996-11-27 2000-05-30 Kao Corporation Polysaccharide derivatives and hydraulic compositions
US20070107638A1 (en) * 2003-12-01 2007-05-17 Byong-Wa Chun Gluconate broth for cement and concrete admixture

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4203530A1 (de) * 1992-02-07 1993-08-12 Wolff Walsrode Ag Verwendung von wasserloeslichen sulfoalkylderivaten der cellulose in gips- und zementhaltigen massen
DE4203529A1 (de) * 1992-02-07 1993-08-12 Wolff Walsrode Ag Wasserloesliche sulfoalkylhydroxyalkylderivate der cellulose und deren verwendung in gips- und zementhaltigen massen
TR27111A (tr) * 1992-06-06 1994-11-09 Hoechst Ag Sulfoakil grubu ihtiva eden alkilhidroksialkil selüloz eterleri.
US5591844A (en) * 1992-06-06 1997-01-07 Hoechst Aktiengesellschaft Alkyl hydroxyalkyl cellulose ethers containing sulfoalkyl groups
US5575840A (en) * 1993-10-29 1996-11-19 National Starch And Chemical Investment Holding Corporation Cement mortar systems using blends of polysaccharides and cold-water-soluble, unmodified starches
DE19543304B4 (de) * 1995-11-21 2005-06-09 Skw Bauchemie Gmbh Zusatzmittel für wasserhaltige Baustoffmischungen und dessen Verwendung
IT1291309B1 (it) * 1997-05-06 1999-01-07 F B C Future Biolog Chemicals Fluidificanti cementizi a base di amidi solfati
DE10209812A1 (de) 2001-03-22 2002-09-26 Degussa Construction Chem Gmbh Verwendung von wasserlöslichen Polysaccharid-Derivaten als Dispergiermittel für mineralische Bindemittelsuspensionen

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2429211A (en) 1944-02-07 1947-10-21 Andes Ralph Verne High-temperature cement modifier
US2562148A (en) 1949-07-11 1951-07-24 Phillips Petroleum Co Low water-loss cement slurry
US2583657A (en) 1949-07-11 1952-01-29 Phillips Petroleum Co Low water-loss cement and process of making
US2795508A (en) 1952-08-22 1957-06-11 Phillips Petroleum Co Sulfoalkyl cellulose ethers and their salts as hydraulic natural cement set retarders
US2820788A (en) 1955-02-24 1958-01-21 Du Pont Process for preparing sodium sulfomethylcellulose
US2891057A (en) 1956-11-09 1959-06-16 Mo Och Domsjoe Ab Methods of making cellulose ethers
US2896715A (en) 1952-05-05 1959-07-28 Phillips Petroleum Co Hydraulic cements
US3530112A (en) 1967-07-24 1970-09-22 Itt Rayonier Inc Process for preparing dispersants useful in hydraulic cement slurries
US4073658A (en) 1976-03-10 1978-02-14 Kao Soap Co., Ltd. Hydraulic cement composition

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3332791A (en) * 1964-05-12 1967-07-25 Rayonier Inc Process for producing portland cement compositions

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2429211A (en) 1944-02-07 1947-10-21 Andes Ralph Verne High-temperature cement modifier
US2562148A (en) 1949-07-11 1951-07-24 Phillips Petroleum Co Low water-loss cement slurry
US2583657A (en) 1949-07-11 1952-01-29 Phillips Petroleum Co Low water-loss cement and process of making
US2896715A (en) 1952-05-05 1959-07-28 Phillips Petroleum Co Hydraulic cements
US2795508A (en) 1952-08-22 1957-06-11 Phillips Petroleum Co Sulfoalkyl cellulose ethers and their salts as hydraulic natural cement set retarders
US2820788A (en) 1955-02-24 1958-01-21 Du Pont Process for preparing sodium sulfomethylcellulose
US2891057A (en) 1956-11-09 1959-06-16 Mo Och Domsjoe Ab Methods of making cellulose ethers
US3530112A (en) 1967-07-24 1970-09-22 Itt Rayonier Inc Process for preparing dispersants useful in hydraulic cement slurries
US4073658A (en) 1976-03-10 1978-02-14 Kao Soap Co., Ltd. Hydraulic cement composition

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Hackh's Chem. Dictionary, pp. 317 and 725.
Kirk-Othmer--Encyclopedia of Chemical Technology--Third Edition vol. 5--pp. 70-88.

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5573589A (en) * 1993-03-10 1996-11-12 Sandoz Ltd. Cement compositions containing a sulfated polysaccharide and method
US5986087A (en) * 1995-05-24 1999-11-16 Dystar Textilfarben Gmbh & Co. Deutschland Kg Sulfonation of regenerated cellulose with sulfonated polymers and use of the thus modified fibres
US6068697A (en) * 1996-11-27 2000-05-30 Kao Corporation Polysaccharide derivatives and hydraulic compositions
US20070107638A1 (en) * 2003-12-01 2007-05-17 Byong-Wa Chun Gluconate broth for cement and concrete admixture
US7462236B2 (en) 2003-12-01 2008-12-09 W. R. Grace & Co.-Conn. Gluconate broth for cement and concrete admixture

Also Published As

Publication number Publication date
GB2138014A (en) 1984-10-17
BE899046A (fr) 1984-07-02
CA1217482A (en) 1987-02-03
IT1161592B (it) 1987-03-18
SE8401151L (sv) 1984-09-04
NL8400642A (nl) 1984-10-01
SE8401151D0 (sv) 1984-03-01
CH659241A5 (de) 1987-01-15
IT8319879A1 (it) 1984-09-03
FR2541990A1 (fr) 1984-09-07
DE3406745A1 (de) 1984-09-06
GB2138014B (en) 1986-04-09
GB8405407D0 (en) 1984-04-04
IT8319879A0 (it) 1983-03-03

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