CA1217482A - Alkylsulfonated polysaccharides and mortar and concrete mixes containing them - Google Patents
Alkylsulfonated polysaccharides and mortar and concrete mixes containing themInfo
- Publication number
- CA1217482A CA1217482A CA000448712A CA448712A CA1217482A CA 1217482 A CA1217482 A CA 1217482A CA 000448712 A CA000448712 A CA 000448712A CA 448712 A CA448712 A CA 448712A CA 1217482 A CA1217482 A CA 1217482A
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- Prior art keywords
- degree
- alkylsulfonated
- sulfonation
- polysaccharide
- mortar
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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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
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- 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
ABSTRACT OF THE DISCLOSURE
Alkylsulfonated polysaccharides, methods of making them and use of said polysaccharides for improving the flowability of mortar and concrete mixes are disclosed.
Alkylsulfonated polysaccharides, methods of making them and use of said polysaccharides for improving the flowability of mortar and concrete mixes are disclosed.
Description
7l3~2-1 The instant invention concerns imprOVeMents in mortar and concrete mixes.
Particularly, the improvement of the instant invention consists of admixing mortar or concrete with a small amount of a fluidizing agent, vis.
alkylsulfonated polysaccharides.
More particularly, 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.
~t is known in the art 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 which would be necessary for the full hydration of the hydraulic binder employed for making the mix.
The water excess, particularly in the case of high workability, 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.).
In order to obtain a good workability of mortar and concrete mixes with lower W/C ratios, particular materials have long been proposed, and a number of them have reached 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, i.e. fluidizing agents and superfluidizing agents. If the agent allows, in standard plastic mortars, a ater reduction of not less than 6% (i.e. ~lR - VA
100-- = 6qo ~nerein VR is the water volume of the reference mix and VA is the water ~olume, inclusive of the fluidizing agent, of the fluidizing-agent-containing ~iX), 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 - VA
100 VR ~ 10%
hherein VR 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 8145 the material is defined as a super-fluidizing agent. Pluidizing and superfluidizing agents as above defined meet roquirements for type A and type F concrete mixes specified in ASTM C 494-80.
Known useFul fluidizing agents are lignine-sulfonates, gluconates and tannates.
Some known industrial carbohydrates such as, e.g. glucose syrups ~v. United States Patent 3,432,317) and modified starch hydrolizates ( v. Appli~can~s' Canadi~an Patent~No. 1,175,QA5 ~ are commonly us~d in cement mixes both for improving the rheologic properties of the mixes as well as-for improving their mechanical strength. Their water reducing capability, th~ugh, is very limited and much inferior to that of the superfluidizers.
Industrially, the use of superfluidizers has acquired importance only during the past five yeàrs or so.
Known superfluidizers are made of polynaphthalene sulonates tv.
e.g. United States Patent 2,141,569; DE-AS 1,238,831 ; CA Patent 993,901) 48~
and of sulfonated malamine resins (v.e.g. IT Patent 801,078).
It has now been found that by sulfonating polysaccharides with suitable sulfonating agents excellent superfluidizing agents having superior properties with respect to all the 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 lO0, a degree of sulfonation (D.S.) as hereinafter defined and determined, of from 0.2 to 3Ø 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.
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. chloromethylsul~onic acid, chloroethane sulfonic acid, chloropropane sulfonic acid and 1,3 propane-sultone.
The preferred inventive superfluidizers are those made oE hydrolized cellulose sulfonated with chloromethane or chloroethane sulfonic acid.
Superfluidizers made of wood molasses sulfonated with chloropropane-sulfonic acid as Nell as hydrolized starches sulfonated with chloroethane or chloropropane sulfonic acid are even more preferred.
At present, the most preferred inventive superfluidizers are those obtained from water soluble st~rch hydrolizates having a polymerization degree ~2~7~
equal or lower than 100 and chloroethanesulfonic acid, as the sulfonating agent.
It would appear that the fluidizing activity of the i-nven~ive agents is a function of the starting polysaccharides and of the sulfonating agents used. This statement is supported by the data shown in the following Table.
FLOW TESTS
FLUIDIZER DO~AGES ~b) FLOW (mm) referred to plain 1) hemicellulose 0.6 +12 sulfopropylate ~a) 1.5 ~24
Particularly, the improvement of the instant invention consists of admixing mortar or concrete with a small amount of a fluidizing agent, vis.
alkylsulfonated polysaccharides.
More particularly, 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.
~t is known in the art 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 which would be necessary for the full hydration of the hydraulic binder employed for making the mix.
The water excess, particularly in the case of high workability, 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.).
In order to obtain a good workability of mortar and concrete mixes with lower W/C ratios, particular materials have long been proposed, and a number of them have reached 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, i.e. fluidizing agents and superfluidizing agents. If the agent allows, in standard plastic mortars, a ater reduction of not less than 6% (i.e. ~lR - VA
100-- = 6qo ~nerein VR is the water volume of the reference mix and VA is the water ~olume, inclusive of the fluidizing agent, of the fluidizing-agent-containing ~iX), 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 - VA
100 VR ~ 10%
hherein VR 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 8145 the material is defined as a super-fluidizing agent. Pluidizing and superfluidizing agents as above defined meet roquirements for type A and type F concrete mixes specified in ASTM C 494-80.
Known useFul fluidizing agents are lignine-sulfonates, gluconates and tannates.
Some known industrial carbohydrates such as, e.g. glucose syrups ~v. United States Patent 3,432,317) and modified starch hydrolizates ( v. Appli~can~s' Canadi~an Patent~No. 1,175,QA5 ~ are commonly us~d in cement mixes both for improving the rheologic properties of the mixes as well as-for improving their mechanical strength. Their water reducing capability, th~ugh, is very limited and much inferior to that of the superfluidizers.
Industrially, the use of superfluidizers has acquired importance only during the past five yeàrs or so.
Known superfluidizers are made of polynaphthalene sulonates tv.
e.g. United States Patent 2,141,569; DE-AS 1,238,831 ; CA Patent 993,901) 48~
and of sulfonated malamine resins (v.e.g. IT Patent 801,078).
It has now been found that by sulfonating polysaccharides with suitable sulfonating agents excellent superfluidizing agents having superior properties with respect to all the 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 lO0, a degree of sulfonation (D.S.) as hereinafter defined and determined, of from 0.2 to 3Ø 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.
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. chloromethylsul~onic acid, chloroethane sulfonic acid, chloropropane sulfonic acid and 1,3 propane-sultone.
The preferred inventive superfluidizers are those made oE hydrolized cellulose sulfonated with chloromethane or chloroethane sulfonic acid.
Superfluidizers made of wood molasses sulfonated with chloropropane-sulfonic acid as Nell as hydrolized starches sulfonated with chloroethane or chloropropane sulfonic acid are even more preferred.
At present, the most preferred inventive superfluidizers are those obtained from water soluble st~rch hydrolizates having a polymerization degree ~2~7~
equal or lower than 100 and chloroethanesulfonic acid, as the sulfonating agent.
It would appear that the fluidizing activity of the i-nven~ive agents is a function of the starting polysaccharides and of the sulfonating agents used. This statement is supported by the data shown in the following Table.
FLOW TESTS
FLUIDIZER DO~AGES ~b) FLOW (mm) 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 respectively.
(b) Dosages are expressed as percent (dry to dry) of the amount of cement in the mix.
As it can be take-n from Table 1~ the fluidizers made of water soluble starches with polymerization degree of up to 100 and chloroethane sulfonic acid yield the best results, never achieved before with any known fluidizers or superfluidzers. The flow tests of Table 1 have been made with plastic mortars according to the Italian Standard UNI 8020, using P~ 325 cement (which is commonly used in industry).
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. Other useful cations can be 179~
chosen from ammonium or the organic amines.
When the cation is derived from an organic amine, 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 following examples are illustrative of the inventive superfluid~
izers, the way of making them as well as the way of using them in mortar and concrete mixes.
E~MPLE 1 Hemicellulose sulfopropylate 100 g of a hemicellulose slightly soluble in water at room temperature suspended in 300 ml water containing 75 g NaOII are added with 450 g of 1,3 propane-sultone and reacted 16 hrs. at 50C under stirring. Then reaction mixture is allowed to stand for 48 hrs. at ambient temperature. The pH is then adjusted to 4 with 2N sodium hydroxide and the title product is precipitated with methyl alcohol.
The yield is 80% of the theory. The substitution degree is 0.9.
~XAMPLE 2 Starch sulfopropylate 80 g of starch not soluble in water at room temperature suspended in 250 ml water containing 60 g ~aOH are added with 350 g of 1J3 propane-sultone and reacted 16 hrs. at 50C under stirring.
The reaction mixture is then allowed to stand ~or 48 hrs. at ambient temperature and the pH is adjusted to 4 with 2N 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 l.l.
E~AMPLE 3 _ = =
Water soluble starch solfoethylate~
lOO g of starch, easily solu~le in water at room temperature suspended in lOOO ml isopropyl alcohol are added with 175 g of the sodium salt of 2-chloroethanesulfonic acid and a solution of ~5 g of NaOH in 100 ml water is reacted, under stirring, for 15 min. at 30C and then further 60 min. at 80C.
The reaction is interrupted by cooling at room temperature.
After neutralizing with acetic acid, the water phase is dialyzed through a 3S00 Dalton cellulose acetate membrane.
The yield is 80% of the theory. The substitution degree is 0.6.
As already said above, the fluidizing activity of the inventive agents appears to be a function of the starting polysaccharides and of the sul~onating agent used.
It further appears that such activity also depends on the sulfona-tion degree, i.e. the mean number of alkyl sulfonic groups per repeating unit of the polysaccharide chain.
It has been ~ound that 0.2 is the minimum degree of sulfonation necessary for improving the fluidi~ing activity of the used polysaccharide, according to the instant invention.
It has further been ascertained that in order to obtain a fluid izing agent with outstanding activity (i.e. an activity greater than what is considered normal in the art) the degree of sulfonation must exceed l.
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 ~ NMR).
The NMR spectra shown in Figure 1 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 corres-ponding to the -Cl-12~ groups of the sulfoethyl and sulfopropyl substitutents.
These signals permit 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 10on the degree of sulfonation.
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 ~9 +17 1.1~ 139 ~67 1.35 151 ~79 1.50 165 -~93 * This corresponds to the starting material, i.e. the unsubstituted or non-sulfoalkylated ~ater soluble starch.
The sulfonated derivatives in Table 2 have been prepared by subject-ing 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.~ of the weight of the cement.
'7~
The data in Table 2 shows that the addition o:E 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 non-additioned mortar).
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, though, 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.
With the addition of 0.4% of an inventive superfluidizer having a D.S. value of 1.10, the fluidizing effect attained is in the range of those obtainable with cm equal amount of commercial superfluidizers.
Finally, the addition of 0.4% of an inventive 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 any known superfluidizer.
The possibility of fluidizing the mortar and concrcte 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.
According to the present invention, interesting results (with respect to flowability) are obtained with dosages between 0.1% and 0.4% (of the weight of the hydraulic binder) and high D.S. values, i.e. greater than 1Ø
For achieving results of the same order of magnitude using fluidizers having a medium degree of sulfonation, i.e. with D.S. values i.n the range of from 0.8 to 1.2, the dosage of the fluidizer shall be in the range of 7~
from 0.2% to 0.6%.
When using flu:idizers having a low degree of sulfonation, i.e.
having D.S. values ranging from between 0.2 to 0.5, dosages greater than 0.6%
are needed.
In particular, when using sulfoethylated water soluble starches (having a polymerization degree of s 100), it has been folmd that with dosages of from 0.35% to 0.55% (of the weight of the hydraulic binder) and a D.S. value in thearea of 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 said starches is in the area of 1, then 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 in the area of 1.3, the flo~bility of the mortar and concrete mix containing it is greater than that obtainable with any of the known superfluidizers.
The following Table 3 outlines the results attained with a commercial water soluble starch having a polymerization degree of ~ 100, at increasing D.S. values, in comparison with fluidizers known in the art.
7~
COhJPARISON OF TIIE INVENrl`IVE SU~ERFLUIDIZERS WITII KNOWN
FLUIDIZERS AND SUPERFLUIDIZERS OF TIE COh~ERCE
_ . COMPRESSIVE
FLUIDIZER FLOW (mm) STREN2GTH
(Kg/cm ) at 7 days _ . _ _ . ... .. ~
~bsolute Referred Absolute Referred value to plain value to plain 1- Commercial water soluble starch sulfoethylate (of the invention) D.S. = 0.8 8g + 17 292 + 66 2- Raw calcium lignine sulfo-nate liquor 85 + 13 260 t 34 _ 3- sodium gluconate mother liquor 90 + 18 253 -~ 27 _ _
(b) Dosages are expressed as percent (dry to dry) of the amount of cement in the mix.
As it can be take-n from Table 1~ the fluidizers made of water soluble starches with polymerization degree of up to 100 and chloroethane sulfonic acid yield the best results, never achieved before with any known fluidizers or superfluidzers. The flow tests of Table 1 have been made with plastic mortars according to the Italian Standard UNI 8020, using P~ 325 cement (which is commonly used in industry).
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. Other useful cations can be 179~
chosen from ammonium or the organic amines.
When the cation is derived from an organic amine, 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 following examples are illustrative of the inventive superfluid~
izers, the way of making them as well as the way of using them in mortar and concrete mixes.
E~MPLE 1 Hemicellulose sulfopropylate 100 g of a hemicellulose slightly soluble in water at room temperature suspended in 300 ml water containing 75 g NaOII are added with 450 g of 1,3 propane-sultone and reacted 16 hrs. at 50C under stirring. Then reaction mixture is allowed to stand for 48 hrs. at ambient temperature. The pH is then adjusted to 4 with 2N sodium hydroxide and the title product is precipitated with methyl alcohol.
The yield is 80% of the theory. The substitution degree is 0.9.
~XAMPLE 2 Starch sulfopropylate 80 g of starch not soluble in water at room temperature suspended in 250 ml water containing 60 g ~aOH are added with 350 g of 1J3 propane-sultone and reacted 16 hrs. at 50C under stirring.
The reaction mixture is then allowed to stand ~or 48 hrs. at ambient temperature and the pH is adjusted to 4 with 2N 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 l.l.
E~AMPLE 3 _ = =
Water soluble starch solfoethylate~
lOO g of starch, easily solu~le in water at room temperature suspended in lOOO ml isopropyl alcohol are added with 175 g of the sodium salt of 2-chloroethanesulfonic acid and a solution of ~5 g of NaOH in 100 ml water is reacted, under stirring, for 15 min. at 30C and then further 60 min. at 80C.
The reaction is interrupted by cooling at room temperature.
After neutralizing with acetic acid, the water phase is dialyzed through a 3S00 Dalton cellulose acetate membrane.
The yield is 80% of the theory. The substitution degree is 0.6.
As already said above, the fluidizing activity of the inventive agents appears to be a function of the starting polysaccharides and of the sul~onating agent used.
It further appears that such activity also depends on the sulfona-tion degree, i.e. the mean number of alkyl sulfonic groups per repeating unit of the polysaccharide chain.
It has been ~ound that 0.2 is the minimum degree of sulfonation necessary for improving the fluidi~ing activity of the used polysaccharide, according to the instant invention.
It has further been ascertained that in order to obtain a fluid izing agent with outstanding activity (i.e. an activity greater than what is considered normal in the art) the degree of sulfonation must exceed l.
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 ~ NMR).
The NMR spectra shown in Figure 1 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 corres-ponding to the -Cl-12~ groups of the sulfoethyl and sulfopropyl substitutents.
These signals permit 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 10on the degree of sulfonation.
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 ~9 +17 1.1~ 139 ~67 1.35 151 ~79 1.50 165 -~93 * This corresponds to the starting material, i.e. the unsubstituted or non-sulfoalkylated ~ater soluble starch.
The sulfonated derivatives in Table 2 have been prepared by subject-ing 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.~ of the weight of the cement.
'7~
The data in Table 2 shows that the addition o:E 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 non-additioned mortar).
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, though, 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.
With the addition of 0.4% of an inventive superfluidizer having a D.S. value of 1.10, the fluidizing effect attained is in the range of those obtainable with cm equal amount of commercial superfluidizers.
Finally, the addition of 0.4% of an inventive 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 any known superfluidizer.
The possibility of fluidizing the mortar and concrcte 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.
According to the present invention, interesting results (with respect to flowability) are obtained with dosages between 0.1% and 0.4% (of the weight of the hydraulic binder) and high D.S. values, i.e. greater than 1Ø
For achieving results of the same order of magnitude using fluidizers having a medium degree of sulfonation, i.e. with D.S. values i.n the range of from 0.8 to 1.2, the dosage of the fluidizer shall be in the range of 7~
from 0.2% to 0.6%.
When using flu:idizers having a low degree of sulfonation, i.e.
having D.S. values ranging from between 0.2 to 0.5, dosages greater than 0.6%
are needed.
In particular, when using sulfoethylated water soluble starches (having a polymerization degree of s 100), it has been folmd that with dosages of from 0.35% to 0.55% (of the weight of the hydraulic binder) and a D.S. value in thearea of 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 said starches is in the area of 1, then 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 in the area of 1.3, the flo~bility of the mortar and concrete mix containing it is greater than that obtainable with any of the known superfluidizers.
The following Table 3 outlines the results attained with a commercial water soluble starch having a polymerization degree of ~ 100, at increasing D.S. values, in comparison with fluidizers known in the art.
7~
COhJPARISON OF TIIE INVENrl`IVE SU~ERFLUIDIZERS WITII KNOWN
FLUIDIZERS AND SUPERFLUIDIZERS OF TIE COh~ERCE
_ . COMPRESSIVE
FLUIDIZER FLOW (mm) STREN2GTH
(Kg/cm ) at 7 days _ . _ _ . ... .. ~
~bsolute Referred Absolute Referred value to plain value to plain 1- Commercial water soluble starch sulfoethylate (of the invention) D.S. = 0.8 8g + 17 292 + 66 2- Raw calcium lignine sulfo-nate liquor 85 + 13 260 t 34 _ 3- sodium gluconate mother liquor 90 + 18 253 -~ 27 _ _
4- Commercial water soluble starch sulfoethylate (of the invention) D.S. = l.O 129 + 47 ?89 ~ 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 ,, _ . __ _ Tlle following Table 4 outlines the superlor 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).
FLUIDIZER ~ W/C flow ; ~ " ~ ) Plain 225 0.5 85 260 Sulfoalkylated starch 1~4 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:
100. 225 1~4 = 14%
is greater than the water reduction obtained with the known superfluidizer (polynaphthalene sulfonate):
100. 225 - 200 = 11 Tests summarized in Table 3 and 4 are 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 weigh* 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 the commerce.
: - 11-~ABLE _ Cement type ¦ CementW/C ¦ slump Compressive strengths dosa3gevalue (kg/cm2) kg/m (cm) 3 days 7 days 28 d~ys 425 Portland 350 0.55 ¦ 8 230 336 400 idem + polynaph-thalene sulfonate 350 0.44 8 388 449 590 idem ~ sulfoalkyl-starch 350 0.44 10 368 460 605 The 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, Port-land-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.
It is expedient to note that the 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.
The 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.
Alternatively, the 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. In this case, it can be mixed with known grinding aids such as~ e.g.
alkanolamines and glycols.
~;~1'7~
Although the instant invention is advantageously applicable to the production of any kind of mortar and concrete, this invention is particularly clirected 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.
FLUIDIZER ~ W/C flow ; ~ " ~ ) Plain 225 0.5 85 260 Sulfoalkylated starch 1~4 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:
100. 225 1~4 = 14%
is greater than the water reduction obtained with the known superfluidizer (polynaphthalene sulfonate):
100. 225 - 200 = 11 Tests summarized in Table 3 and 4 are 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 weigh* 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 the commerce.
: - 11-~ABLE _ Cement type ¦ CementW/C ¦ slump Compressive strengths dosa3gevalue (kg/cm2) kg/m (cm) 3 days 7 days 28 d~ys 425 Portland 350 0.55 ¦ 8 230 336 400 idem + polynaph-thalene sulfonate 350 0.44 8 388 449 590 idem ~ sulfoalkyl-starch 350 0.44 10 368 460 605 The 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, Port-land-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.
It is expedient to note that the 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.
The 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.
Alternatively, the 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. In this case, it can be mixed with known grinding aids such as~ e.g.
alkanolamines and glycols.
~;~1'7~
Although the instant invention is advantageously applicable to the production of any kind of mortar and concrete, this invention is particularly clirected 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.
Claims (14)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A superfluidizing agent for mortar or concrete compris-ing an alkylsulfonated polysaccharide, chosen from hemicellulose, wood molasses, or starch, having a degree of polymerization of up to 100 and a degree of sulfonation of from 0.2 to 3Ø
2. A superfluidizing agent of claim 1 wherein said degree of sulfonation is from 0.2 to 1.5.
3. A superfluidizing agent of claim l wherein said alkylsulfonated polysaccharide is an alkylsulfonated water soluble starch.
4. A superfluidizing agent of claim 3 wherein said alkylsulfonated water soluble starch is prepared by a process com-prising alkylsulfonation of a water soluble starch with chloroeth-anesulfonic acid.
5. A superfluidizing agent of claim 3 wherein said degree of sulfonation is about 1.3 or greater.
6. A hydraulic cementitious composition comprising a hydraulic cement binder and an alkylsulfonated polysaccharide, chosen from hemicellulose, wood molasses, or starch, having a degree of polymerization of up to 100 and a degree of sulfonation of from 0.2 to 3Ø
7. A composition of claim 6 wherein said alkyl sulfonated polysaccharide is present in an amount of from 0.1% to 0.4% of the weight of said binder and said degree of sulfonation is greater than 1Ø
8. A composition of claim 6 wherein said alkylsulfonated polysaccharide is present in an amount of from 0.2% to 0.6% of the weight of said binder and said degree of sulfonation is from 0.8 to 1.2.
9. A composition of claim 6 wherein said alkylsulfonated polysaccharide is present in an amount greater than 0.6% by weight of said binder and said degree of sulfonation is from 0.2 to 0.5.
10. A composition of claim 6 wherein said alkylsulfonated polysaccharide is an alkylsulfonated water soluble starch.
11. A composition of claim 10 wherein said alkylsulfonated polysaccharide is a sulfoethylated water soluble starch which is present in an amount of from 0.35% to 0.55% of the weight of said hydraulic binder and said degree of sulfonation is from about 0.8 to about 1.3.
12. 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 alkylsul-fonated polysaccharide, chosen from hemicellulose, wood molasses, or starch, having a degree of polymerization of up to 100 and a degree of sulfonation of from 0.2 to 3Ø
by weight, based on the weight of said binder, of an alkylsul-fonated polysaccharide, chosen from hemicellulose, wood molasses, or starch, having a degree of polymerization of up to 100 and a degree of sulfonation of from 0.2 to 3Ø
13. A method of claim 12 wherein said degree of sulfonation is from 0.2 to 1.5.
14. A method of claim 12 wherein said alkylsulfonated poly-saccharide is a sulfoethylated water soluble starch which is incor-porated into 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 about 0.8 to about 1.3.
Applications Claiming Priority (2)
| 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 |
| IT19879A/83 | 1983-03-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1217482A true CA1217482A (en) | 1987-02-03 |
Family
ID=11162016
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000448712A Expired CA1217482A (en) | 1983-03-03 | 1984-03-02 | 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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4203530A1 (en) * | 1992-02-07 | 1993-08-12 | Wolff Walsrode Ag | USE OF WATER SOLUBLE SULFOALKYL DERIVATIVES OF CELLULOSE IN PLASTER AND CEMENT CONTAINERS |
| DE4203529A1 (en) * | 1992-02-07 | 1993-08-12 | Wolff Walsrode Ag | WATER-SOLUBLE SULFOALKYL HYDROXYALKYL DERIVATIVES OF CELLULOSE AND THEIR USE IN PLASTER AND CEMENT CONTAINERS |
| US5591844A (en) * | 1992-06-06 | 1997-01-07 | Hoechst Aktiengesellschaft | Alkyl hydroxyalkyl cellulose ethers containing sulfoalkyl groups |
| TR27111A (en) * | 1992-06-06 | 1994-11-09 | Hoechst Ag | Alkylhydroxyalkyl cellulose ethers containing sulfoacyl group. |
| US5573589A (en) * | 1993-03-10 | 1996-11-12 | Sandoz Ltd. | Cement compositions containing a sulfated polysaccharide and method |
| 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 (en) * | 1995-11-21 | 2005-06-09 | Skw Bauchemie Gmbh | Additive for water-containing building material mixtures and its use |
| WO1998023647A1 (en) * | 1996-11-27 | 1998-06-04 | Kao Corporation | Polysaccharide derivatives and hydraulic compositions |
| IT1291309B1 (en) * | 1997-05-06 | 1999-01-07 | F B C Future Biolog Chemicals | CEMENTITIOUS FLUIDIZERS BASED ON SULPHATES |
| DE10209812A1 (en) | 2001-03-22 | 2002-09-26 | Degussa Construction Chem Gmbh | Water-soluble polysaccharide derivatives used as dispersants for mineral binder suspensions, optionally contain hydroxyalkyl and/or sulfate groups |
| KR20060109471A (en) * | 2003-12-01 | 2006-10-20 | 더블유.알. 그레이스 앤드 캄파니-콘. | Gluconate broth for cement and concrete admixture |
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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8405407D0 (en) | 1984-04-04 |
| SE8401151D0 (en) | 1984-03-01 |
| GB2138014B (en) | 1986-04-09 |
| IT8319879A0 (en) | 1983-03-03 |
| CH659241A5 (en) | 1987-01-15 |
| NL8400642A (en) | 1984-10-01 |
| SE8401151L (en) | 1984-09-04 |
| USH493H (en) | 1988-07-05 |
| DE3406745A1 (en) | 1984-09-06 |
| GB2138014A (en) | 1984-10-17 |
| FR2541990A1 (en) | 1984-09-07 |
| BE899046A (en) | 1984-07-02 |
| IT8319879A1 (en) | 1984-09-03 |
| IT1161592B (en) | 1987-03-18 |
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