EP3230345A1 - Procede continu d'esterification et/ou d'amidification, sans solvant organique, d'un homopolymere ou copolymere acide - Google Patents
Procede continu d'esterification et/ou d'amidification, sans solvant organique, d'un homopolymere ou copolymere acideInfo
- Publication number
- EP3230345A1 EP3230345A1 EP15817484.7A EP15817484A EP3230345A1 EP 3230345 A1 EP3230345 A1 EP 3230345A1 EP 15817484 A EP15817484 A EP 15817484A EP 3230345 A1 EP3230345 A1 EP 3230345A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- homopolymer
- acid
- esterification
- copolymer
- poly
- 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.)
- Pending
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
- B29C48/402—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders the screws having intermeshing parts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
- B29C48/405—Intermeshing co-rotating screws
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/04—Silica-rich materials; Silicates
- C04B14/06—Quartz; Sand
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- 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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- 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
- C04B28/04—Portland cements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
- C08G81/025—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyether sequences
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0045—Polymers chosen for their physico-chemical characteristics
- C04B2103/0059—Graft (co-)polymers
- C04B2103/006—Comb polymers
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- C—CHEMISTRY; METALLURGY
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/304—Air-entrainers
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- 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
- C04B2103/308—Slump-loss preventing agents
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- 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
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/40—Surface-active agents, dispersants
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/128—Copolymers graft
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/05—Polymer mixtures characterised by other features containing polymer components which can react with one another
Definitions
- the present invention relates to the technical field of continuous esterification and / or amidation processes for polymers, making it possible to provide acidic acrylic polymers comprising at least one poly (alkylene glycol) side chain.
- Acidic acrylic copolymers having at least one poly (alkylene glycol) side chain are sometimes referred to as comb structure polymers. These are copolymers having a skeleton essentially of carboxylic nature on which are grafted side chains (also called “hanging chains") of poly (alkylene glycol) type.
- the first synthetic route of these copolymers is copolymerization in the presence of acidic acrylic monomers and polymerizable macromonomers comprising poly (alkylene glycol) chains.
- the second route of preparation of the comb structure copolymers is the esterification and / or amidation of acrylic acid polymers with polyalkylene glycols.
- an acidic acrylic polymer is prepared by conventional polymerization techniques, for example radical polymerization, and then the esterification and / or amidification of this acidic acrylic polymer is carried out in the presence of poly (alkylene glycol) compounds.
- the esterification and amidation processes described in the prior art for example WO 2007/132322, WO 2009/090471, WO 2013/021029, US 2008/0119602
- the method of the present invention is based on the use of a continuous reactor called tubular reactor, for example an extruder.
- a tubular reactor the material can be subjected for a very short time to high temperatures (for example from 100 to 300 ° C.), with the possibility also of applying high local pressures (50 to 150 bars).
- the tubular reactor may also be equipped with devices ensuring homogeneity of the melt during its flow.
- Extruders are generally used in continuous processes of transformation, for example shaped, thermoplastic polymers or thermosetting polymers. During these extrusion and injection processes, the polymers are completely melted to give them the shape and appearance desired to obtain the part to be manufactured.
- the material is subjected for a very short time to high temperatures (for example from 100 to 300 ° C), to high local pressures (50 to 150 bar), and to a very intense shear.
- high temperatures for example from 100 to 300 ° C
- high local pressures 50 to 150 bar
- Extrusion is particularly suitable for resistant materials having a high melting point.
- Tubular reactors such as extruders
- extruders can also be used to chemically modify the molten material.
- the use of an extruder to perform a chemical reaction is called reactive extrusion (REX).
- REX reactive extrusion
- Extrusion offers, because of its intrinsic characteristics (temperature, pressure, shear), a solution adapted to react two polymeric materials, inert or otherwise difficult to react.
- Reactive extrusion is, moreover, described in the context of the aqueous radical polymerization.
- Polymers of the poly (alkylene glycol) type for example poly (ethylene glycol) or PEG, are sensitive to temperature. The degradation of these polymers, under the effect of temperature, by oxidative decomposition, leads to by-products of water type, CO 2 , aldehyde, simple alcohols, acids, glycol esters and vinyl by-products.
- comb-type polymers consisting of pendant chains of poly (alkylene glycol) type.
- the high temperatures can lead to side reactions, for example release of the pendant chains of the comb polymer and unexpected crosslinking, and thus degrade the quality of the polymer obtained.
- Substantial crosslinking can also lead to gelation of the assembly, to polymers finally insoluble in water.
- An object of the present invention is to provide a process for the preparation of comb-type polymers consisting of poly (alkylene glycol) pendant chains by esterification and / or amidification of an acidic polymer by means of poly (alkylene glycol) compounds, said process being of continuous type and at high temperatures.
- the use of such high temperatures makes it possible to reduce the residence time in the reactor. In doing so, the cost of producing such polymers is reduced and the regularity of the products.
- the operating conditions of the process are such that the degree of degradation of the side chains and the degree of crosslinking are very low. This makes it possible to obtain polymers having a high homogeneity, a low polymolecularity index, and therefore polymers of better quality.
- Such a continuous process is very advantageous from an industrial point of view. It considerably reduces the reaction time, and thus increases the profitability of production. Moreover, such a process is more flexible because the use of a tubular reactor, such as an extruder makes it possible to adjust the operating conditions during the process, much faster than in batch or semi-batch process. . Since the total volume is distributed over the length of the reactor and possibly in reaction zones having different temperatures, the volume of reagents to be brought to the desired temperature (at least 170 ° C. in the case of the present invention) is much smaller than that of a batch or semi-batch type reactor and therefore requires less time to perform regulation and temperature corrections. The continuous system therefore has a greater reactivity than non-continuous type systems. Such a method thus makes it possible, for example, to fix the esterification and / or amidation yield as a function of the desired degree of grafting on the comb-type polymer, much more easily.
- An object of the present invention is a continuous process for preparing a comb polymer, without organic solvent, by esterification and / or amidification of an acidic homopolymer or copolymer, comprising esterifying and / or amide-forming said homopolymer / copolymer by hot reaction in the mixing and conveying zone of a tubular reactor, such as an extruder, optionally equipped with a water removal system, in the presence of at least one poly (alkylene) glycol) in solid or melt form and an antioxidant, said esterification and / or amidification occurring at a temperature greater than or equal to 170 ° C, optionally in the presence of an esterification catalyst and / or amidif ⁇ cation, optionally under reduced pressure and / or under a stream of inert gas.
- a tubular reactor such as an extruder, optionally equipped with a water removal system, in the presence of at least one poly (alkylene) glycol) in solid or melt form and an antioxidant, said esterification and /
- the mixing zone comprises a homogenization of the mixture.
- the esterification and / or amidification of said homopolymer / copolymer is carried out by hot kneading in the mixing and transport zone of the extruder, optionally equipped with an elimination system of the extruder. water, said esterification and / or amidification occurring at a temperature greater than or equal to 170 ° C, optionally in the presence of an esterification catalyst and / or amidation, optionally at reduced pressure and / or under a flow of inert gas.
- Such a method makes it possible to obtain a polymer of comb structure also called "comb polymer".
- comb polymer These are polymers or copolymers having a backbone of carboxylic nature on which are grafted side chains (also called “hanging chains") of poly (alkylene glycol) type. These side chains are sometimes referred to as polyoxyalkyl side groups.
- the acidic skeleton for example, of carboxylic nature, may have a more or less anionic charge. If the degree of esterification and / or amidation is close to 100%, it means that a large part of the acid functions of the acid polymer, for example the carboxylic groups of an acrylic acid polymer, have been subjected to an esterification and / or amidation reaction and the skeleton of the final polymer is very lightly anionically charged.
- the degree of esterification and / or amidation of the comb polymer obtained can, for example, be determined by the titration of the acid functions (for example, acid number in mgKOH / g).
- These acidic functions may be in the free acid or acid anhydride form or in the partially neutralized form.
- the molar proportion of free acid and acid anhydride functional groups in the final comb polymer may vary from 0 to 99%, for example from 5 to 60%.
- An advantage of the process of the present invention is to allow easy adjustment of the rate of esterification and / or amidation as required. To do this, it is possible to adjust the residence time parameters and / or molar ratio of the constituents at the inlet of the reactor.
- said comb polymer obtained by the process of the present invention advantageously has an acid number of between 35 and 234 mg KOH / g (mass of potassium hydroxide, expressed in mg, necessary to neutralize the acidity one gram of polymer).
- said comb polymer obtained by the process of the present invention has an acid number of between 46 and 156 mg KOH / g.
- the process of the present invention is carried out continuously.
- the introduction of constituents into the tabular reactor, for example the extruder is "continuous", that is to say at constant or variable speed, but without stopping the introduction.
- the introduction of the constituents into the synthesis reactor is "simultaneous", that is to say that the various constituents are introduced concomitantly.
- the introduction of the constituents into the synthesis reactor is "proportional", that is to say that the proportion of each component of the mixture introduced into the reactor synthesis remains constant over the reaction time, vis-à-vis the other constituents of the mixture.
- the constituents are introduced into the tubular reactor in the form of a homogeneous mixture.
- the mixture of constituents is homogenized at the inlet of the reactor.
- the process of the present invention is carried out without organic solvent. Indeed, processes using solvents generate volatile organic compounds (VOCs or English VOC). On the one hand, it is necessary to eliminate these solvents at the end of the reaction, which has the effect of complicating the industrial process for preparing the polymer. On the other hand, the effects on health and the environment of these solvents are recognized as very harmful, so that we try to avoid producing them. Finally, even after purification (distillation), there are still traces of solvent in the polymers obtained.
- solvent means any substance which is inert to reactants and reaction products in the liquid phase at its temperature of use, the function of which is to dilute other substances without modifying them chemically and without to modify himself.
- the process of the invention is carried out at high temperatures, the esterification and / or amidification of the homopolymer / copolymer taking place at a temperature greater than or equal to 170 ° C.
- the esterification and / or amidification of the homopolymer / copolymer takes place at a temperature greater than or equal to 180 ° C, for example greater than or equal to 200 ° C, 210 ° C or 220 ° C.
- the product obtained at the outlet of the tabular reactor is likely to be in the form of a resin (high temperature at the outlet of the tabular reactor, for example at the extrusion outlet) or wax (temperature at the outlet of the tabular reactor, for example extruder, lower than the melting temperature of the comb polymer obtained).
- the product has a very high solids content, for example greater than 90%, or for example greater than 95% by weight.
- Such a product can then be transformed, for example milled, to be in the form of a solid powder, flakes, pellets, rushes, granules ...
- the product obtained at the outlet of a tabular reactor may be solubilized at the end of the reaction, by addition of water, and optionally an alkali.
- the amount of water added to the product of the esterification and / or amidification reaction is adjusted to obtain a solution having a defined active ingredient content.
- the process of the present invention makes it possible to obtain a product having a high solids content, for example greater than 60% of its weight, while retaining its liquid nature, that is to say that it is perfectly easy to handle and in particular pumpable by judiciously choosing the composition of poly (alkylene glycol) side chains.
- the neutralizing agent is chosen so that the counterion present in the polymer solution after neutralization is, for example, selected from the group consisting of calcium ion, sodium ion, potassium ion lithium ion, magnesium ion, barium ion, zinc ion, aluminum ion, ammonium ion and amine (for example, 2-amino-2-methylpropanol, triethanolamine, etc.).
- the neutralization of the polymer obtained can be total or partial.
- the molar percentage of neutralization of the active acid sites of the polymer with a neutralizing agent may, for example, vary between 10% and 90%, for example between 15% and 85%.
- the neutralization of the polymer obtained can also be simple (a single neutralization agent) or multiple (several neutralization agents).
- a molar percentage of neutralization of the active acid sites of the polymer by a neutralization agent containing the calcium ion of between 15% and 40%, for example between 20% and 35%
- a molar percentage of neutralization of the active acid sites of the polymer with one or more mono-functional neutralization agents containing the sodium ion of between 7% and 70%, for example between 20% and 60%,
- a molar percentage of neutralization of the active acid sites of the polymer by a neutralization agent containing magnesium, barium, zinc, aluminum or an amine ion or mixtures thereof and in particular by a neutralization agent containing the magnesium ion of between 0 and % and 30%, for example between 5% and 25%.
- a neutralization agent containing magnesium, barium, zinc, aluminum or an amine ion or mixtures thereof in particular by a neutralization agent containing the magnesium ion of between 0 and % and 30%, for example between 5% and 25%.
- tubular reactor defines an enclosure, for example cylindrical, preferably closed, equipped with at least one inlet orifice at one end of the enclosure and at least one orifice of exit at the opposite end of the enclosure.
- tubular reactor may be straight but it is not necessarily.
- tubular reactor or “piston reactor” may alternatively be used. In this case, it is incorrectly assumed that the flow in said reactor is of the piston type, that is to say that the distribution of the residence times in the reactor is monomodal with a very low dispersion.
- Said reactor may or may not be equipped with devices, for example mechanical, guaranteeing a homogenization of the fluid during its flow.
- the tubular reactor is an extruder as described below.
- the mixing within the tubular reactor can also result from the use of non-moving parts, for example static mixers.
- This kind of Mixing devices is marketed by multiple companies, among which, JLS, Samwha, Mixel, Horus-Environment or Sulzer Ltd.
- the SMX, SMV, SMI type mixers of this company are, for example, equipment capable of performing mixing functions.
- the tabular reactor may consist of one, several or even many segments connected in series. It will thus be easy to vary the length of said reactor.
- the tabular reactor is preferably equipped with one or more devices for the introduction or removal of reagents or products. For example, it will be possible to connect pumps to said tabular reactor.
- the tabular reactor may also be equipped with adjustment systems to adjust the temperature within it.
- a double jacket system could be used to circulate a heat transfer fluid to the reactor wall. It will also be possible to circulate a heat transfer fluid in an exchanger system within the reactor itself.
- There are static mixers whose shape is such that they also act as mixing devices.
- the tabular reactor can also be equipped with adjustment systems to adjust the (de) pressure within it.
- adjustment systems to adjust the (de) pressure within it.
- a tubular reactor composed of metal tubes interconnected by a system of joints and collars which guarantee a perfect seal of the system can be used.
- the residence time can be approximately 30 minutes with an overall flow rate of 10 Kg / h.
- the residence time can be about 20 minutes with an overall flow rate of 35 Kg / h.
- the tabular reactor is an extruder.
- the process of the invention is based on the use of a tabular reactor such as an extruder.
- the term "extruder” defines an enclosure, for example cylindrical, preferably closed, equipped with at least one inlet orifice at one end of the enclosure and at least one orifice of outlet at the opposite end of the enclosure, and which comprises a mixing zone, a transport zone, and optionally one or more screws. It should be noted that the enclosure may be straight but it is not necessarily.
- the term “kneader” is alternately used when said extruder does not comprise a transport screw.
- the extruder may consist of one or more tabular segments connected in series.
- the extruder allows hot kneading in the mixing zone raw materials introduced into the enclosure, and then transport to the outlet port.
- the extruder is preferably equipped with at least one water removal system.
- the extruder can be equipped with several water removal systems arranged at multiple locations on the enclosure. These water evacuation systems make it possible to eliminate the water, which also has the effect of displacing the equilibrium of the reaction and thus facilitating the esterification / amidation reaction of the homopolymer / acidic copolymer, for example (meth) acrylic acid polymer.
- an extruder comprising at least one water removal system may also be advantageous because, in this case, the product obtained at the end of the esterification and / or amidation reaction has a solids content. high, for example greater than 90% by weight. It is conceivable to preserve such a dry extract and to transform, for example, the product in the form of solid powder, granules, etc. (reduction of the temperature below the melting point of the polymer and then grinding / crushing / spraying). Alternatively, the product obtained is solubilized at the end of the esterification / amidation reaction in order to have a product in liquid form. Solubilization can take place in the extruder which is then equipped with a water inlet for example. The solubilization can also be physically separated from the extruder.
- the extruder can also be equipped with adjustment systems allowing for example to adjust the temperature, the pressure and the rates of the various reagents. Furthermore, the extruder may also be equipped with one or more cooling systems.
- the starting homopolymer and / or acidic copolymer has acid functions, for example carboxylic functions, which are the seat of reactions esterification / amidification during the process according to the invention.
- the proportion of acidic functions in the polymer can be evaluated by measuring the acid number of the polymer. As the number of acid functions decreases during the process of the invention, the variation of the acid number of the polymer makes it possible to monitor the degree of progress of the reaction. Concretely, the acid number can be determined by acid-base measurement using, for example, an aqueous solution of KOH or NaOH (mass of KOH or NaOH, expressed in mg, necessary to neutralize the acidity of a gram of polymer).
- said extruder comprises at least one screw, for example two screws.
- said tubular reactor in particular said extruder, comprises several reaction zones having different temperatures varying between ambient temperature and 250 ° C., of which at least one reaction zone having a temperature greater than or equal to 170 ° C. ° C.
- said tubular reactor in particular said extruder comprises three reaction zones having incremental temperatures varying between room temperature (e.g. 20-25 ° C) and 250 ° C, including a reaction zone having a temperature above 180 ° C.
- room temperature e.g. 20-25 ° C
- 250 ° C e.g. 20-25 ° C
- a reaction zone having a temperature above 180 ° C e.g. 20-25 ° C
- Such a configuration allows the introduction of the reactants into the tubular reactor, for example extruder, without prior heating thereof.
- the use of a tubular reactor, in particular an extruder, makes it possible to rapidly bring the reactants to the esterification and / or amidation temperature.
- the preheating and then cooling times which are generally important in batch processes, are within the scope of the present invention reduced or even negligible. However, these preheating and cooling times generally correspond to uncertainties as to the quality of the polymer obtained. Reducing the warm-up time further reduces the risks associated with these uncertainties.
- the residence time in said tubular reactor, in particular the extruder is greater than or equal to 4 minutes, for example between 4 to 40 minutes or between 6 to 30 minutes, as a function of the number of conveying screws present in said tubular reactor, in particular the extruder.
- said acid homopolymer or copolymer to be esterified and / or amidified results from the polymerization or copolymerization of at least one of the monomers selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid and maleic anhydride.
- said acid homopolymer or copolymer to be esterified and / or amidified results from the polymerization or copolymerization of a monomer represented by the formula (1):
- Ri, R 2 and R 3 independently of one another, a hydrogen atom, methyl or (CH 2) Z - 2 COOM,
- said homopolymer or copolymer to be esterified and / or amidified is of acrylic acid type and results from the polymerization or copolymerization of acrylic acid and / or methacrylic acid.
- said homopolymer or copolymer to be esterified and / or amidified is substantially linear.
- the sequence of monomer units is linear but may have some random or regular branches.
- Said homopolymer or acidic copolymer can be obtained by any radical polymerization process, for example in solution, in direct or inverse emulsion, in suspension or precipitation in appropriate solvents, in the presence of catalytic systems and transfer agents.
- Mono functional or multifunctional chain transfer agents are used. It can be a controlled radical polymerization process, for example by nitroxides (NMP) or cobaloxymes, or a radical atom transfer polymerization (ATRP) process.
- NMP nitroxides
- ATRP radical atom transfer polymerization
- hydrogen peroxide or a persulfate which acts as an initiator may be used, as well as, for example, copper sulfate which acts as a catalyst and a chain transfer agent.
- thio lactic acid or another mercaptan having one or more SH functions, is used as an additional chain transfer agent.
- sodium hypophosphite of the chemical formula NaPO 2 H 2 , as a chain transfer agent and oxy-reductant, in the presence of hydrogen peroxide or hydrogen peroxide generator. radicals such as persulfate.
- Said homopolymer or acidic copolymer may be in the form of an aqueous solution or in dry form.
- Said homopolymer or acidic copolymer can be in completely acidic or partially neutralized form.
- the molar percentage of neutralization of the active acid sites of said acid homopolymer or copolymer to be esterified and / or to be amidified by a neutralization agent may, for example, be less than or equal to 90%, for example less than or equal to 80%, or less or equal to 70%.
- the polymer to be esterified and / or amidified is partially neutralized, it may be by means of a single neutralizing agent or several neutralizing agents.
- a molar percentage of neutralization of the active acid sites of the polymer by a neutralization agent containing the calcium ion of between 15% and 40%, for example between 20% and 35%
- a molar percentage of neutralization of the active acid sites of the polymer with one or more monofunctional neutralization agents containing the sodium ion and / or the lithium ion of between 7% and 70%, for example between 20% and 60%,
- the polymers, in particular the acidic polymers of the present invention may be characterized by two following indices:
- IP polymolecularity index also referred to as PD equivalent polydispersity
- the polymolecularity index corresponds to the molecular weight distribution of the different macromolecules within the polymer. If all the macromolecules have the same degree of polymerization (and therefore the same molecular weight), this index is close to 1. If on the other hand, the macro molecules have different lengths (and therefore different molecular weights), the IP index is greater than 1.
- said acid homopolymer or copolymer to be esterified and / or amidified has a polydispersity index IP (Mw / Mn ratio) of between 1 and 3, for example between 1.5 and 3 or between 2 and 2.5.
- IP polydispersity index
- the molecular weight Mw of such polymers may for example be determined by size exclusion chromatography (CES) or in English “Gel Permeation Chromatography” (GPC).
- said acid homopolymer or copolymer to be esterified and / or amidified is a polymer of acrylic acid and / or methacrylic acid of molecular weight Mw between 1000 and 20 000 g / mol, as determined by GPC, for example between 1,000 and 15,000 g / mol, between 1,000 and 10,000 g / mol or alternatively between 1,500 and 8,000 g / mol.
- said acid homopolymer or copolymer to be esterified and / or amidified has a molecular weight of less than 8000 g / mol and a polydispersibility index IP of between 2 and 3.
- Said homopolymer or acid copolymer to be esterified and / or amidified can be characterized by its acid number. This acid number may in particular correspond to the presence of carboxylic groups.
- said comb polymer obtained by the process of the present invention has an acid number advantageously between 35 and 234 mg KOH / g (mass of potassium hydroxide, expressed in mg, necessary to neutralize the acidity one gram of polymer). According to one embodiment, said comb polymer obtained by the process of the present invention has an acid number of between 46 and 156 mg KOH / g.
- poly (alkylene glycol) compounds are used.
- poly (alkylene glycol) (abbreviated PAG) or, equivalently, “poly (oxyalkylene)” (abbreviated POA)
- PAG poly (alkylene glycol)
- POA poly (oxyalkylene)
- poly (alkylene glycol) compounds are advantageously monofunctional, that is to say that they comprise:
- R represents H or a hydrocarbon chain containing from 1 to 10 carbon atoms
- a hydrocarbon chain having 1 to 100 carbon atoms, for example 1 to 70, 1 to 50, 1 to 30 or 1 to 10 carbon atoms.
- alkoxy poly (oxyalkylene glycol) or “monoalkylether poly (alkylene glycol)” can also be used.
- Such a mono-functional compound is grafted onto the acidic polymer by esterification.
- At least one other poly (alkylene glycol) compound may also be used, and it may also be monofunctional or alternatively it may be difunctional, that is to say it may comprise a reactive function of OH or -NHR (wherein R is H or a hydrocarbon chain having from 1 to 10 carbon atoms) at each of its ends.
- the poly (alkylene glycol) compounds used in the context of the present invention may comprise compounds consisting of polymerized epoxides, for example ethylene oxide (-O-CH 2 -CH 2 -, abbreviation: OE), propylene oxide (abbreviation: OP) and / or 1-butylene oxide (abbreviation: OB).
- OE ethylene oxide
- OP propylene oxide
- OB 1-butylene oxide
- the poly (alkylene glycol) compound used in the continuous process of the present invention has a formula (I):
- A represents a polymeric chain consisting of:
- Ra represents a hydrocarbon chain, linear or branched, comprising from 1 to 100 carbon atoms, for example from 1 to 70, from 1 to 60, from 1 to 50 or from 1 to 30 carbon atoms.
- the poly (alkylene glycol) compound used in the continuous process of the present invention has a formula ( ⁇ ):
- the propylene oxide units -O-CH 2 -CH (-CH 3 ) - and the ethylene oxide units -O-CH 2 -CH 2 - are arranged alternately or randomly or in blocks;
- the poly (alkylene glycol) compound used in the continuous process of the present invention consists of polyethylene oxide units and / or polypropylene oxide units and have at their free end. an alkyl group comprising from 1 to 4 carbon atoms, which is a linear or branched chain.
- the poly (alkylene glycol) compound as represented in formulas (I) and ( ⁇ ) includes at least 80 mol%, for example at least 85 mol% of ethylene oxide groups. This gives a very good balance between hydrophobicity and hydrophilicity in the comb polymer obtained.
- the esterification is carried out in the presence, besides the poly (alkylene glycol) compound of formula (I) or ( ⁇ ), of a poly (alkylene glycol) having a formula (II): (II) HO - [(CHR 6 -CH 2 -O) r - (CHR 7 -CH 2 -O) s - (CH 2 -CH 2 -O) t ] - H
- R O and R 7i independently of one another represent an alkyl group comprising from 1 to 4 carbon atoms
- r and s independently of one another, vary from 0 to 150,
- the alkylene oxide units of the formula -CHR 6 -CH 2 -O-, the alkylene oxide of the formula -CHR 7 -CH 2 -O- and the ethylene oxide units -CH 2 - CH 2 -0- are arranged alternately or statistically or in blocks.
- the poly (alkylene glycol) having a formula (II) is present at a content of less than 5% by weight, relative to the total of the copolymer obtained at the end of the process, for example at a lower content or equal to 4% by weight or 3% by weight.
- the esterification is carried out in the presence, in addition to the poly (alkylene glycol) compound of formula (I) or ( ⁇ ), of a poly (alkylene glycol) having a formula (III) :
- the poly (alkylene glycol) compounds comprise polyethylene oxide units and / or polypropylene oxide units and have at their free end a hydroxide group.
- the poly (alkylene glycol) compounds used in the context of the present invention may, for example, comprise a dominant proportion of ethylene-oxy group in combination with a secondary proportion of propylene group. oxy.
- Specific examples of the alkylene glycol polymer include: polyalkylene glycols having an average molecular weight of 1,000, 4,000, 6,000 and 10,000 g / mol; polyethylene polypropylenes glycols having a percentage of ethylene oxide of between 20 and 80% by weight and a percentage of propylene oxide of between 20 and 80% by weight. Such compounds are commercially available.
- poly (alkylene glycol) compounds comprise a mixture:
- poly (alkylene glycol) compounds comprising polyethylene oxide units and / or polypropylene oxide units and having at their free end an alkyl group comprising from 1 to 4 carbon atoms, which is a chain or branched, and
- poly (alkylene glycol) compounds comprising polyethylene oxide units and / or polypropylene oxide units and having at their free end H.
- esterification process of the present invention takes place in the presence of at least one poly (alkylene glycol) introduced in powder form or in the molten state, for example using a hopper.
- an antioxidant agent also called simply “antioxidant” or “thermal stabilizer”
- an antioxidant agent also called simply “antioxidant” or “thermal stabilizer”
- the use of an antioxidant agent maintains the expected quality of the polymer.
- the minimum temperature of esterification and / or amidification existing in said tubular reactor, in particular the extruder has been fixed at 170 ° C, which allows to significantly reduce the residence time in the reactor and thus improve the profitability of the polymer obtained.
- antioxidants in polymer preparation processes varies with the structure and chemical composition of antioxidants. They are intended to slow down or prevent the oxidation of reagents or reaction products during the process.
- the antioxidants include heteroatoms, for example nitrogen atoms, which can lead to changes in the behavior of the polymers obtained in the applications.
- the antioxidants are not intended to be incorporated into the comb structure polymer. Nevertheless, it is possible that some of these agents remain grafted onto the polymer, exceptionally and unexpectedly. In this case, the amounts of said agents are very small.
- the antioxidant used in said esterification and / or amidification process comprises an aromatic amine, a phosphine group, an organophosphate group and / or a piperidine ring.
- the antioxidant is an amine having at least one aromatic group substituted by an alkyl chain.
- the antioxidant comprises two aromatic groups, at least one of which is substituted with an alkyl chain having from 3 to 9 carbon atoms.
- this is the compound with CAS number 68411-46-1.
- Irganox TM 5057 sold by CIBA TM is a commercial example of such a compound.
- the antioxidant is an organophosphate compound.
- the antioxidant is an aromatic and / or aliphatic phosphite.
- this is the compound whose CAS number is 25550-98-5 or 101-02-0.
- Doverphos TM 7 and Doverphos TM 10 marketed by the company DOVER TM are commercial examples of such compounds.
- the antioxidant is selected from the group consisting of trimethyl dihydroquinoline polymer, diphenylamine derivatives, phenothiazine, phenyl-alpha-naphthylamine, 4,4'-methylene-bis-2, 6-di-tert-butylphenol, butylated hydroxyanisole (BHA), methoxyphenol (hydroxyanisole), dihydrobenzene (DHB), a compound of the family of hydroxyphenols (for example hydroquinone or pyrocatechol) or a mixture of these agents.
- BHA butylated hydroxyanisole
- DVB dihydrobenzene
- a compound of the family of hydroxyphenols for example hydroquinone or pyrocatechol
- Such agents are commercially available.
- the molar ratio between said poly (alkylene glycol) and said acid homopolymer or copolymer varies between 100: 1 and 1: 1, for example 50: 1 and 5: 1 or between 25: 1 and 10: 1.
- the esterification and / or amidification process uses from 1% to 30% by weight of (meth) acrylic acid polymer, for example from 2% to 20% of the polymer of the (meth) acrylic acid, and from 70% to 99% by weight of at least one poly (alkylene glycol) compound, for example from 80% to 98% of at least one poly ( alkylene glycol).
- an esterification and / or amidation catalyst in the context of the present invention.
- an alkaline or alkaline-earth salt of a strong protic acid that is to say capable of releasing protons and having a pKa of less than 0, is used. .
- the catalyst is a salt of a strong protic acid having a hydrocarbon group.
- Alkyl sulphonic, aryl sulphonic or aryl alkyl sulphonic acid salts such as the sodium, potassium, lithium, calcium and magnesium salts of para-toluene sulphonic acid, are more particularly mentioned.
- a strong neutralized protic acid makes it possible to improve the conversion rate of the poly (alkylenes glycols) without chain cleavage, while having a catalytic activity sufficient to promote the esterification / amidation reaction.
- it may, for example, be para toluene sulfonic acid, methanesulfonic acid, sulfuric acid, Lewis acid.
- Pentavalent phosphorus catalysts such as phosphoric acid (H 3 PO 4 ), phosphorous acid (H 3 PO 3 ), hypophosphorous acid (H 3 PO 2 ), phenylphosphinic acid (H 2 PO 3 ) are also mentioned.
- polyphosphoric acids such as phosphoric anhydride, tetrapolyphosphoric acid, pyrophosphoric acid (H 4 P 2 O 7 ), trimetaphosphoric acid, phosphoric pentachloride, a phosphorous ester such as triphenyl phosphite ( P (OPh) 3 ), a hypophosphite such as ammonium hypophosphite, sodium hypophosphite, boric acid and its derivatives such as boric anhydride (B 2 O 3 ), phosphoric anhydride (P 2 O 5 ) and pyrophosphoric acid (H4P2O7).
- P (OPh) 3 ) triphenyl phosphite
- a hypophosphite such as ammonium hypophosphite, sodium hypophosphite
- boric acid and its derivatives such as boric anhydride (B 2 O 3 ), phosphoric anhydride (P 2 O 5 ) and pyrophosphoric acid (H
- the esterification and / or amidation catalyst can be used in an amount of from 0.04% to 10% molar, based on the number of acid functions, for example carboxylic acid, of the acidic polymer.
- the continuous process comprises at least the following steps:
- step b) introducing the mixture of step a) into said tubular reactor, in particular the extruder,
- the antioxidant is introduced during step a) and / or into said tubular reactor, in particular the extruder in one or more times, and
- the esterification and / or amidation of said homopolymer / copolymer is carried out by hot reaction in the tubular reactor, for example in the mixing and transport zone of the extruder, optionally equipped with a system of removal of water, said esterification and / or amidification taking place at a temperature greater than or equal to 170 ° C, optionally in the presence of an esterification and / or amidation catalyst, optionally at reduced pressure and / or under a flow of inert gas.
- the mixing zone comprises a homogenization of the mixture.
- the esterification and / or amidation of said homopolymer / copolymer is carried out by hot kneading in the mixing and transport zone of the extruder, optionally equipped with a water removal system, said esterification and / or amidification taking place at a temperature greater than or equal to 170 ° C, optionally in the presence of an esterification and / or amidation catalyst, optionally under reduced pressure and / or under a flow of inert gas.
- the continuous process comprises at least the following steps:
- the esterification and / or amidation of said homopolymer / copolymer is carried out by hot reaction in the tubular reactor, for example in the mixing and transport zone of the extruder, possibly equipped with an elimination system water, said esterification and / or amidification taking place at a temperature greater than or equal to 170 ° C, optionally in the presence of an esterification and / or amidation catalyst, optionally at reduced pressure and / or under a stream of inert gas.
- the mixing zone comprises a homogenization of the mixture.
- the esterification and / or amidification of said homopolymer / copolymer is carried out by hot kneading in the mixing and transport zone of the extruder, optionally equipped with a water removal system, said esterification and / or amidification occurring at a temperature greater than or equal to 170 ° C, optionally in the presence of an esterification and / or amidation catalyst, optionally at pressure reduced and / or under a stream of inert gas.
- Another object of the present invention relates to the polymer, having a hydrocarbon chain and poly (oxyalkylated) side groups, also called comb polymer, obtainable by the continuous process described above.
- said polymer having a hydrocarbon chain and poly (oxyalkylated) side groups obtained by the continuous esterification and / or amidation process has a molecular weight Mw of between 15,000 and 400,000 g. / mol, for example between 20 000 and 200 000 g / mol, between 25 000 and 150 000 g / mol or between 30 000 and 125 000 g / mol.
- this polymer has an IP polydispersity index of less than 2.5, for example less than 2.
- this polymer has an IP polydispersity index of less than 2.5, for example less than 2 or 1.6.
- the process of the present invention makes it possible to obtain a comb polymer having a low IP polydispersity index.
- the technical characteristics of the process are such that the rate of degradation of the side chains and the degree of crosslinking are indeed very low.
- the method of the present invention thus makes it possible to obtain a polymer of better quality, while improving the production yield.
- the comb polymer thus obtained is characterized in that it has a degree of polymeric purity such that the content of free poly (alkylene glycol) is less than 15% by weight (by relative to the total weight introduced into the reactor), as measured by CES (see details below).
- the comb polymer thus obtained is characterized in that it has a degree of polymeric purity such that the content of free poly (alkylene glycol) is less than 13% by weight (relative to to the total weight introduced into the reactor), as measured by HPLC.
- the molecular weights Mp are expressed in g / mol.
- the measured molecular weight ratio Mp / theoretical molecular weight Mp can be calculated.
- the calculation of such a ratio makes it possible in particular to evaluate the efficiency of the process of the present invention.
- the molecular weight Mp of the comb polymer (PP) obtained by the process of the present invention is measured by CES. This quantity is called MPM PP in the context of the present invention.
- Mpt PP The theoretical molecular weight of the comb polymer (PP) is calculated according to the following formula. This quantity is called Mpt PP in the context of the present invention.
- Mpt PP is the theoretical molecular weight Mp of the comb polymer (PP),
- Mp PAL is the molecular weight Mp of the acidic polymer (PAL),
- Mp PAG is the molecular weight Mp of polyalkylene glycols (PAG),
- N PAL is the number of moles of acidic polymers introduced into the reactor
- N PAG is the number of moles of poly (alkylene glycol) introduced into the reactor
- N res is the number of moles of residual poly (alkylene glycol) measured by CES at the reactor outlet.
- the comb polymer obtained is such that the ratio Mp measured / Mp theoretical is between 0.3 and 3, for example between 0.5 and 2.
- the comb polymer obtained is such that the ratio Mp measured / theoretical Mp is between 0.8 and 1.2, for example between 0.85 and 1.15 or between 0.9 and 1 1.
- the comb polymer obtained is such that the Mpmpp / Mptpp ratio is between 0.8 and 1.2.
- the process conditions are such that it tends to a rate of use of polyalkylene glycols introduced into the extruder close to 100%.
- it is ensured that the degradation rate of these polyalkylene glycols, as well as pendant chains grafted onto the acidic polymer, tends to 0%.
- thermal crosslinking inducing crosslinking is limited, so that the measured Mp tends to the theoretical Mp when the grafting rate of polyalkylene glycols tends to 100%.
- the comb polymer thus obtained can be used as an adjunct for hydraulic composition.
- the adjuvant can be presented as a solution in a suitable solvent.
- the appropriate solvent comprises or consists of water.
- another solvent such as an alcohol or a glycol may be considered in addition or alternatively, for example to facilitate solubilization.
- the concentration of the adjuvant polymer depends mainly on the intended application.
- the formulation of the adjuvant comprises 1 to 50% by weight, preferably 10 to 40% by weight of polymer relative to the total weight. Process for the preparation of the comb polymer by polymerization then esterification / amidification
- Another subject of the present invention relates to a process for preparing a comb polymer, said process comprising the following steps:
- step b) esterification / continuous amidation of said homopolymer or acidic copolymer obtained according to step a), as described above, in the presence of at least one poly (alkylene glycol) in solid or melt form and an antioxidant, to obtain said comb polymer,
- step b) optionally, solubilization of the comb polymer obtained according to step b), d) optionally, complete or partial neutralization of the comb polymer obtained according to step b) and / or c),
- step e) optionally, powdering the comb polymer obtained according to step b) and / or c) and / or d).
- step a) of this process said homopolymer or acidic copolymer is prepared by controlled radical polymerization, as described above.
- said process comprises the following steps:
- step b) esterification / continuous amidation of said homopolymer or acidic copolymer obtained according to step a), as described above, in the presence of at least one poly (alkylene glycol) in solid form or in the molten state, and an antioxidant, to obtain said comb polymer,
- Another subject of the present invention relates to a polymer having a hydrocarbon chain and poly (oxyalkylated) side groups, also called comb polymer, obtainable by the polymerization and esterification and / or amidification process described above. .
- the present invention also relates to the dispersant additive for hydraulic composition comprising the comb polymer, as described above, obtainable by the polymerization and esterification / amidation process described above.
- the subject of the present invention is the use of a polymer also called comb polymer, obtainable by the polymerization process and esterification / amidation described above, to reduce the water content of the hydraulic compositions.
- Such a technique implements a WATERS TM brand liquid chromatography apparatus equipped with a detector.
- This detector is a WATERS TM refractometric concentration detector.
- the liquid chromatography apparatus is provided with a steric exclusion column appropriately chosen by those skilled in the art in order to separate the different molecular weights of the polymers studied.
- the liquid elution phase is an aqueous phase adjusted to pH 9 with 1N sodium hydroxide containing 0.05M NaHCO 3 , 0.1M NaNO 3 , 0.02M trietanolamine and 0.03% NaN 3 .
- the polymerization solution is diluted to 0.9% dry in the solubilization solvent of the CES, which corresponds to the liquid phase of elution of the CES to which 0.04% is added. of dimethylformamide which acts as a flow marker or internal standard. Then filtered at 0.2 ⁇ . 100% are then injected into the chromatography apparatus (eluent: an aqueous phase adjusted to pH 9.00 with 1N sodium hydroxide containing 0.05M NaHCO 3 , 0.1M NaNO 3 , 0.02M trietanolamine and 0 , 03% NaN 3 ).
- the liquid chromatography apparatus contains an isocratic pump (WATERS TM 515) with a flow rate of 0.8 ml / min.
- the chromatography apparatus also comprises an oven which itself comprises in series the following column system: a precolumn of the GUARD COLUMN ULTRAH type YDRO GEL WATERS TM of 6 cm long and 40 mm inside diameter, and a column of type ULTRAHYDROGEL WATERS TM 30 cm long and 7.8 mm inside diameter.
- the detection system consists of a RI WATERS TM 410 type refractometric detector. The oven is heated to a temperature of 60 ° C and the refractometer is heated to a temperature of 45 ° C.
- the chromatography apparatus is calibrated by standards of powdered polyacrylate of various molecular weights certified by the supplier: POLYMER STANDARD SERVICE or AMERICAN POLYMER STANDARDS CORPORATION.
- the molecular weight of the comb polymers according to the invention is determined by CES.
- One such technique uses a WATERS TM brand liquid chromatograph with two detectors, one of which combines the static scattering of light at 90 ° C to the viscometry measured by one MALVER TM detector and the other. being a WATERS TM refractometric concentration detector.
- This liquid chromatography apparatus is provided with steric exclusion columns appropriately chosen by those skilled in the art in order to separate the different molecular weights of the polymers studied.
- the liquid phase of elution is an aqueous phase containing 1% of K 0 3 .
- the polymerization solution is diluted to 0.9% in the eluent of the CES, and then filtered at 0.2 ⁇ . 100 are then injected into the CES apparatus.
- the eluent of the CES is a 1% solution of KN0 3 .
- the liquid chromatography apparatus contains an isocratic pump (Waters 515) with a flow rate of 0.8 ml / min, a furnace containing the following column system as standard: a 6 cm GUARD COLUMN ULTRAHYDROGEL WATERS TM precolumn long and 40 mm internal diameter, one column ULTRAHYDROGEL WATERS TM type 30 cm long and 7.8 mm inside diameter and two columns ULTRAHYDROGEL 120 ANGSTROM WATERS TM 30 cm long and 7.8 mm inside diameter and then comes in parallel the detection system: on one side a refractometric detector type RI WATERSTM 410 and on the other side a dual detector viscometer and light scattering at a 90 ° angle of 270 type DUAL DETECTOR MALVERN TM .
- the oven is heated to 55 ° C, and the refractometer is heated to 45 ° C.
- the CES device is calibrated by a universal / multidetector type calibration by a single standard of PEV 19k type PolyCAL TM MALVERN TM with the following characteristics are known: concentration, IV, Mw, Mn, PI, thus allowing to calibrate each detector. Acid number of a polymer
- the acid number of the polymer is determined by acid-base measurement by dissolving 1 g of polymer in 100 g of methanol and then titrating the solution with 1 N of aqueous KOH solution using an automatic titrator.
- the acid number is measured in mg KOH / g, that is to say, mass of KOH necessary to neutralize the acidity of the polymer.
- This example illustrates the reactive extrusion condensation of a homopolymer of methacrylic acid with a methoxy poly (ethylene glycol) (MPEG) of molecular weight 5,000 g / mol (commercially available).
- MPEG methoxy poly (ethylene glycol)
- TSA® corotative twin-screw extruder is used, the geometric parameters of which are as follows:
- the flow rates are then proportionally modified to adjust the residence time in the extruder.
- Said residence time is measured by adding a colored tracer.
- the molar ratio between MPEG and the acidic homopolymer is 7.1: 1.
- the extruder has a reaction zone whose temperature is set at 220 ° C.
- the flow rate is set so that the residence time of the reagents and products in the extruder is 25 minutes ⁇ 1.
- the product obtained at the extruder outlet is in the form of a molten resin.
- Ratio Mpm pp / Mpt pp 1.13.
- This example illustrates the reactive extrusion condensation of a homopolymer of methacrylic acid with a methoxy poly (ethylene glycol) (MPEG) of molecular weight 2,000 g / mol (commercially available).
- MPEG methoxy poly (ethylene glycol)
- the flow rates are then proportionally modified to adjust the residence time in the extruder. Said residence time is measured by adding a colored tracer.
- the molar ratio between MPEG and the acidic homopolymer is 13.4: 1.
- the extruder has a reaction zone whose temperature is set at 220 ° C.
- the flow rate is set so that the residence time of the reagents and products in the extruder is 24 minutes ⁇ 1.
- the product obtained at the extruder outlet is in the form of a molten resin.
- the product is then solubilized by adding water and neutralized with sodium hydroxide (50%) until a solids content of 41.1% by weight is obtained.
- Ratio Mpm pp / Mpt pp 1.5.
- This example illustrates the reactive extrusion condensation of a homopolymer of methacrylic acid with a methoxy poly (ethylene glycol) (MPEG) of molecular weight 2,000 g / mol (commercially available).
- MPEG methoxy poly (ethylene glycol)
- the flow rates are then proportionally modified to adjust the residence time in the extruder.
- Said residence time is measured by adding a colored tracer.
- the mole ratio between MPEG and acidic rhomopolymer is 8.8: 1.
- the extruder has a reaction zone whose temperature is set at 220 ° C.
- the flow rate is set so that the residence time of the reagents and products in the extruder is 30 minutes ⁇ 1.
- the product obtained at the extruder outlet is in the form of a molten resin.
- the product is then solubilized by adding water and neutralized with sodium hydroxide (50%) until a solids content of 40.4% by weight is obtained. Characterization of the polymer obtained
- Ratio Mpm pp / Mpt pp 1.7.
- This example illustrates the reactive extrusion condensation of a homopolymer of methacrylic acid with a methoxy poly (ethylene glycol) (MPEG) of molecular weight 5,000 g / mol (commercially available).
- MPEG methoxy poly (ethylene glycol)
- the flow rates are then proportionally modified to adjust the residence time in the extruder.
- Said residence time is measured by adding a colored tracer.
- the molar ratio between MPEG and acidic rhomopolymer is 20: 1.
- the extruder has a reaction zone whose temperature is set at 220 ° C.
- the flow rate is set so that the residence time of the reagents and products in the extruder is 30 minutes ⁇ 1.
- the product obtained at the extruder outlet is in the form of a molten resin.
- the product is then solubilized by adding water and neutralized with sodium hydroxide (50%) until a solids content of 40.3% by weight is obtained.
- Ratio Mpm pp / Mpt pp 1.7.
- This example illustrates the reactive extrusion condensation of a homopolymer of acrylic acid with a methoxy poly (ethylene glycol) (MPEG) of molecular weight 2,000 g / mol (commercially available).
- MPEG methoxy poly (ethylene glycol)
- the flow rates are then proportionally modified to adjust the residence time in the extruder. Said residence time is measured by adding a colored tracer.
- the extruder has a reaction zone whose temperature is set at 220 ° C. The flow rate is set so that the residence time of the reagents and products in the extruder is 30 minutes ⁇ 1.
- the product obtained at the extruder outlet is in the form of a molten resin.
- the product is then solubilized by adding water and neutralized with sodium hydroxide (50%) until a solids content of 39.3% by weight is obtained. Characterization of the polymer obtained
- This example illustrates the use of the polymers obtained according to Examples 1 to 5 in a mortar composition whose constitution is given in Table 1 below. The workability of the composition is measured at T0. It is demonstrated that the polymers prepared according to the process of the present invention can be qualified as water reducers.
- the cone is placed on a plate moistened with a sponge.
- the cone is then filled with a determined quantity of each of the preparations. The filling lasts 2 minutes. The contents of the cone are packed with a metal rod.
- Examples 1 to 5 are tested on a mortar formulation according to EN 196-1 by mixing with stirring, standardized sand (EN 196-1), cement (CEM I 52.5 N), water and a dispersant additive according to the invention.
- the proportions are given in Table 1 below.
- Test 1-1 is a negative control. It illustrates a reference mortar composition without adjuvant, that is to say without dispersant additive according to the invention.
- the use of a dispersant additive reduces the amount of water in the hydraulic composition while maintaining initial handling similar to that of the negative control.
- the dispersant additive may be described as a high water reducer in accordance with the standard ADJUVANT NF EN 934-2 according to which is qualified as "high water reducer” or “superplasticizer” an adjuvant that allows a reduction of water for the water.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ceramic Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Mechanical Engineering (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Civil Engineering (AREA)
- Polyethers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR1462027A FR3029524B1 (fr) | 2014-12-08 | 2014-12-08 | Procede continu d'esterification et ou d'amidification, sans solvant organique, d'un homopolymere ou copolymere acide |
PCT/FR2015/053349 WO2016092190A1 (fr) | 2014-12-08 | 2015-12-07 | Procede continu d'esterification et/ou d'amidification, sans solvant organique, d'un homopolymere ou copolymere acide |
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EP3230345A1 true EP3230345A1 (fr) | 2017-10-18 |
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EP15817484.7A Pending EP3230345A1 (fr) | 2014-12-08 | 2015-12-07 | Procede continu d'esterification et/ou d'amidification, sans solvant organique, d'un homopolymere ou copolymere acide |
Country Status (10)
Country | Link |
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US (1) | US10207446B2 (es) |
EP (1) | EP3230345A1 (es) |
JP (1) | JP2018500397A (es) |
KR (1) | KR20170092531A (es) |
CN (1) | CN106795367B (es) |
CA (1) | CA2963864A1 (es) |
FR (1) | FR3029524B1 (es) |
MX (1) | MX2017007439A (es) |
MY (1) | MY191556A (es) |
WO (1) | WO2016092190A1 (es) |
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AU2017368100B2 (en) | 2016-12-01 | 2022-03-10 | Huntsman International Llc | Functionalized polyacrylate polymer compositions |
US20210040000A1 (en) * | 2018-01-24 | 2021-02-11 | Sika Technology Ag | Dispersant for reducing the mixing times of mineral binder systems |
FR3130808A1 (fr) * | 2021-12-20 | 2023-06-23 | Coatex | Composition polyacrylique réactive |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0669364A1 (en) * | 1993-12-24 | 1995-08-30 | Marubishi Oil Chemical Co., Ltd. | Modifier for resin and rubber |
JP3344109B2 (ja) * | 1994-10-03 | 2002-11-11 | 住友化学工業株式会社 | 樹脂組成物 |
US6103839A (en) | 1998-05-11 | 2000-08-15 | Nalco Chemical Company | Horizontally flowing continuous free radical polymerization process for manufacturing water-soluble polymers from monomers in aqueous solution |
JP2000144114A (ja) * | 1998-11-11 | 2000-05-26 | Nagase Kasei Kogyo Kk | 帯電防止用樹脂改質剤 |
DE10015135A1 (de) * | 2000-03-29 | 2001-10-04 | Basf Ag | Verfahren zur Modifizierung von Säuregruppen enthaltenden Polymerisaten |
FR2821620B1 (fr) | 2001-03-02 | 2003-06-27 | Coatex Sas | Procede de polymerisation radicalaire controlee de l'acide acrylique et de ses sels, les polymeres de faible polydispersite obtenus, et leurs applications |
FR2868068B1 (fr) | 2004-03-29 | 2006-07-14 | Coatex Soc Par Actions Simplif | Nouveaux composes soufres : utilisation comme agent de transfert pour la polymerisation radicalaire controlee de l'acide acrylique, polymeres obtenus et leurs applications |
EP1348729A1 (de) | 2002-03-25 | 2003-10-01 | Sika Schweiz AG | Polymere in festem Aggregatzustand |
FR2866891B1 (fr) | 2004-02-27 | 2006-05-26 | Arkema | Compositions thermoplastiques de copolymeres d'ethylene greffes par des motifs polyethers |
FR2868072B1 (fr) | 2004-07-28 | 2006-06-30 | Coatex Soc Par Actions Simplif | Polymeres obtenus par l'utilisation de composes soufres comme agents de transfert pour la polymerisation radicalaire controlee de l'acide acrylique et leurs applications |
FR2877670B1 (fr) * | 2004-11-09 | 2007-02-02 | Arkema Sa | Dispersants acryliques hydrosolubles obtenus par polymerisation radicalaire controlee |
US7592413B2 (en) * | 2005-09-22 | 2009-09-22 | E. I. Du Pont De Nemours And Company | Manufacture of aromatic polyester |
FR2900930B1 (fr) * | 2006-05-12 | 2008-08-08 | Coatex Sas | Procede de fabrication de polymeres peigne par sechage puis fonctionnalisation de la chaine principale (meth)acrylique, polymeres obtenus et leurs utilisations |
FR2926558B1 (fr) * | 2008-01-17 | 2010-03-05 | Coatex Sas | Amelioration d'un procede de fabrication de polymeres peignes par ajout d'un antioxydant, polymeres obtenus et leurs applications |
FR2956663B1 (fr) | 2010-02-24 | 2012-05-18 | Coatex Sas | Solution aqueuse de polymere peigne (meth)acrylique fluide avec un extrait sec superieur a 60 %, procede de fabrication et utilisation comme agent fluidifiant. |
DE102010056566A1 (de) * | 2010-12-30 | 2012-07-05 | Clariant International Ltd. | Kontinuierliches Verfahren zur Veresterung Säuregruppen tragender Polymere |
FR2974090B1 (fr) * | 2011-04-15 | 2013-05-31 | Chryso | Copolymeres a groupements gem-bisphosphones |
FR2978965B1 (fr) | 2011-08-11 | 2015-02-13 | Chryso | Polymeres dispersants a stabilite thermique amelioree |
US9499642B2 (en) * | 2011-11-11 | 2016-11-22 | Rohm And Haas Company | Small particle size hypophosphite telomers of unsaturated carboxylic acids |
FR2993887B1 (fr) | 2012-07-27 | 2014-12-19 | Setup Performance | Procede de preparation de polyamide par extrusion reactive et extrudeuse adaptee pour la mise en oeuvre d'un tel procede |
FR2995899B1 (fr) | 2012-09-26 | 2014-10-03 | Coatex Sas | Procede de polymerisation de l'acide (meth)acrylique en solution, solutions de polymeres obtenues et leurs utilisations. |
-
2014
- 2014-12-08 FR FR1462027A patent/FR3029524B1/fr active Active
-
2015
- 2015-12-07 MX MX2017007439A patent/MX2017007439A/es unknown
- 2015-12-07 CN CN201580055817.1A patent/CN106795367B/zh active Active
- 2015-12-07 MY MYPI2017700953A patent/MY191556A/en unknown
- 2015-12-07 US US15/516,733 patent/US10207446B2/en active Active
- 2015-12-07 JP JP2017515726A patent/JP2018500397A/ja active Pending
- 2015-12-07 WO PCT/FR2015/053349 patent/WO2016092190A1/fr active Application Filing
- 2015-12-07 EP EP15817484.7A patent/EP3230345A1/fr active Pending
- 2015-12-07 CA CA2963864A patent/CA2963864A1/fr not_active Abandoned
- 2015-12-07 KR KR1020177010074A patent/KR20170092531A/ko active IP Right Grant
Also Published As
Publication number | Publication date |
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FR3029524B1 (fr) | 2018-03-02 |
CN106795367B (zh) | 2019-11-01 |
US20170297255A1 (en) | 2017-10-19 |
US10207446B2 (en) | 2019-02-19 |
MY191556A (en) | 2022-06-30 |
KR20170092531A (ko) | 2017-08-11 |
WO2016092190A1 (fr) | 2016-06-16 |
JP2018500397A (ja) | 2018-01-11 |
CN106795367A (zh) | 2017-05-31 |
MX2017007439A (es) | 2017-09-28 |
CA2963864A1 (fr) | 2016-06-16 |
FR3029524A1 (fr) | 2016-06-10 |
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