FR2595347A1 - Synthesis of new oligomers for concretes - Google Patents

Abstract

Synthesis of new oligomers originating from a reaction between one or a number of water-soluble mercaptans and one or a number of chiefly sulphonic water-soluble monomers which have at least one sulphonic acid functional group or the corresponding sodium salt. Application of these oligomers in hydraulic binders such as cements, plasters, clays, anhydrites and others, as plasticisers.

Description

The subject of the present invention is the synthesis of new so-called oligomeric fluidifiers, and their application in hydraulic binders such as cements, plasters, clays, anhydrite and others.
The present invention also relates to inorganic binders comprising the fluidifiers according to the invention
Until now the fluidifiers also known as plasticizers reducing glands are mainly polycondensates calcium formalin-naphthalenesulphonate or sodium German patent
OS 1,941,576 and formaldehyde-melamine polycondensates modified with sodium hydrogen sulfite German Patent No. 1,745,441.

ou F est une fonction solubilisante du type hydroxyle, acide carboxylique, acide sufonique, amine, amide, urée, thiourée, guanidine où E l'alkylène à chaine linéaire ou ramifiée avec 1 à 10 atomes de carbone où E l'alkylène à chaine aliphatique ou ramifiée avec 1 à 8 atomes de carbone du type
-CO-N (R)-E" , -S2N(R)-E" , E"-CO-N(R)-E"
-E"-S-E"- , -E"-N(R)-E"- , E"-SO2-N(R)-E"
R'représente ici l'hydrogène ou l'alkyl avec 1 à 4 atomes de carbone, E" l'alkylène avec 1 à 8 atomes de carbone et l'alkylène avec 1 à 4 atomes de carbone où M1 une unité dérivée d'un monomère sulfonique et M2 une unitédérivée d'un monomère carboxylique, la somme de x et y est comprise entre 4 et 800 ; x entre 1 et 0,9 , x est
x+y un nombre entier de 4 à 800 et y = O ou un nombre entier allant jusqu'à 50
Les nouveaux oligomères du brevet-, conformément à l'invention sont synthétisés par le fait qu'on polymérise un ou plusieurs monomères.sulfoniques de type M1 , le cas échéant avec un ou plusieurs monomères carboxyliques de type M2 en présence d'un mercaptan de formule
F-E-E~-SH (2)
F , E et E' ayant signification plus haut
Les mercaptans préférés sont : le mercaptoéthanol, l'acide thioglycolique, le thioglycérol ainsi que les suivants de formule
HO-CHE CH2- S-CH2-0H2-SH
HO-CH2-CH2-O -CH2- 0112511
HO-CIH;-N(CH,)-CH2-CH2'CH2-SH
HO-CH2-CH2-SO2-NH-CH2-CH2-CH2-SH
HO-CH2-SO2-N(CH3)-CH2-CH2-SH
HO-CH2-CH2-CO-NH-CH2-CH2-CH2-SH HO-CH2- CH2- S02-NHCH2-CH2-SH
HO-CH2-CH2-SO2-N(CH3)-CH2-CH2-SH où la fonction hydroxyle peut être substituée par une fonction du type carboxylique, acide sulfonique, amine, amide, urée, thiourée, guanidine, etc
Les monomères sulfoniques du type M1 sont caractérisés par le fait qu'ils possèdent au moins une fonction acide sulfonique.Recently, in European patent 99,954 are described water-soluble condensation products of amine sulfonic acids with one or more aromatic rings of nitrogen products with several amine functional groups or of polyamine products, the product structures described in the recent European patents are essentially lignosulphonates. and more particularly polycondensates of naphthalenesulfonic acids condensed with European patent formalin 73 606, 32 730
7390, 4,628, 3,362
The object of the invention is to obtain oligomers having a low polydispersity (ratio of the degree of polymerization by weight to the average degree of polymerization by number). Indeed, these water-soluble oligomers have a low polydispersity of the order of 1 , 1 to 1.2, and thus give better results with regard to their action in concrete mortars and the like, ie a greater water reduction with identical plasticity obtained under the same conditions by polynaphthalenesulfonates and polymelaminesulfonates which have a polydispersity of the order of 2, Q
The oligomers of the invention are characterized in that they result from the synthesis between at least one optionally branched aliphatic or aromatic mercaptan having at least one solubilizing function, and one or more predominantly sulfonic monomers polymerized in aqueous phase under conditions radical
In general, the oligomers of the invention are described by the following formula

or F is a solubilizing function of the hydroxyl, carboxylic acid, sufonic acid, amine, amide, urea, thiourea or guanidine type where E is the linear or branched chain alkylene with 1 to 10 carbon atoms where E is the aliphatic chain alkylene or branched with 1 to 8 carbon atoms of the type
-CO-N (R) -E ", -S2N (R) -E", E "-CO-N (R) -E"
-E "-SE" -, -E "-N (R) -E" -, E "-SO 2 -N (R) -E"
Here is hydrogen or alkyl with 1 to 4 carbon atoms, E "alkylene with 1 to 8 carbon atoms and alkylene with 1 to 4 carbon atoms where M 1 a unit derived from a sulphonic monomer and M2 a derived unit of a carboxylic monomer, the sum of x and y is between 4 and 800, x between 1 and 0.9, x is
x + y an integer from 4 to 800 and y = 0 or an integer of up to 50
The novel oligomers of the patent according to the invention are synthesized by the fact that one or more monomers M1 type sulfonates, optionally with one or more carboxyl type monomers M2 in the presence of a mercaptan of the type M1, are polymerized. formula
FEE ~ -SH (2)
F, E and E 'having higher meanings
The preferred mercaptans are: mercaptoethanol, thioglycolic acid, thioglycerol and the following formulas
HO-CH CH2- S-CH2-OH2-SH
HO-CH2-CH2-O-CH2-0112511
HO-CIH; -N (CH,) - CH2-SH-CH2'CH2
HO-CH2-CH2-SO2-NH-CH2-CH2-CH2-SH
HO-CH2-SO2-N (CH3) -CH2-CH2-SH
HO-CH2-CH2-CO-NH-CH2-CH2-CH2-SH HO-CH2-CH2-SO2-NHCH2-CH2-SH
HO-CH2-CH2-SO2-N (CH3) -CH2-CH2-SH wherein the hydroxyl function may be substituted by a function of the carboxylic, sulfonic acid, amine, amide, urea, thiourea, guanidine, etc.
The M1-type sulfonic monomers are characterized in that they have at least one sulfonic acid function.

The molar ratio of monomers to telogens (mercaptans) is between 4 and 800.

The sulfonic monomers have general formulas

R1 = H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
tert,
methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy,
phenyl, benzyl, naphthyl, methylenenaphthyl.

R1 = H or CH3
R2 s R1
R2 = R1
R3 = R1
X = o, NH, N (R) or R is H or CH3 n is between 1 and 10, preferably between 2 and 4
Preferred monomers of the sulfonic type (M1) are vinylsulfonic acid, vinyldisulphonic acid, 2-phenylsulfonic acid, phenyl vinyldisulphonic acid, vinyl-1-naphthyl-2-vinylsulfonic acid and the like. naphthylvinylsulfonic acid, 1-naphthylvinyldisulfonic acid, 2,2-diphenylvinylsulfonic acid, 4-tert-butylphenylvinylsulfonic acid, 4-acetamido-4-phenylvinylsulfonic acid and their sodium or calcium salts correspondents.

Then we can mention the main allylsulphonic and methallylsulphonic acids such as allylsulphonic acid, methallylsulphonic acid, ethylallylsulphonic acid, phenylallylsulphonic acid, naphthylallylsulphonic acid, 2,2-diphenylallylsulphonic acid and para-substituted-allylsulphonic acid. , paracéta midophénylaliylsulfonique acid, N-chloroethyl-2 allylsulfonique acid, glycidylallylsulfonique acid and their corresponding sodium and calcium salts
Another family of sulfonic monomers is that of acids comprising the acryloyl function such as acryloalkylenesulphonic acids, acryloarylsulphonic acids, acrylamidoalkylenesulphonic acids, acrylamidoarylsulphonic acids, methacryloalkylenesulphonic acids, methacryloarylsulphonic acids, methacrylamidoalkylenesulphonic acids, methacrylamidoarylsufonic acids.

Here we state the main monomers of this family
1-Acrylomethyl-3,6-disulfonic acid, 1-acrylomethyl-dimethylsulfonic acid-3,7, 1-acrylomethyl-dimethylsulfonic acid-4,8 etc. and their corresponding sodium or calcium salts
2-sulfoethylacrylic acid, 2-sulphoethyl methacrylic acid, 3-sulphopropylacrylic acid, 3-sulphopropylmethacrylic acid, acrylamidoethanesulphonic acid, 2-methacrylethanesulphonic acid and acrylamido n-acid. butanesulfonic acid, methacrylamido-2-n-butanesulfonic acid, acrylamidoisobutanesulfonic acid, 2-methacrylamido-isobutanesulfonic acid, 2-acrylamidodimethyl-ethanesulfonic acid, 2-acrylomethyl-5-naphthalenesulfonic acid, methacryloacetic acid, 2-methyl-naphthalenesulfonic-5-acrylamido-2-naphthalenesulfonic acid-5-acrylomethyl-2-methylsulfon-5-naphthalene, 1-methacrylomethyl-methylsulfon-5-naphthalene, 1-acrylamidomethyl-methylsulfo-5-naphthalene;
In addition we add the acid acrylomethylamino-2-diaminomethyl sulfonic-4,6 triazine-1,3,5, the acid (methacrylamido-2) methylamino-2-diaminomethylsulfonic-4,6 triazin-1,315 the acid (methacrylo -2) 2-methylaminodinomethyl-4-aminomethylsulfonic-6-triazine-1,3,5 and their corresponding sodium or calcium salts.

However, this list is not exhaustive
The type M2 monomers are reagents having at least one carboxylic acid function or the corresponding sodium salt.

the main ones are acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid
These latter monomers are used in amounts of from 0 to 12% by weight relative to the total weight of the monomers, preferably from
O and 3k
Various methods of homopolymerization and aqueous phase copolymerization of sulfonated monomers such as sodium vinylsulfonate have been investigated.

BRESLOW and KUTNER in Journal Polymer of Science 27; 295-312 (1958) optimized at 62 ffi the concentration of sodium vinylsulfonate
KANGAS meanwhile studied the homopolymerization of 2-sulfoethyl methacrylate in Journal Polymer of Science; 1813-1821; (1970).

Recently GORRETTA and OTREMBA have developed a process for the continuous production of an acrylic acid sodium vinylsulfonate copolymer in. US Patent 4,331,792
Thus, the sulfonyl monomers have been the subject of numerous homopolymerization and copolymerization studies either in the organic phase or in the aqueous phase; however, we have not encountered any work relating to the obtaining and use of telomeres as described in the present invention.
Said telomerization reaction is catalyzed by inorganic or organic peroxides, preferably inorganic. These catalysts, also known as chain initiators, are percompounds such as: ammonium peroxydisulfate, potassium peroxydisulfate, sodium peroxydiphosphate, peroxydiphosphate ammonium, potassium peroxydiphosphate and hydrogen peroxide. These initiators are used in a proportion of 0.1 to 1% by weight relative to the total weight of monomers, preferably between 0.1 and 0.3% by weight. relative to the weight of monomers, preferably between 0.1 and 0.5 ffi, more precisely the amount of molar double with respect to the initiators
These reducing agents are: sodium hydrogencarbonate, sodium hydrogen sulphite, ammonium hydrogen sulphite, sodium sulphite, sodium pyrosulphite, sodium thiosulfate and ammonium and potassium salts.

The reaction is carried out under a stream of inert gas, preferably nitrogen. The temperature of the reaction is between 0 and 150 ° C., preferably between 60 and 1300 ° C.
In a reactor equipped with a stirring system, a heating device and a nitrogen sweep; already containing water at a temperature between 60 and 1000C two reagent stream arrive separately. In one of the streams, the telogen (s), that is to say the mercaptan or mercaptans, are shipped at a concentration varying between 20 and 90% by weight in solution in water, preferably between 40 and 60%, containing the catalyst
In the other stream, the monomer or monomers are sent at a concentration ranging from 20 to 80%, preferably from 50 to 80%, containing the reducing agent. The initiators and reductant reactants are introduced in 30 minutes. let react then between 30 minutes to 2 hours
This same reaction can be done with all the partners in the reactor
There are nevertheless several advantages when operating in continuous addition, they are the following - the control of the temperature of the reaction because it is exothermic - a speed of conversion of the reagents into products - a high yield, almost quantitative
EXAMPLE 1
The assembly consists of a reactor containing 50 g of water at 950C, equipped with a stirring system, a heating device, a refrigerant, a nitrogen sweeping system and two balanced casting ampoules
One of the casting ampoules contains 3.8375 g of thioglycolic acid, 1.3500 g of potassium persulfate and all in solution in 12 g of water.
The other ampoule contains 194 g of 2-sulfoethyl methacrylic acid, 76 g of water and 0.8400 g of sodium hydrogencarbonate.
The contents of both casting ampoules are poured simultaneously into the reactor in 30 minutes
0.675 g of potassium persulfate are then introduced and the mixture is left to react again for 30 minutes.
The reaction mixture is then brought to pH 8
EXAMPLE 2
According to a mounting identical to Example 1, the reactor contains 28 g of water at 860C.

In one of the ampoules, 1.14 g of ammonium persulfate, 8 g of water and 0.0975 g of mercaptoethanol are introduced.
The other ampoule contains 130 g of sodium vinylsulfonate, 62 g of water, 1.0400 g of sodium hydrogen sulfite and 1 g of phosphoric acid so that the pH of the reaction mixture is equal to 2.

The contents of the two casting ampoules are poured within 30 minutes into the reactor, where a temperature of 85 ° -88 ° C. is maintained. 0.5700 g of ammonium persulfate are then added to complete the reaction, allowing another 1 hour to react.

The pH is then adjusted to 8
EXAMPLE 3
According to the assembly described in Example 1, the following telomerization reaction is carried out
In the reactor 40 g of water are maintained at 1000C 1.12 g of thioglycerol, 0.8438 g of potassium persulfate and 10 g of water are shipped together with 65 g of sodium vinylsulfonate 57 g of diaminomethylsulphonate of sodium-4,6 (2-aminomethylmethacrylo) -2-triazine-1,3,5 8 g of water and 0,650 g of sodium hydrogen sulfite, in the space of 30 minutes. 0.4219 g of potassium persulfate are added and then allowed to react for 30 minutes
The reaction mixture is then adjusted to a pH equal to 8.5.

EXAMPLE 4
Following the assembly used for Example 1, 50 g of water are introduced into the reactor where a temperature of 880C is maintained.

One of the two casting ampoules contains 1.5000 g of thioglycerol 20 g of water and 0.3375 g of potassium persulfate
The other ampoule contains 104.75 g of sodium (4,6-methacryloyl) methyl-4,6-disulphonate naphthalene, 4.7778 g of methacrylic acid, 0.3177 g of sodium hydrogen sulfite and 80 g of water
In 30 minutes, the contents of the two ampoules are sent to the reactor and 0.18688 g of potassium persulfate are then added and the reaction mixture is stirred for another 30 minutes.
The reaction mixture is brought to a pH equal to 9.0
The solutions thus obtained can be added to the hydraulic mineral binder in proportions ranging from 0.04 to 12%, preferably from 0.8 to 5%, relative to the solids content of the solution relative to the weight of inorganic binder.
However, we have found that all homopolymers or mixtures of homopolymers and copolymers from all monomers as well as families of monomers cited in the present invention have the property of fluidizers and reducing plasticizers-water in hydraulic binders
They can therefore be used as such or in mixture with the oligomers of the invention in all proportions
In addition, the oligomers obtained according to the invention are miscible and compatible with existing conventional thinners such as lignosulphonates, polycondensates formalin-naphthalene calcium sulphonate, formaldehyde-melamine sulphonate polycondensates and the like; the oligomers of the invention can therefore be used in all proportions with these polycondensates or other
In order to test the fluidizing power of the oligomers according to the invention, a control concrete whose composition is as follows is prepared
Rolled 4/8 gravel: 37.7 Kg
River sand 0/4: 29.2 Kg
Portland cement A.55R: 17.3 Kg
Water: 8.1 Kg
The ABRAMS cone collapse test is carried out according to standard NF P 18451 of this reference concrete.
The sag is 4.5 centimeters
The same concrete composition is again made by introducing 31 g of dry telomer obtained according to Example 4, and the slump is measured again; the latter is then 20 centimeters
The table below makes it possible to better understand the fluidifying and plasticizing reducing effect of the oligomers obtained according to the present invention.

<tb><SEP> E <SEP>% <SEP> of <SEP> Sagging <SEP>% <SEP> of <SEP> Resistance
<tb><SEP> C <SEP> product <SEP> at <SEP> c8ne <SEP> reduction <SEP> at <SEP> compr
<SEP> expressed <SEP> in <SEP> cm <SEP> water <SEP> session
<tb><SEP> in <SEP> sec <SEP> in <SEP> M.Pa
<tb> Control <SEP> 0.467 <SEP> - <SEP> 4.5 <SEP> - <SEP> 21.9
<tb><SEP> Example <SEP> 1 <SEP> 0.467 <SEP> 1.2 <SEP> 20 <SEP> - <SEP> 21.9
<tb><SEP> Example <SEP> 2 <SEP> 0.42 <SEP> 1.8 <SEP> 8 <SEP> 10 <SEP> 30.4
<tb> PNS <SEP> 0.44 <SEP> 2.6 <SEP> 8 <SEP> 6 <SEP> 25.8
<tb> PMS <SEP> 0.42 <SEP> 2.6 <SEP> 9 <SEP> 10.3 <SEP> 30.3 <SEP>
<tb><SEP> Example <SEP> 3 <SEP> 0.40 <SEP> 2.6 <SEP> 6 <SEP> 14.3 <SEP> 32.8
<tb> Example <SEP> 4 <SEP> 0.38 <SEP> 3.0 <SEP> 6 <SEP> 18.7 <SEP> 37.2
<Tb>
PNS: Calcium Polynaphthalenesulfonate
PMS: Polyalkylamine modified with sodium hydrogen sulphite expressed after 24h at 280 ° C.

Claims (8)

 1. A process for obtaining water-soluble oligomers characterized in that these oligomers are obtained by a radical route in an aqueous medium, by reacting water-soluble mercaptans called telogen with water-soluble monomers having at least one sulfonic acid or sodium sulfonate function or of calcium, and their use as fluidifiers for hydraulic binders such as for example cements, anhydrites, plasters, clays, lime, and others. 2. Process for obtaining water-soluble oligomers according to claim 1, characterized in that the monomer to telogen ratio ranges from 4 to 800. 3. Process for obtaining water-soluble oligomers according to claims 1 and 2, characterized in that these oligomers have the general formula

 where F is a solubilizing function of the hydroxyl, carboxylic, sulfonic acid, amine, urea, thiourea, guanidine, etc. type where E is the aliphatic chain alkylene with 1 to 10 carbon atoms where E is the aliphatic chain alkyl with 1 to 8 atoms type carbon  -CO-N (R) -E, -N, E-CO-N (R) -E  I, I, I, J  -E N-N (R) -E-, E-SO 2 -N (R) -E R represents here hydrogen or alkyl with 1 to 4 carbon atoms E alkylene with 1 to 8 carbon atoms E alkylene with 1 to 4 carbon atoms M1 a unit derived from a sulfonic monomer and M2 a unit derived from a carboxylic monomer, the sum of x and y is between 4 and 800, xxy between 1 and 0.9, x is an integer between 4 and 800 and y = 0 or an integer of up to 50. 4. A method for obtaining water-soluble oligomers according to claims 1 to 3 characterized by the use as mercaptans preferred thioglycolic acid, mercaptoethanol, thioglycerol. 5. Process according to Claims 1 to 4, characterized in that the main sulphonic monomers are vinylsulphonic acid, vinyldisulphonic acid, 2-phenylsulphonic acid, allyl sulphonic acid, methallylsulphonic acid and sulphoethyl acid. 2-methacrylic acid, 3-sulfopropyl methacrylic acid 2-acrylomethyl-naphthalenesulfonic acid, 2-acrylomethylamino-diaminomethylsulfonic acid-4,6-triazine-1,3,5, 1-acrylomethyl-3,6-disulphonic acid 1-acrylomethyl-disulphonic acid-3,7, acrylomethyl-1-dimethylsulfonic acid-4,8 etc. and their corresponding sodium or calcium salts 6. Process according to claim 3, characterized in that the monomers of the M2 type are carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid and acid. itaconic acid. 7. Process according to Claims 3 and 6, characterized in that the monomers of the M2 type are used in a proportion of from 0 to 12% by weight relative to the total weight of the monomers. 8. Process according to any one of claims 1 to 7, characterized in that the sulphonic and carboxylic functions are neutralized with sodium hydroxide or calcium dihydroxide.