WO2006037888A1 - Superplastifiants a fonctions silane - Google Patents
Superplastifiants a fonctions silane Download PDFInfo
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- WO2006037888A1 WO2006037888A1 PCT/FR2005/002438 FR2005002438W WO2006037888A1 WO 2006037888 A1 WO2006037888 A1 WO 2006037888A1 FR 2005002438 W FR2005002438 W FR 2005002438W WO 2006037888 A1 WO2006037888 A1 WO 2006037888A1
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- polymer
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- silyl
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Classifications
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- 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
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2641—Polyacrylates; Polymethacrylates
- C04B24/2647—Polyacrylates; Polymethacrylates containing polyether side chains
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- 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
- C04B24/40—Compounds containing silicon, titanium or zirconium or other organo-metallic compounds; Organo-clays; Organo-inorganic complexes
- C04B24/42—Organo-silicon compounds
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- 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
- C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
-
- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/32—Superplasticisers
-
- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/40—Surface-active agents, dispersants
- C04B2103/408—Dispersants
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- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00034—Physico-chemical characteristics of the mixtures
- C04B2111/00103—Self-compacting mixtures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
- C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
Definitions
- the present invention relates to the field of admixtures for hydraulic binders, and in particular plasticizers and superplasticizers.
- hydraulic binders such as cement compositions.
- basic properties of hydraulic binders are the rheological properties and their evolution over time, related to workability.
- plasticizers are used which have the effect of fluidifying hydraulic binders and make it possible to reduce the amount of water added. That's why they are also referred to as water reducers.
- the hydraulic binder then has a higher density and results in a material having a higher mechanical strength.
- PCP polyalkoxylated polycarboxylic acid
- hydroaulic binder is understood to mean any material with a hydraulic setting, that is to say in particular in addition to cements such as Portland cements, mortars further comprising fine aggregates, or concretes, further comprising coarse aggregates.
- cements such as Portland cements, mortars further comprising fine aggregates, or concretes, further comprising coarse aggregates.
- the term also includes anhydrous or hemihydrated calcium sulphates.
- hydrocarbon chain is intended to mean a group comprising carbon, hydrogen, aliphatic, saturated or unsaturated, aromatic, arylalkyl or alkylaryl atoms, linear or branched and optionally interrupted and / or terminated by one or more heteroatoms such as HIS P.
- alkyl group means a linear, branched or cyclic alkyl group.
- the invention proposes the use of a polymer comprising a main hydrocarbon chain and silyl side groups and polyoxyalkyl side groups as an adjuvant for hydraulic binders.
- the proportion of the respective groups in the polymer can vary widely.
- the polymer preferably comprises 0.001 to 50%, in particular 1 to 30% and most preferably 5 to 20% by number of silyl groups.
- the polymer comprises a proportion of polyoxyalkyl groups of 1 80% by number, in particular from 10 to 50.
- the polyoxyalkyl groups may be linked to the main chain or through different groups. Preferably, they are linked to the main chain via an ester, ether or amide linkage.
- the polymer may further comprise carboxyl groups, from 0 to 80%, in particular from 10 to 60% and most preferably 15 to 30% by number of carboxylic groups. These groups can be in free acid form or partially or completely neutralized.
- the polymer generally has an average molar mass of between 10 000 and 220 000 (Mw), preferably between 10 000 and 110 000 (Mw), as determined by GPC according to the protocol indicated in the experimental part.
- the polymerization index Ip is preferably between 1 and 5, preferably between 1, 5 and 3.
- reaction may be suitable for the preparation of the described polymer.
- it can be prepared by copolymerization of several comonomers or by introducing onto a polymer one or more types of side groups. This latter process is also called post-grafting.
- the described polymer is prepared by copolymerization, in the presence of a suitable catalyst, polymerizable monomers bearing respectively the desired groups.
- the polymer can be prepared by copolymerization in the presence of a suitable catalyst of the following monomers: (a) an unsaturated derivative, or its corresponding ester, amide or salt, comprising a silyl group capable of releasing a silanol group during hydrolysis;
- the monomer (a) is advantageously an ethylenically unsaturated carboxylic acid, or its corresponding ester, amide or salt.
- the unsaturated acid may in particular be chosen from acrylic acid, methacrylic acid or the dicarboxylic acids listed below.
- the alcohols carrying a silyl group can be derived in particular from alkyl alcohols such as methanol, ethanol, isopropanol, propanol, butanol, isobutanol, tert. butanol.
- Silyl groups are groups comprising at least one silicon atom and at least one group capable of being hydrolyzed to silanol group, for example a Si-OR group, where R is preferably alkyl to C 6.
- R is preferably alkyl to C 6.
- R are alkyl groups, preferably C 1 to C 6
- x is an integer of 0 to 2
- y is an integer of 1 to 3, the sum of x and y being 3 to satisfy the valence of silicon.
- the central silicon atom itself carries one or more silyl groups as defined above, provided that at least one silanol group is hydrolyzable.
- the monomer (a) preferably corresponds to formula (I) below: in which :
- R a represents H or a C1-C4 alkyl group, in particular methyl;
- X is a spacer group, in particular an alkylene Ci to C 6 or a sequence of groups of formula - (QO) n - wherein:
- Q represents an alkylene group of 2 to 4 carbon atoms or a mixture of these alkylene groups; n is an integer group ranging from 3 to 500;
- Y represents a silyl group of formula Si (OR e ) i (Rf) j, R e and Rf being independently of one another a Ci-Cs alkyl group, preferably methyl or ethyl, or a group of formula Si (OR g ) j (Rh) j; Rg and Rh being independently of each other a C1-C6 alkyl group and i being an integer of 1 to 3 and j an integer of 3-i.
- the spacer X is an ethylene or propylene group.
- the monomer (b) preferably corresponds to formula (II) below:
- R b is H or C 1 -C 6 alkyl, preferably methyl
- Q represents an alkylene group of 2 to 4 carbon atoms or a mixture of these alkylene groups; n is an integer group ranging from 3 to 500; and
- P represents a hydrogen atom or an alkyl, aryl group, alkylaryl or arylalkyl Ci-Ci 2, preferably from 1 to 4 carbon atoms and especially methyl.
- the monomer (b) may be chosen in particular from the group consisting of monoesters, preferably methacrylates or acrylates, polyethylene glycol or polypropylene glycol or copolymers thereof, and their derivatives in which the terminal group is etherified.
- the molecular weight of the polyalkylene glycols is preferably from 100 to 10,000, in particular from 500 to 7,000.
- a carboxylic acid anhydride is preferably chosen as monomer (c).
- R 0 is H or alkyl to C 6, preferably methyl; and Rd represents H or a C 1 -C 12 alkyl, aryl, alkylaryl or arylalkyl group, preferably methyl or ethyl.
- the monomer (c) may be chosen from the group consisting of methacrylic acid, acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) propyl acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert. butyl, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate.
- the monomer (c) may also carry more than one carboxylic function.
- dicarboxylic acids such as crotonic acid, maleic acid and fumaric, itaconic acid, citraconic acid and their derivatives including the corresponding anhydrides, esters, salts and amide.
- the mixture to be polymerized optionally also comprises other additives usually used, such as a transfer agent and / or an initiator.
- any compounding agent usually contemplated for this purpose can be used. Mention may in particular be made of thioglycolic acid or mercaptoacetic acid.
- the initiator may be selected from commercially available compounds for radical polymerizations. In this context, mention may be made, for example, of azo compounds.
- the polymerization reaction is advantageously a radical polymerization. This type of reaction is known as such.
- the polymerization reaction can be carried out in a suitable solvent, preferably apolar.
- the duration of the reaction depends on the reactivity of the monomers and the temperature. It is usually between 30 minutes and 10 hours.
- the temperature of the reaction is chosen in particular according to the starting temperature of the catalyst. It is advantageously between 20 and 80 ° C.
- the solvent is separated. It may also be advantageous to completely or partially neutralize the carboxylic groups.
- the product is then ready for formulation.
- the polymer is prepared by a process called "post-grafting".
- This process then comprises the grafting of silylated and / or polyoxyalkylated side groups on a polymer comprising a hydrocarbon chain and reactive groups, for example carboxylic groups.
- the grafting is carried out by reacting the polymer with a silylated and / or polyoxyalkylated alcohol or amine, respectively.
- the reagents used for the grafting are chosen in particular from the corresponding alcohols or amines, the amines being preferred because of their better reactivity at low temperature.
- the post-grafting method may comprise the steps of:
- the monomer (c) can be polymerized and then the carboxylic groups are esterified to the desired degree with polyoxyalkyl compounds and the resulting product grafted with a silylated reactive compound.
- the carboxylic groups present in the reaction product can then be totally or partially neutralized.
- the invention provides an adjuvant for hydraulic binders comprising the described polymer in combination with a suitable solvent and, if desired, conventional additives.
- a suitable solvent comprises water or consists of water.
- the concentration of the adjuvant polymer depends mainly on the intended application. Generally, the adjuvant comprises from 10 to 50, preferably 20 to 40,% by weight of polymer relative to the total weight.
- the adjuvant formulation may further include other conventional additives such as defoamers, accelerators, retarders or water repellents.
- the formulation may further comprise formulation additives, such as anti-foam stabilizers for example.
- the invention proposes a process for fluidizing and maintaining the workability of suspensions of mineral particles, especially hydraulic binders such as Portland cements, mortars, concretes, and anhydrous calcium sulphates. or hemihydrates, comprising the step of adding to the suspension an appropriate amount of adjuvant as described above, optionally after a basic hydrolysis step.
- concrete especially prefabricated concrete and ready-to-use concretes. These concretes can be intended in particular for building and civil engineering.
- the amount of adjuvant to be added to the suspension of mineral particles depends of course on the desired properties and the intended application. However, it depends little on the chemical nature of mineral particles such as cements, and thus reveals the low sensitivity to the chemical nature of the cements used.
- an adjuvant dosage of 0.01 to 2%, preferably 0.5 to 1% by weight of polymer based on the weight of the cement is suitable for most standard applications.
- an effective adjuvant dosage for the preparation of a ready-to-use concrete composition is from 0.7 to 1.5% of a formulation containing 20% by weight of dry extract relative to the weight. of cement.
- the mechanism of action of the described polymers is not completely understood, it being understood that that of superplasticizers in cements is not yet fully elucidated in a general manner.
- the fluidifying effect of the superplasticizers results mainly from repulsive forces involved between the copolymers adsorbed on the surface of the grains.
- the sensitivity of the superplasticizers is related to the amount of ettringite (aluminum-calcium sulphate hydrate) because of their preferential adsorption thereon.
- Ettringite is formed during the hydration of the C 3 A phase (tricalcium aluminate) in the presence of soluble sulphates.
- the amount of ettringite would depend on the content of the cements in these components, which varies greatly between different cements.
- the silylated polymers according to the invention comprise Si-OR groups which are hydrolyzed in aqueous medium at basic pH to silanol groups.
- Silanol groups having high chemical affinity with silica hydrates (CSH) formed by the hydration of calcium silicates (C 2 S and C 3 S).
- the content of the tricalcium silicate cements (C 3 S) is higher, it results that its relative variation is smaller compared to that of the tricalcium aluminate content (typically 55 to 65% of C 3 S against 2 to 10% C 3 A).
- the better maintenance of the fluidity and the prolonged workability observed with the polymers according to the invention could be due to a strengthening of the effect of the silica hydrates limiting the diffusion of the water and thus delaying the setting due to the adsorbed superplasticizers .
- the mechanism of action of the polymer as described makes it useful even outside the field of hydraulic setting compositions such as cements, mortars, concretes and plasters.
- the described polymer may be useful as a dispersant of mineral fillers in many other compositions, particularly in the field of paints, paper and plastics.
- the invention is directed to a hydraulic binder composition comprising the adjuvant described, where appropriate in its hydrolysed form.
- the silyl groups are capable of being hydrolyzed silanol groups in the basic aqueous medium of the hydraulic binder composition.
- These hydraulic binder compositions have the main advantage of prolonged workability, and in particular compatible with a wide range of applications, including ready-mix concrete and self-compacting concrete.
- a solution of an initiator is prepared by weighing 0.49 g of 2,2'-Azobis- (2,4-dimethylvaleronitrile) (Vazo 52 from Dupont) in 10.0 g of tetrahydrofuran (THF).
- the reaction medium is heated at 60 ° C. with stirring, and ensuring degassing under N 2 .
- the initiator solution is added to the reaction medium and the mixture is left to react for 5 hours at a temperature of 60 ° C.
- a small amount of water is added. It is then distilled under vacuum to remove the solvent.
- the product obtained is a viscous liquid which is diluted with water to obtain a solution of concentration in the region of 30% by weight.
- a solution of an initiator is prepared by weighing 0.68 g of
- the reaction medium is heated at 60 ° C. with stirring, and ensuring degassing under N 2 .
- the initiator solution is added to the reaction medium and the solution is left to react for 5 hours at a temperature of 60 ° C.
- a small amount of water is added. It is then distilled under vacuum to remove the solvent.
- the product obtained is a viscous liquid which is diluted with water to obtain a solution of concentration close to 30% by weight.
- a solution of an initiator is prepared by weighing 0.61 g of 2,2 I- Azobis- (2,4-dimethylvaleronitrile) (Vazo 52 from Dupont) in 10.0 g of tetrahydrofuran (THF).
- the reaction medium is heated at 60 ° C. with stirring, and ensuring degassing under N 2 .
- the initiator solution is added to the reaction medium and the solution is allowed to act for 5 hours at a temperature of 60 ° C.
- a small amount of water is added. It is then distilled under vacuum to remove the solvent.
- the product obtained is a viscous liquid which is diluted with water to obtain a solution of concentration in the region of 30% by weight.
- a solution of an initiator is prepared by weighing 0.59 g of 2,2'-Azobis- (2,4-dimethylvaleronitrile) (Vazo 52 from Dupont) in 10.0 g of tetrahydrofuran (THF).
- THF tetrahydrofuran
- the reaction medium is heated at 60 ° C. with stirring, and ensuring degassing under N 2 .
- the initiator solution is added to the reaction medium and the solution is allowed to act for 5 hours at a temperature of 60 ° C.
- a small amount of water is added. It is then distilled under vacuum to remove the solvent.
- the product obtained is a viscous liquid which is diluted with water to obtain a solution of concentration in the region of 30% by weight.
- a solution of an initiator is prepared by weighing 0.59 g of 2,2'-Azobis- (2,4-dimethylvaleronitrile) (Vazo 52 from Dupont) in 10.0 g of tetrahydrofuran (THF).
- the reaction medium is heated at 60 ° C. with stirring, and ensuring degassing under N 2 .
- the initiator solution is added to the reaction medium and the solution is allowed to react for 5 hours at a temperature of 60 ° C.
- a small amount of water is added. It is then distilled under vacuum to remove the solvent.
- reaction medium is heated at 60 ° C. with stirring, and ensuring degassing under N 2 .
- 0.59 g of 2,2'-Azobis (2,4-dimethylvaleronitrile) (Vazo 52 from Dupont) is added as an initiator to the reaction medium and the solution is left to react for 5 hours at a temperature of 60 ° C. .
- the product obtained is a viscous liquid which is diluted with water to obtain a solution of concentration in the region of 30% by weight.
- a solution of an initiator is prepared by weighing 0.61 g of 2,2 I- Azobis- (2,4-dimethylvaleronitrile) (Vazo 52 from Dupont) in 10.0 g of tetrahydrofuran (THF).
- THF tetrahydrofuran
- the reaction medium is heated at 60 ° C. with stirring, and degassing under N 2 is carried out.
- the initiator solution is added to the reaction medium and the solution is left to react for 5 hours at a temperature of 60 ° C.
- a small amount of water is added. It is then distilled under vacuum to remove the solvent.
- the product obtained is a viscous liquid which is diluted with water to obtain a solution of concentration in the region of 30% by weight.
- a solution of an initiator is prepared by weighing 0.62 g of 2,2'-Azobis- (2,4-dimethylvaleronitrile) (Vazo 52 from Dupont) in 10.0 g of tetrahydrofuran (THF).
- the reaction medium is heated at 60 ° C. with stirring, and ensuring degassing under N 2.
- the initiator solution is added to the reaction medium and the solution is left to react for 5 hours at a temperature of 60 ° C.
- a small amount of water is added. It is then distilled under vacuum to remove the solvent.
- the product obtained is a viscous liquid which is diluted with water to obtain a solution of concentration in the region of 30% by weight.
- a solution of an initiator is prepared by weighing 0.63 g of
- the reaction medium is heated at 60 ° C. with stirring, and ensuring degassing under N 2 .
- the catalyst solution is added to the reaction medium and the solution is allowed to react for 5h30 at a temperature of
- the product obtained is a viscous liquid which is diluted with water to obtain a solution of concentration in the region of 30% by weight.
- Methacrylic polyacid ES 30% 250 g
- Methoxy polyethylene glycol 750 128 g
- the molar mass of the copolymers prepared is determined by gel permeation chromatography (GPC) in the aqueous route under the following conditions: flow rate 1 ml / min;
- the spreading of the cement compositions is determined according to the following protocol at constant temperature.
- a frustoconical bottomless mold is used, a scale reproduction Vz of the Abrams cone, characterized by the following dimensions: diameter of the circle of the upper base 50 mm diameter of the circle of the lower base 100 mm and height 150 mm.
- This cone is filled with the fresh sample in three layers of identical volume, stitching the sample between each layer using a steel rod 6 mm in diameter and 300 in length. mm with spherical end. Then, the upper surface of the cone is leveled off and then demolded on a clean surface and raises the cone vertically. The sag is measured at the highest point and the spreading at four diameters at 45 ° with a caliper. The spread is given by the average between these four measurements.
- the adjuvant according to Example 9 prepared like the other polymers, but without silylated compound, has a difference comparable to the product marketed and in any case much greater than that of the copolymers having a silanol group.
- the mortars were prepared according to the protocol described above.
- the adjuvant dosage for each of the four cements determined according to the standard N 196 and expressed as a percentage relative to the cement weight of the mortar, is shown in Table 3 below.
- Maintaining workability is substantially equal to Glenium 27 but with a lower dosage which is respectively for Glenium 27 0.11 0.50 - 0.33 - 0.25.
- Maintaining workability is substantially equal to Glenium 27 but with a lower dosage which is respectively for Glenium 27 0.11 0.50 - 0.33 - 0.25.
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- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Structural Engineering (AREA)
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- Curing Cements, Concrete, And Artificial Stone (AREA)
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Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP05809302A EP1797128A1 (fr) | 2004-10-05 | 2005-10-04 | Superplastifiants a fonctions silane |
CA002582433A CA2582433A1 (fr) | 2004-10-05 | 2005-10-04 | Superplastifiants a fonctions silane |
US11/576,760 US20080085952A1 (en) | 2004-10-05 | 2005-10-04 | Superplasticisers Having Silane Functions |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0410499 | 2004-10-05 | ||
FR0410499A FR2876108B1 (fr) | 2004-10-05 | 2004-10-05 | Superplastifiants a fonctions silane |
Publications (1)
Publication Number | Publication Date |
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WO2006037888A1 true WO2006037888A1 (fr) | 2006-04-13 |
Family
ID=34951137
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/FR2005/002438 WO2006037888A1 (fr) | 2004-10-05 | 2005-10-04 | Superplastifiants a fonctions silane |
Country Status (6)
Country | Link |
---|---|
US (1) | US20080085952A1 (fr) |
EP (1) | EP1797128A1 (fr) |
CA (1) | CA2582433A1 (fr) |
FR (1) | FR2876108B1 (fr) |
WO (1) | WO2006037888A1 (fr) |
ZA (1) | ZA200702920B (fr) |
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US20110196164A1 (en) * | 2007-08-08 | 2011-08-11 | Tewodros Asefa | Selective and efficient bifunctional and trifunctional nanoporous catalysts and methods of synthesis thereof |
US8563631B2 (en) | 2009-04-01 | 2013-10-22 | Lafarge | Viscosity-reducing super-plasticising copolymers |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105612134A (zh) * | 2013-10-02 | 2016-05-25 | 巴斯夫欧洲公司 | 聚(氧化烯)氧基-和/或聚(氧化烯)氨基烷基三烷氧基硅烷作为分散剂的用途 |
JP6433282B2 (ja) * | 2014-12-18 | 2018-12-05 | 株式会社日本触媒 | セメント混和剤用ポリマー、セメント混和剤、およびセメント組成物 |
JP2022533306A (ja) * | 2019-05-21 | 2022-07-22 | シーカ テクノロジー アクチェンゲゼルシャフト | 可撓性モルタル組成物 |
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DE4445569A1 (de) * | 1993-12-21 | 1995-06-22 | Sandoz Ag | Additionspolymer |
EP0736553A2 (fr) * | 1995-04-07 | 1996-10-09 | SKW Trostberg Aktiengesellschaft | Copolymères à base d'oxyalkylèneglykol et dérivés d'acides dicarboxyliques insaturés |
WO1998030615A1 (fr) * | 1997-01-10 | 1998-07-16 | Biocompatibles Limited | Polymeres |
JP2000072505A (ja) * | 1998-08-28 | 2000-03-07 | Lion Corp | セメント混和剤 |
EP1233031A2 (fr) * | 2001-02-16 | 2002-08-21 | Kusumoto Chemicals, Ltd. | Agent de fluidification et d'écoulement pour peintures et encres |
FR2846972A1 (fr) * | 2002-11-08 | 2004-05-14 | Omya Ag | Suspensions aqueuses de matieres minerales broyees, faiblement chargees ioniquement et leurs utilisations |
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US4567228A (en) * | 1984-05-21 | 1986-01-28 | Ppg Industries, Inc. | Aqueous dispersion, internally silylated and dispersed polyurethane resins, and surfaces containing same |
JPS63162563A (ja) * | 1986-12-25 | 1988-07-06 | 大日本インキ化学工業株式会社 | セメント分散剤 |
IT1301974B1 (it) * | 1998-07-31 | 2000-07-20 | Atochem Elf Italia | Copolimeri acrilici idrosolubili |
FR2810314B1 (fr) * | 2000-06-20 | 2003-09-19 | Lafarge Aluminates | Liant rapide pour beton autocompactant, utilisation et applications d'un tel liant |
DE10040825A1 (de) * | 2000-08-21 | 2002-03-07 | Basf Ag | Verwendung von Ammoniak-freien Polymerdispersionen als Zusatz in Baumaterialien auf Basis hydraulischer Bindemittel |
FR2821073A1 (fr) * | 2001-02-21 | 2002-08-23 | Lafarge Sa | Composition pour couche de roulement |
US20030191214A1 (en) * | 2002-04-03 | 2003-10-09 | Mari Masanaga | Admixture composition for hydraulic material |
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2004
- 2004-10-05 FR FR0410499A patent/FR2876108B1/fr not_active Expired - Fee Related
-
2005
- 2005-10-04 WO PCT/FR2005/002438 patent/WO2006037888A1/fr active Application Filing
- 2005-10-04 EP EP05809302A patent/EP1797128A1/fr not_active Withdrawn
- 2005-10-04 CA CA002582433A patent/CA2582433A1/fr not_active Abandoned
- 2005-10-04 US US11/576,760 patent/US20080085952A1/en not_active Abandoned
-
2007
- 2007-04-10 ZA ZA200702920A patent/ZA200702920B/xx unknown
Patent Citations (6)
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DE4445569A1 (de) * | 1993-12-21 | 1995-06-22 | Sandoz Ag | Additionspolymer |
EP0736553A2 (fr) * | 1995-04-07 | 1996-10-09 | SKW Trostberg Aktiengesellschaft | Copolymères à base d'oxyalkylèneglykol et dérivés d'acides dicarboxyliques insaturés |
WO1998030615A1 (fr) * | 1997-01-10 | 1998-07-16 | Biocompatibles Limited | Polymeres |
JP2000072505A (ja) * | 1998-08-28 | 2000-03-07 | Lion Corp | セメント混和剤 |
EP1233031A2 (fr) * | 2001-02-16 | 2002-08-21 | Kusumoto Chemicals, Ltd. | Agent de fluidification et d'écoulement pour peintures et encres |
FR2846972A1 (fr) * | 2002-11-08 | 2004-05-14 | Omya Ag | Suspensions aqueuses de matieres minerales broyees, faiblement chargees ioniquement et leurs utilisations |
Non-Patent Citations (1)
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20110196164A1 (en) * | 2007-08-08 | 2011-08-11 | Tewodros Asefa | Selective and efficient bifunctional and trifunctional nanoporous catalysts and methods of synthesis thereof |
US9174203B2 (en) * | 2007-08-08 | 2015-11-03 | Tewodros Asefa | Selective and efficient bifunctional and trifunctional nanoporous catalysts and methods of synthesis thereof |
US8563631B2 (en) | 2009-04-01 | 2013-10-22 | Lafarge | Viscosity-reducing super-plasticising copolymers |
Also Published As
Publication number | Publication date |
---|---|
FR2876108B1 (fr) | 2007-11-23 |
CA2582433A1 (fr) | 2006-04-13 |
EP1797128A1 (fr) | 2007-06-20 |
FR2876108A1 (fr) | 2006-04-07 |
US20080085952A1 (en) | 2008-04-10 |
ZA200702920B (en) | 2008-09-25 |
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