GB2138014A - Alkylsulfonated polysaccharides and mortar and concrete mixes containing them - Google Patents
Alkylsulfonated polysaccharides and mortar and concrete mixes containing them Download PDFInfo
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- GB2138014A GB2138014A GB08405407A GB8405407A GB2138014A GB 2138014 A GB2138014 A GB 2138014A GB 08405407 A GB08405407 A GB 08405407A GB 8405407 A GB8405407 A GB 8405407A GB 2138014 A GB2138014 A GB 2138014A
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- alkylsulfonated
- degree
- polysaccharide
- water
- sulfonation
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- 239000004570 mortar (masonry) Substances 0.000 title claims abstract description 29
- 239000004567 concrete Substances 0.000 title claims abstract description 24
- 150000004676 glycans Chemical class 0.000 title claims abstract description 22
- 229920001282 polysaccharide Polymers 0.000 title claims abstract description 22
- 239000005017 polysaccharide Substances 0.000 title claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 35
- 229920002472 Starch Polymers 0.000 claims description 33
- 235000019698 starch Nutrition 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 31
- 239000008107 starch Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 238000006277 sulfonation reaction Methods 0.000 claims description 21
- 239000011230 binding agent Substances 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 229920002488 Hemicellulose Polymers 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- LHORZPMPPHTXFQ-UHFFFAOYSA-N 1-chloroethanesulfonic acid Chemical compound CC(Cl)S(O)(=O)=O LHORZPMPPHTXFQ-UHFFFAOYSA-N 0.000 claims description 5
- 229920002678 cellulose Polymers 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 235000013379 molasses Nutrition 0.000 claims description 2
- 239000011396 hydraulic cement Substances 0.000 claims 2
- 239000002023 wood Substances 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 230000000694 effects Effects 0.000 description 15
- 239000004568 cement Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- -1 e.g. Chemical class 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920000417 polynaphthalene Polymers 0.000 description 4
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 3
- MCXZBEZHTYZNRE-UHFFFAOYSA-N 1-chloropropane-1-sulfonic acid Chemical compound CCC(Cl)S(O)(=O)=O MCXZBEZHTYZNRE-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- FXKMTSIKHBYZSZ-UHFFFAOYSA-N 2-chloroethanesulfonic acid Chemical compound OS(=O)(=O)CCCl FXKMTSIKHBYZSZ-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 150000007974 melamines Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical class [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920002253 Tannate Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011400 blast furnace cement Substances 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- HMPHJJBZKIZRHG-UHFFFAOYSA-N chloromethanesulfonic acid Chemical compound OS(=O)(=O)CCl HMPHJJBZKIZRHG-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 150000004804 polysaccharides Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000011178 precast concrete Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Ceramic Engineering (AREA)
- Structural Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
Alkylsulfonated polysaccharides are incorporated into mortar and concrete mixes to improve their flowability.
Description
SPECIFICATION
Alkylsulfonated polysaccharides and mortar and concrete mixes containing them
The instant invention relates to improvements in mortar and concrete mixes, and more especially mortar and concrete mixes which are mixtures of cementitious material and aggregates as defined in ASTM specifications C270 and C125 respectively.
It is known that in mortar and concrete mixes the initial weight ratio of water to cement, more commonly referred to as W/C ratio, is an important factor governing the so-called workability of the cement mix. The amount of water required for a convenient workability is much greater than that necessary for the full hydration of the hydraulic binder employed for making the mix. The water excess, particularly in the case of mixes having high workability, may cause serious handicaps both to the fresh mix (excessive bleeding, segregation, etc.) and to the hardened mix (excessive shrinkage, high porosity, lower resistance, etc.).
In order to obtain a good workability of mortar and concrete mixes with lower W/C ratios, it has been proposed to incorporate various materials into the mixes and a number of these have achieved commercial importance.
Usually, such materials are designated as fluidizing agents. More particularly, according to the
Italian Standards for Testing Materials (UNI), these materials are grouped into two classes, viz.
fluidizing agents and superfluidizing agents. If the agents allows, in standard plastic mortars, a water reduction of not less than 6% (i.e.
VR VA 100 ~6% VR wherein VA is the water volume of the reference mix and VA 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.
VR ~ VA 100 ~10% VA wherein VA is the water volume of the reference mix and VA is the water volume, inclusive of the fluidizing agent, of the fluidizing-agent-containing-mix), then according to the 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.
Known useful fluidizing agents are ligninsulfonates, gluconates and tannates.
Some known industrial carbohydrates such as, e.g., glucose syrups (see US Patent 3,432,317) and modified starch hydrolyzates (see Applicant's Italian Patent Application No.
21680 A/80 filed on April 28, 1980) are commonly used in cement mixes both for improving the rheologic properties of the mixes and for improving their mechanical strength. Their water reducing capability is however, very limited and much inferior to that of superfluidizers.
Industrially, the use of superfluidizers has acquired importance only during the past five years or so.
Known superfluidizers are made of polynaphthalene sulfonates (see, e.g., US patent 2,141,569; DE-AS 1,238,831; CA Patent 993,901), or of sulfonated melamine resins (see, e.g., IT Patent 801,078).
It has now been found that by sulfonating polysaccharides with suitable sulfonating agents excellent superfluidizing agents have superior properties to known fluidizing and superfluidizing agents can be obtained.
The alkyl sulfonated polysaccharide superfluidizing agents of the invention are characterized by a degree of polymerization (D.P.) of up to 100, and 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, inasmuch as the addition of 0.4% of a fluidizer of the invention 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.
Examples of useful polysaccharides for making the superfluidizers of the invention include cellulose, hemicellulose, starches and hydrolysates thereof.
Examples of sulfonating agents for making the superfkuidizer of the invention include chloromethylsulfonic acid, chloroethane sulfonic acid, chloropropane sulfonic acid and 1,3propane-sultone.
Preferred superfluidizers are those made by sulfonating hydrolysed cellulose with chloromethane or chlorethane sulfonic acid. More preferred superfluidizers are made by sulfonating work molasses with chloropropanesulfonic acid or hydrolysed starches with chloroethane or chloropropane sulfonic acid.
At present, the most preferred superfluidizers are those obtained by sulfonating water-soluble starch hydrolysates having a polymerization degree equal or lower than 100 with chloroethanesulfonic acid.
It appears that the fluidizing activity of the superfluidizing agents of the invention depends on the starting polysaccharide and the sulfonating agent used. This statement is supported by the data shown in the following Table.
TABLE 1
FLOW TESTS
SUPERFLUIDIZER PROPORTION (b) FLOW (mm)
USED referred to plain 1) hemicellulose 0.6 + 12
sulfopropylate (a) 1.5 + 24 2) Starch 0.3 + 24
sulfopropylate (a) 0.5 + 35 3) Soluble starch 0.3 + 24
solfoethylate (a) 0.5 + 50 (a) prepared as in Examples 1, 2 and 3 below respectively.
(b) Proportions are expressed as percent (dry to dry) of the amount of cement in the mix.
The figures shown in Table 1 show that the fluidizers made from water-soluble starches with polymerization degree of up to 100 and chloroethane sulfonic acid yield the best results, and indeed results which have not been acheived with known fluidizers or superfluidizers. The flow tests of Table 1 were made with plastic mortars according to the Italian Standard UNI 8020, using Pt 325 cement (which is commonly used in industry).
The sulfonate groups of the new fluidizing agents can either be in the free acid form or can be salified with a Group 1A and IIA metal cation, preferably sodium, potassium or calcium. Other useful cations include ammonium and the cations of organic amines. When the cation is derived from an organic amine, the amines 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 superfluidizers of the invention are readily prepared by methods known per se.
The following Examples illustrate the superfluidizers of the invention, the way of making them, and the way of using them in mortar and concrete mixes.
EXAMPLE 1
Hemicellulose sulfopropylate
To 100 g of a hemicellulose slightly soluble in water at room temperature suspended in 300 ml water containing 75 g NaOH are added 450 g of 1,3-propanesultone and the reaction is continued for 1 6 hrs. at 50"C with stirring. The reaction mixture is then allowed to stand for 48 hrs. at ambient temperature. The pH is adjusted to 4 with 2N sodium hydroxide and the title product is precipitated with methyl alcohol. The yield is 80% of theory. The degree of substitution is 0.9.
EXAMPLE 2
Starch sulfopropylate
To 80 g of starch insoluble in water at room temperature suspended in 250 ml water containing 60 g NaOH, are added 350 g of 1,3-propane-sultone and the reaction is continued 1 6 hrs. at 50"C with stirring. The 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/acetate mixture.
The said product is dissolved in water and dialysed through a 3500 Dalton cellulose acetate membrane. The yield is 45% of theory. The substituted degree is 1.1.
EXAMPLE 3
Water-soluble starch sulfoeth ylate To 100 g of starch, easily soluble in water at room temperature suspended in 1000 ml isopropyl alcohol, are added 1 75 g of the sodium salt of 2-chloroethanesulfonic acid and a solution of 95 g of NaOH in 100 ml water. The reaction is continued with stirring for 1 5 min. at 30"C and then a further 60 min. at 80"C. The reaction is interrupted by cooling to room temperature. After neutralization with acetic acid, the water phase is dialysed through a 3500
Dalton cellulose acetate membrane.
The yield is 80% of theory. The substitution degree is 0.6.
As stated above, fluidizing activity of the agents of the invention appears to be a function of the starting polysaccharide and of the sulfonating agent used. It further appears that the activity also depends on the sulfonation degree, i.e. the mean number of alkyl sulfonic groups per repeating unit of the polysaccharide chain. It has been found that 0.2 is the minimum degree of sulfonation necessary for improving the fluidizing activity of the polysaccharide used. It has further been ascertained that in order to obtain a fluidizing agent with outstanding activity (i.e.
an activity greater than what is considered normal in the art) the degree of sulfonation must exceed 1.
The sulfonation degree (also referred to herein as D.S.) of the sulfoalkyl-polysaccharides of the invention has been determined by means of nuclear magnetic resonance spectroscopy (tH-NMR). The NMR Spectra shown in Fig. 1 of the accompanying drawings correspond to a typical water soluble starch and to its sulfoethyl derivative (D.S.-0.5) as well as to its sulfopropyl derivative (D.S.=1 .1). The asterisks identify signals corresponding to the -CH2groups of the sulfoethyl and sulfopropyl substituents. These signals make it possible to determine the sulfonation degree by relating their area to that of the anomeric signals (H-l).
The following Table 2 shows the dependence of the fluidizing activity on the degree of sulfonation.
TABLE 2
EFFECT OF THE DEGREE OF SULFONATION
D.S. FLOW (mm) INCREASE OVER THE
PLAIN (mm) plain 72 0.00* 70 - 2 0.20 77 + 5 0.80 89 +17 1.10 139 + 67 1.35 151 + 79 1.50 165 + 93 * This corresponds to the starting material, i.e. the unsubstituted or non-sulfoalkylated watersoluble starch.
The sulfonated derivatives in Table 2 were prepared by subjecting a commercial water-soluble starch having a polymerization degree of 80 to 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 data in Table 2 shows that the addition of 0.4% of non-sulfoalkylated water-soluble starch to mortar causes a slight decrease in the flowability of said mortar with respect to the plain (or mortar with no addition). The fluidizing effect becomes noticeable after addition of 0.4% of superfluidizer of the invention having a D.S. value of 0.20. The resulting effect, though, is of little interest from an industrial point of view. A fluidizing effect in the same range as those obtainable with known fluidizing agents is achieved by adding 0.4% of superfluidizer of the invention, having a D.S. value of 0.80. With the addition of 0.4% of a superfluidizer having a D.S. value of 1.10, the fluidizing effect attained is in the range of those obtainable with an equal amount of commercial superfluidizers.Finally, with the addition of 0.4% of a superfluidizer, having a D.S. value of at least 1.35, the fluidizing effect attained is outstanding, i.e. much greater than the fluidizing effect achievable with an equal amount of a known superfluidizer.
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 to the mix and is the lower the higher is the degree of sulfonation.
According to the present invention, interesting results (with respect to flowability) are obtained with proportions between 0.1 % and 0.4% (of the weight of the hydraulic binder) and high D.S.
values, i.e. greater then 1.0.
For achieving results of the same order of magnitude using fluidizers having a medium degree of sulfonation, i.e. with D.S. values in the range of from 0.8 to 1.2, the proportion of the fluidizer should be in the range of from 0.2% to 0.6%.
When using fluidizers having a low degree of sulfonation, i.e. having D.S. values ranging from between 0.2 to 0.5, proportions greater than 0.6% are needed.
In particular, when using sulfoethylated water-soluble starches (having a polymerization degree of (100), it has been found that with proportions of from 0.35% to 0.55% (of the weight of the hydraulic binder) and a D.S. value of about 0.8, the flowability of the mortar and concrete mix is of the same order of magnitude as that achievable using known fluidizers. When the D.S. value of the said starches is about 1, the flowability of the mortar and concrete mix is equivalent to that of a mortar and concrete mix with a known superfluidizer. Finally, using a sulfoethylated starch of this invention having a D.S. value of about 1.3, the flowability of the mortar and concrete mix containing it is greater than that obtainable with known superfluidizers.
The following Table 3 outlines the results attained with a commercial water-soluble starch having a polymerization degree of r100, at increasing D.S. values, in comparison with fluidizers known in the art.
TABLE 3
COMPARISON OF THE SUPERFLUIDIZERS OF THE INVENTION WITH
KNOWN FLUIDIZERS AND SUPERFLUIDIZERS FLUIDIZER FLOW (mm) COMPRESSIVE
STRENGTH
(Kg/cm2) at 7 days
Absolute Referred Absolute Referred
value to plain value to plain 1-Commercial water-soluble starch sulfoethylate (of the invention) D.S.=O.8 89 + 17 292 + 66 2-Raw calcium lignine sulfonate liquor 85 + 1 3 260 + 34 3-sodium gluconate mother liquor 90 + 18 253 + 27 4-Commercial water soluble starch sulfoethylate (of the invention)
D.S. = 1.0 129 +47 289 + 63 5-Sodium polynaphthalene sulfonate 120 + 38 280 + 54 6-Sulfonated melamine resin 115 + 33 295 + 69 7-Commercial water soluble starch sulfoethylate (of the invention)
D.S. = 1.30 159 + 67 267 + 41
The following Table 4 outlines the superior reduction of water demand obtained with a commercial water-soluble starch having a polymerization degree of '100 and a D.S. value of 1.25, in comparison with a commercial known superfluidizer (polynaphthalene sulfonate).
TABLE 4
FLUIDIZER ml of W/C flow Compressive
strength at
7 days (kg/cm2)
Plain 225 0.5 85 260
Sulfoalkylated starch 1 94 0.43 86 358
Naphthalene sulfonate 200 0.44 86 342
According to UNI Standard 8145, the water reduction, as hereinafter defined, obtained with the sulfoalkylated starch, viz.
225 194 100. = 14% 225 is greater than the water reduction obtained, with the known superfluidizer (polynaphthalene sulfonate), viz.
225 - 200 100. =11% 225
The tests summarized in Tables 3 and 4 were carried out with plastic mortar, according to
UNI Standard 8020, using a Pt 325 commercial cement. 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).
The following Table 5 shows data obtained with concrete tests carried out according to Italian
Standards (UNI 7163), using Pt425 cement of commerce.
TABLE 5
Cement type Cement W/C Slump Compressive strengths
dosage value (kg/cm2)
kg/m3 (cm)
3 days 7 days 28 days 425 Portland 350 0.55 8 230 336 400 idem + polynapthalene sulfonate 350 0.44 8 388 449 590 idem + sulfoalkylstarch 350 0.44 10 368 460 605
The alkylsulfonated polysaccharides of the invention are usefule 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). The mortar or concrete mix may contain other additives, such as hardening agents, air-entraining agents, plasticizer, accelerators and retarders known in the art. The hydraulic binders used for making mortar and concrete mixes of the invention may already contain additives used in the clinkergrinding process and/or in the hydraulic binder manufacturing process.
The superfluidizers of the invention 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. Alternatively, the fluidizers can be pre-mixed with one or more of the ingredients of the mix. If it is pre-mixed with cement, the fluidizers must necassarily be in the dry state. The fluidizing can also be added to the clinker during grinding. In this case, it can be mixed with known grinding aids such as, e.g., alkanolamines and glycols.
Although the present invention is advantageously applicable to the production of any kind of mortar and concrete, the invention is particularly useful in the field of additives which improve the workability of concrete used in civil buildings or massive buildings (as bridges or roads), as well as in pre-cast concrete manufacturing.
Claims (13)
1. A superfluidizing agent for mortar or concrete comprising an alkylsulfonated polysaccharide having a degree of polymerization of up to 100 and a degree of sulfonation of from 0.2 to 3.0.
2. A superfluidizing agent according to claim 1 wherein the said degree of sulfonation is from 0.2 to 1.5.
3. A superfluidizing agent according to claim 1 or 2 wherein the said alkylsulfonated polysaccharide is an alkylsulfonated cellulose, hemicellulose, hydrolyzed cellulose, wood molasses, or starch.
4. A superfluidizing agent according to claim 1 or 2 wherein the said alkylsulfonated polysaccharide is an alkylsulfonated water-soluble starch.
5. A superfluidizing agent according to claim 4 wherein the said alkylsulfonated water soluble starch is the product of an alkylsulfonation of a water soluble starch with chloroethanesulfonic acid.
6. A superfluidizing agent according to claim 4 wherein the degree of sulfonation of the water-soluble starch is about 1.3 or greater.
7. A superfluidizing agent according to claim 1 comprising hemicellulose sulfopropylate starch sulfopropylate, or water-soluble starch sulfoethylate.
8. A superfluidizing agent according to claim 1 substantially as described in any one of
Examples 1 to 3.
9. A hydraulic cementitious composition comprising a hydraulic cement binder and an alkylsulfonated polysaccharide as defined in any of claims 1 to 8.
10. A composition according to claim 9 wherein the said alkylsulfonated polysaccharide is present in an amount of from 0.1 % to 0.4% of the weight of the said binder and the alkylsulfonated polysaccharide has a degree of sulfonation greater than 1.0.
11. A composition according to claim 9 wherein the said alkylsulfonated polysaccharide is present in an amount of from 0.2% to 0.6% of the weight of the said binder has a degree of sulfonation from 0.8 to
1.2.
1 2. A composition according to claim 9 wherein the said alkylsulfonated polysaccharide is present in an amount greater than 0.6% by weight of the said binder and has a degree of sulfonation from 0.2 to 0.5.
1 3. A composition according to claim 9 wherein the said alkylsulfonated polysaccharide is a sulfoethylated water-solution starch which is present in an amount of from 0.35% to 0.55% of the weight of the said hydraulic binder and has a degree of sulfonation from about 0.8 to about
1.3.
1 4. A method for increasing the flowability of a mortar or concrete mix containing a hydraulic cement binder which comprises the step of incorporating into said mix about 0.1 % to about 1.0% by weight, based on the weight of said binder, of an alkylsulfonated polysaccharide as defined in any of claims 1 to 8.
1 5. A method according to claim 14 wherein the said alkylsulfonated polysaccharide is a sulfoethylated water-soluble starch which is incorporated into the said mix in an amount of from 0.35% to 0.55% of the weight of said binder and has a degree of sulfonation of from 0.8 to about 1.3.
1 6. Mortar or concrete produced from a composition as defined in any one of claims 9 to 13.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT19879/83A IT1161592B (en) | 1983-03-03 | 1983-03-03 | ALCHYL SULPHONATED POLYSACCHARIDS WITH FLUIDIFYING ACTIVITY AND MATLE AND CONCRETE CONTAINING THOSE POLYSACCHARIDES |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8405407D0 GB8405407D0 (en) | 1984-04-04 |
| GB2138014A true GB2138014A (en) | 1984-10-17 |
| GB2138014B GB2138014B (en) | 1986-04-09 |
Family
ID=11162016
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08405407A Expired GB2138014B (en) | 1983-03-03 | 1984-03-01 | Alkylsulfonated polysaccharides and mortar and concrete mixes containing them |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | USH493H (en) |
| BE (1) | BE899046A (en) |
| CA (1) | CA1217482A (en) |
| CH (1) | CH659241A5 (en) |
| DE (1) | DE3406745A1 (en) |
| FR (1) | FR2541990A1 (en) |
| GB (1) | GB2138014B (en) |
| IT (1) | IT1161592B (en) |
| NL (1) | NL8400642A (en) |
| SE (1) | SE8401151L (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0554749A3 (en) * | 1992-02-07 | 1993-09-29 | Wolff Walsrode Aktiengesellschaft | Water soluble sulfoalkyl hydroxyalkyl derivatives of cellulose and their use in gypsum and cement compositions |
| EP0573852A1 (en) * | 1992-06-06 | 1993-12-15 | Hoechst Aktiengesellschaft | Sulphoalkyl groups containing alkyl hydroxyalkyl cellulose ether |
| US5358561A (en) * | 1992-02-07 | 1994-10-25 | Wolff Warlsrode Ag | Use of water-soluble sulphoalkyl derivatives of cellulose in gypsum-and cement-containing compounds |
| 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 |
| US5591844A (en) * | 1992-06-06 | 1997-01-07 | Hoechst Aktiengesellschaft | Alkyl hydroxyalkyl cellulose ethers containing sulfoalkyl groups |
| DE19543304A1 (en) * | 1995-11-21 | 1997-05-22 | Sueddeutsche Kalkstickstoff | Environmentally friendly additive for building material mix |
| WO1998050320A1 (en) * | 1997-05-06 | 1998-11-12 | F.B.C. Future Biologic Chemicals S.R.L. | Cement fluidifiers having a starch sulphate base |
| US6893497B2 (en) | 2001-03-22 | 2005-05-17 | Degussa Construction Chemicals Gmbh | Use of water-soluble polysaccharide derivatives as dispersing agents for mineral binder suspensions |
Families Citing this family (4)
| 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 |
| DE19519025C1 (en) * | 1995-05-24 | 1996-12-05 | Hoechst Ag | Starch etherified to a high degree with alkyl sulfonic acid residues |
| US6068697A (en) * | 1996-11-27 | 2000-05-30 | Kao Corporation | Polysaccharide derivatives and hydraulic compositions |
| BRPI0417144B1 (en) * | 2003-12-01 | 2017-03-28 | Gcp Applied Tech Inc | method for modifying a cementitious composition |
Family Cites Families (10)
| 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 |
| US3332791A (en) * | 1964-05-12 | 1967-07-25 | Rayonier Inc | Process for producing portland cement compositions |
| US3530112A (en) | 1967-07-24 | 1970-09-22 | Itt Rayonier Inc | Process for preparing dispersants useful in hydraulic cement slurries |
| JPS6018615B2 (en) | 1976-03-10 | 1985-05-11 | 花王株式会社 | Hydraulic cement composition |
-
1983
- 1983-03-03 IT IT19879/83A patent/IT1161592B/en active
-
1984
- 1984-02-01 US US06/575,733 patent/USH493H/en not_active Abandoned
- 1984-02-24 DE DE19843406745 patent/DE3406745A1/en not_active Withdrawn
- 1984-02-29 NL NL8400642A patent/NL8400642A/en not_active Application Discontinuation
- 1984-02-29 FR FR8403166A patent/FR2541990A1/en not_active Withdrawn
- 1984-03-01 GB GB08405407A patent/GB2138014B/en not_active Expired
- 1984-03-01 SE SE8401151A patent/SE8401151L/en not_active Application Discontinuation
- 1984-03-01 BE BE212480A patent/BE899046A/en unknown
- 1984-03-02 CH CH1020/84A patent/CH659241A5/en not_active IP Right Cessation
- 1984-03-02 CA CA000448712A patent/CA1217482A/en not_active Expired
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0554749A3 (en) * | 1992-02-07 | 1993-09-29 | Wolff Walsrode Aktiengesellschaft | Water soluble sulfoalkyl hydroxyalkyl derivatives of cellulose and their use in gypsum and cement compositions |
| US5358561A (en) * | 1992-02-07 | 1994-10-25 | Wolff Warlsrode Ag | Use of water-soluble sulphoalkyl derivatives of cellulose in gypsum-and cement-containing compounds |
| US5385607A (en) * | 1992-02-07 | 1995-01-31 | Wolff Walsrode Ag | Water-soluble sulphoalkyl hydroxyalkyl derivatives of cellulose and their use in gypsum- and cement-containing compounds |
| EP0573852A1 (en) * | 1992-06-06 | 1993-12-15 | Hoechst Aktiengesellschaft | Sulphoalkyl groups containing alkyl hydroxyalkyl cellulose ether |
| US5395930A (en) * | 1992-06-06 | 1995-03-07 | Hoechst Ag | Alkyl hydroxyalkyl cellulose ethers containing sulfoalkyl substituents |
| 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 |
| DE19543304A1 (en) * | 1995-11-21 | 1997-05-22 | Sueddeutsche Kalkstickstoff | Environmentally friendly additive for building material mix |
| DE19543304B4 (en) * | 1995-11-21 | 2005-06-09 | Skw Bauchemie Gmbh | Additive for water-containing building material mixtures and its use |
| WO1998050320A1 (en) * | 1997-05-06 | 1998-11-12 | F.B.C. Future Biologic Chemicals S.R.L. | Cement fluidifiers having a starch sulphate base |
| US6893497B2 (en) | 2001-03-22 | 2005-05-17 | Degussa Construction Chemicals Gmbh | Use of water-soluble polysaccharide derivatives as dispersing agents for mineral binder suspensions |
Also Published As
| Publication number | Publication date |
|---|---|
| CA1217482A (en) | 1987-02-03 |
| IT8319879A1 (en) | 1984-09-03 |
| GB8405407D0 (en) | 1984-04-04 |
| IT1161592B (en) | 1987-03-18 |
| USH493H (en) | 1988-07-05 |
| FR2541990A1 (en) | 1984-09-07 |
| DE3406745A1 (en) | 1984-09-06 |
| IT8319879A0 (en) | 1983-03-03 |
| BE899046A (en) | 1984-07-02 |
| SE8401151D0 (en) | 1984-03-01 |
| SE8401151L (en) | 1984-09-04 |
| GB2138014B (en) | 1986-04-09 |
| NL8400642A (en) | 1984-10-01 |
| CH659241A5 (en) | 1987-01-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 732 | Registration of transactions, instruments or events in the register (sect. 32/1977) | ||
| PCNP | Patent ceased through non-payment of renewal fee |