EP1373326A1 - Method for obtaining polybutadiene-based aqueous dispersions - Google Patents

Method for obtaining polybutadiene-based aqueous dispersions

Info

Publication number
EP1373326A1
EP1373326A1 EP02704849A EP02704849A EP1373326A1 EP 1373326 A1 EP1373326 A1 EP 1373326A1 EP 02704849 A EP02704849 A EP 02704849A EP 02704849 A EP02704849 A EP 02704849A EP 1373326 A1 EP1373326 A1 EP 1373326A1
Authority
EP
European Patent Office
Prior art keywords
initiator
azobisisobutyrate
weight
initiators
alkoxy
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.)
Ceased
Application number
EP02704849A
Other languages
German (de)
French (fr)
Inventor
Damien Colombie
Frédéric LEMAHIEU
Denis Tembou N'zudie
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Atofina SA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Atofina SA filed Critical Atofina SA
Publication of EP1373326A1 publication Critical patent/EP1373326A1/en
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/06—Butadiene

Definitions

  • the present invention relates to a process for the preparation of aqueous dispersions of copolymers by emulsion polymerization of ethylenically unsaturated monomers in the presence of at least one initiator or initiator of free radicals.
  • Aqueous dispersions based on butadiene, in particular styrene / butadiene and acrylonitrile / butadiene latexes are widely used in various applications, such as paper processing agent and the manufacture of rubber, for example tires. It is well known that the emulsion polymerization of butadiene or its copolymerization with other monomers leads to a crosslinked polymer whose degree of branching increases with the conversion rate. This crosslinking has a detrimental effect on the use properties of the latexes obtained. For example, it can affect the coalescence of latex particles during coating applications, such as coating paper, or contribute to poor control of the hardness of rubber, thereby limiting its processability.
  • the commonly used transfer agents are mercaptans which, although having a very low residual content in the final latexes, induce an undesirable characteristic odor.
  • the object of the present invention is to remedy the drawbacks of the prior art by proposing an effective polymerization process, resulting in good conversion of the monomers, which leads to latexes of copolymers having a low degree of crosslinking.
  • This weak crosslinking can be used to reduce the mercaptan level and thus decrease the odor or increase the conversion rate without obtaining prohibitive crosslinking rates.
  • the process for obtaining aqueous dispersions of copolymers consisting in polymerizing a mixture of monomers containing at least 60% by weight of butadiene and at least one monomer chosen from styrene, acrylic esters, vinyl nitriles optionally with up to 40% by weight of one or more other copolymerizable unsaturated monomers, in aqueous emulsion in the presence of one or more initiator (s) or initiator (s) free radicals is characterized in that at least one of the initiators or initiators or that the initiator or initiator is an ester of azocarboxylic acid of formula (I):
  • Ri, R2, R3, and R are independently selected from the group consisting of - linear or branched al yl having from 1 to 9 carbon atoms, preferably from 1 to 4 carbon atoms, optionally substituted by one or several substituents selected from the hydroxyl, C1 to C6 alkoxy, halogen substituents;
  • - aralkyl optionally substituted by one or more alkyl groups -C 6 -alkoxy-C @, hydroxy and halogen;
  • R - aryls optionally substituted with one or more substituents selected from C1 to C6 alkyl, C1 to C6 alkoxy, hydroxy and halogen; with at least one of the combinations R ⁇ -R 2 and R 3 -R which may optionally form an aliphatic cycle;
  • R "and R ' are the same or different from each other and are selected independently from the group consisting of linear or branched aliphatic radicals in Ci to C1 0 , preferably in Ci to C.
  • the advantage of these esters d azocarboxylic acids is their low melting point, generally below 27 ° C.
  • the preferred azocarboxylic acid esters are those in which R "and R 'represent methyl or ethyl and in which Ri, R 2 , R 3 , and R 4 advantageously represent the alkyl groups of Ci to C 4 . In addition, they generate neither toxic byproducts, nor even cyan compounds.
  • the particularly preferred azocarboxylic acid ester is diethyl 2, 2'-azobisisobutyrate, that is to say with R ⁇ R 2 , R 3 , and R 4 representing methyl and R 'and R "representing A mixture of diethyl 2, 2'-azobisisobutyrate (DEAB) and of dimethyl 2,2'-azobisisobutyrate (DMAB) with a mass content of DEAB, preferably greater than 50%, has given very interesting results.
  • DEAB diethyl 2, 2'-azobisisobutyrate
  • DMAB dimethyl 2,2'-azobisisobutyrate
  • Mixtures of DEAB, DMAB and methyl 2, ethyl 2 '-azobisisobutyrate with preferably a COOMe / COOEt ⁇ 10 molar ratio may be suitable.
  • the azocarboxylic acid esters of formula (I) can be prepared by a conventional two-step process comprising a first step of conversion of the azonitrile, by reaction with an alcohol, in the presence of HCl, according to the Pinner reaction, leading with the corresponding azoiminoether hydrochloride and a second hydrolysis step in the presence of the hydrochloride thus obtained. They can also be prepared by improved methods as described in documents DE 2 254 572, EP 80 275 and EP 230 586.
  • esters can be prepared by reacting an azonitrile with an alcohol and hydrochloric acid in an aromatic solvent, with an HCl / azonitrile molar ratio> 2 when the alcohol is methanol and> 3 when the alcohol is ethanol or higher alcohol.
  • the azocarboxylic acid ester is used in combination with the usual initiators in emulsion polymerization, such as hydroperoxides, in particular tert-butyl or di-isopropylbenzene hydroperoxide, and sodium, potassium or sodium persulfates. 'ammonium.
  • the amount of azocarboxylic acid ester is preferably between 5 and 95% by weight relative to the total weight of the initiators and better still between 30 and 70%.
  • the total amount of initiators involved is between 0.05 and 4% by weight relative to the weight of the monomers used.
  • the initiators can be introduced in batch, continuous, semi-batch or semi-continuous.
  • initiators can be associated with a reducing agent such as, for example, bisulfite or metabisulfite.
  • acrylic esters denotes the esters of acrylic acid and of methacrylic acid with the alkanols in C ⁇ -C ⁇ 2 , preferably C ⁇ -C 8 , such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, methacrylate d isobutyl.
  • Vinyl nitriles include those having 3 to 12 carbon atoms, in particular acrylonitrile and methacrylonitrile.
  • Styrene can be replaced in whole or in part by ⁇ methylstyrene or vinyltoluene.
  • ethylenically unsaturated monomers which can be polymerized with the above monomers, and the amount of which can range up to 40% by weight of the total of the monomers, mention may be made of:
  • ethylene monomers comprising a sulfonic acid group and its alkali or ammonium salts, for example vinylsulfonic acid, vinylbenzene sulfonic acid, ⁇ -acrylamido methylpropane-sulfonic acid,
  • - unsaturated ethylene monomers comprising a secondary, tertiary or quaternary amino group or a heterocyclic group containing nitrogen, for example vinylpyridines, vinylimidazole, aminoalkyl (meth) acrylates and aminoalkyl (meth) acrylamides such as dimethylaminoethylacrylate or
  • esters of (meth) acrylic acids with alkanediols preferably containing 2-8 carbon atoms such as glycol mono (meth) acrylate, hydroxypropyl mono (meth) acrylate, mono (meth) acrylate of 1 -4 butanediol as well as the monomers comprising two polymerizable double bonds such as ethylene glycol dimethacrylate.
  • the polymerization can be carried out in the presence of a transfer agent such as mercaptans, in particular t-dodecyl mercaptan, substituted diphenyl disulfides, in particular bis methoxyphenyldisulfide.
  • a transfer agent such as mercaptans, in particular t-dodecyl mercaptan, substituted diphenyl disulfides, in particular bis methoxyphenyldisulfide.
  • the amount of transfer agent used is preferably between 0.05 and 5% by weight relative to the weight of the monomers.
  • the polymerization temperature depending on the initiator used, is generally between 40 ° C and 100 ° C, preferably between 50 and 90 ° C. Stabilization of the particles is ensured, if necessary, by any colloidal stabilization system known as anionic, cationic, amphoteric and non-ionic emulsifiers.
  • Anionic emulsifiers are, for example, alkyl sulfates, alkyl sulfonates, alkylarylsulfonates and alkaline alkylphosphates; dialkylsufosuccinates; sodium, potassium or ammonium salts of saturated and unsaturated fatty acids.
  • Examples of cationic emulsifiers are the alkylpyridinium or alkylammonium salts such as N-ethyl dodecylammonium chloride or bromide, cetylammonium chloride or bromide.
  • nonionic emulsifiers mention is made in particular of polyoxyethylene and / or polyoxypropylene derivatives of fatty alcohols, fatty acids or alkylphenols.
  • the polymerization can be carried out continuously, batchwise or semi-continuously with the introduction of a portion of the monomers continuously and be of the "seeded” or “incremental” type according to any known variant for obtaining particles of homogeneous and heterogeneous structure .
  • the method according to the present invention allows the same crosslinking rate to operate in the absence of transfer agent or in the presence of a reduced amount of transfer agent or to continue the polymerization at a higher conversion by compared to state of the art processes.
  • aqueous dispersions thus obtained can advantageously be used as binders in coating compositions for coating paper in the textile industry, in particular for the manufacture of nonwovens, as an additive in paints and adhesive formulations.
  • DEAB stands for diethyl 2,2 '-azobisisobutyrate
  • AZOCARBOXY stands for 2,2 'azobis cyanopentanoic acid
  • CT means t-dodecyl mercaptan
  • KPS potassium persulfate
  • NaPS sodium persulfate Seed preparation
  • the mixture is heated to 75 ° C. and then introduced quickly
  • the uncooked seed thus obtained has a dry extract of 11.6% by weight and the average particle diameter is 58.3 mm.
  • the procedure is as described above except that after one hour at 82 ° C, the mixture is brought to 90 ° C for 14 hours in order to remove the excess of NaPS.
  • a cooked seed is obtained with a dry extract of 13.4% by weight and an average particle diameter of 58.7 mm.
  • the seed previously prepared is loaded into a three-liter reactor to which the initiator is added, then the temperature of the reaction medium is brought to 30 ° C. and the pressure to 12 bars and the pressure is waited for stability in order to verify that there is no leak that could cause a loss of pressure.
  • the reactor is brought to atmospheric pressure in 15 minutes and the temperature is brought to 75 ° C.
  • a vacuum of -1 bar is made in the overhead space of the reactor for 3 minutes followed by the pouring of the styrene / butadiene / acrylic acid / TDM mixture contained in the manifold in 5 hours.
  • the polymerization is then left to take place for 20 hours followed by cooling to 30 ° C. and degassing for 30 seconds at atmospheric pressure.
  • the latex is recovered and analyzed in terms of dry extract, insoluble rate, swelling index and particle size. Determination of the swelling index and the percentage of insoluble latex.
  • a quantity of latex is deposited in order to obtain a dry film 2 mm thick which will be dried for at least 24 hours at room temperature and then in an oven between 50 and 60 ° C. for 24 to 48 hours, until the film is peelable from the Teflon container.
  • test pieces Two 10 x 25 mm test pieces are cut using a cookie cutter in this film, that is PO, the weight of the test piece.
  • the test tube is introduced into a 60 ml bottle containing 50 g of THF solvent, to immerse it completely.
  • the results obtained with tests 1 to 8 are reported in Table I.
  • the bottle containing the test tube and the solvent is placed on a roller shaker also provided with a rocking movement (roller shaking speed ⁇ 50 rpm).
  • test piece After 24 hours of immersion, the test piece is extracted from the bottle and dried superficially on a filter and weighed as quickly as possible, ie P1 the test piece swollen with solvent.
  • the assembly is then weighed.
  • the tare of the crystallizer and of the filter is subtracted from the weight of the assembly to obtain P2, the weight of the test piece.
  • the dry extract is determined according to a gravimetric method consisting in drying in an oven for one hour, 1 gram of latex.
  • the particle size is measured by light scattering with a COULTER LS 230 device.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)
  • Polymerization Catalysts (AREA)
  • Paper (AREA)

Abstract

The invention relates to a method for preparing butadiene-based aqueous dispersions in the presence of at least one azocarboxylic acid ester.

Description

PROCEDE D'OBTENTION DE DISPERSIONS AQUEUSES A BASE DE POLYBUTADIENΞ PROCESS FOR OBTAINING AQUEOUS POLYBUTADIENΞ-BASED DISPERSIONS
La présente invention concerne un procédé de préparation de dispersions aqueuses de copolymères par polymérisation en émulsion de monomères éthyléniquement insaturés en présence d'au moins un initiateur ou amorceur de radicaux libres.The present invention relates to a process for the preparation of aqueous dispersions of copolymers by emulsion polymerization of ethylenically unsaturated monomers in the presence of at least one initiator or initiator of free radicals.
Les dispersions aqueuses à base de butadiène, notamment les latex styrène/butadiène et acrylonitrile/butadiène, sont largement utilisées dans différentes applications, telles que agent de traitement de papier et la fabrication du caoutchouc, par exemple le pneu. Il est bien connu que la polymérisation en émulsion du butadiène ou sa copolymérisation avec d'autres monomères conduit à un polymère réticulé dont le degré de branchement augmente avec le taux de conversion. Cette réticulation a un effet néfaste sur les propriétés d'usage des latex obtenus. Par exemple, elle peut avoir une incidence sur la coalescence des particules de latex pendant les applications de revêtement, comme le couchage de papier, ou contribuer à un mauvais contrôle de la dureté du caoutchouc limitant ainsi sa processabilité.Aqueous dispersions based on butadiene, in particular styrene / butadiene and acrylonitrile / butadiene latexes, are widely used in various applications, such as paper processing agent and the manufacture of rubber, for example tires. It is well known that the emulsion polymerization of butadiene or its copolymerization with other monomers leads to a crosslinked polymer whose degree of branching increases with the conversion rate. This crosslinking has a detrimental effect on the use properties of the latexes obtained. For example, it can affect the coalescence of latex particles during coating applications, such as coating paper, or contribute to poor control of the hardness of rubber, thereby limiting its processability.
Pour limiter le degré de réticulation et ou la masse moléculaire du copolymère formé, on peut soit travailler à conversion limitée, soit utiliser un agent de transfert de chaîne au cours de la polymérisation. Les agents de transfert couramment utilisés sont les mercaptans qui, bien qu'ayant une teneur résiduelle très faible dans les latex finaux, induisent une odeur caractéristique indésirable.To limit the degree of crosslinking and or the molecular weight of the copolymer formed, it is possible either to work with limited conversion, or to use a chain transfer agent during the polymerization. The commonly used transfer agents are mercaptans which, although having a very low residual content in the final latexes, induce an undesirable characteristic odor.
La présente invention a pour but de remédier aux inconvénients de l'art antérieur en proposant un procédé de polymérisation efficace, résultant en une bonne conversion des monomères, qui conduit à des latex de copolymères présentant un faible taux de réticulation. Cette faible réticulation peut être mise à profit pour diminuer le taux de mercaptans et ainsi diminuer l'odeur ou augmenter le taux de conversion sans obtenir des taux de réticulation redhibitoires.The object of the present invention is to remedy the drawbacks of the prior art by proposing an effective polymerization process, resulting in good conversion of the monomers, which leads to latexes of copolymers having a low degree of crosslinking. This weak crosslinking can be used to reduce the mercaptan level and thus decrease the odor or increase the conversion rate without obtaining prohibitive crosslinking rates.
Selon la présente invention, le procédé d'obtention de dispersions aqueuses de copolymères consistant à polymériser un mélange de monomères contenant au moins 60 % en poids de butadiène et d'au moins un monomère choisi parmi le styrène, les esters acryliques, les nitriles vinyliques avec éventuellement jusqu'à 40 % en poids d'un ou plusieurs autres monomères insaturés copolymérisables, en émulsion aqueuse en présence d'un ou de plusieurs initiateur(s) ou amorceur(s) de radicaux libres est caractérisé en ce qu'au moins un des initiateurs ou amorceurs ou que l'initiateur ou l'amorceur est un ester d'acide azocarboxylique de formule (I) :According to the present invention, the process for obtaining aqueous dispersions of copolymers consisting in polymerizing a mixture of monomers containing at least 60% by weight of butadiene and at least one monomer chosen from styrene, acrylic esters, vinyl nitriles optionally with up to 40% by weight of one or more other copolymerizable unsaturated monomers, in aqueous emulsion in the presence of one or more initiator (s) or initiator (s) free radicals is characterized in that at least one of the initiators or initiators or that the initiator or initiator is an ester of azocarboxylic acid of formula (I):
O Ri R3 O i i //O Ri R 3 O ii //
C - C - N = N - C - CC - C - N = N - C - C
/ \/ \
R"0 R? R4 OR'R "0 R? R 4 OR '
(I) dans laquelle :(I) in which:
R-i, R2, R3, et R , identiques ou différents sont sélectionnés indépendamment dans le groupe consistant en - al yles linéaires ou ramifiés ayant de 1 à 9 atomes de carbone, de préférence de 1 à 4 atomes de carbone, éventuellement substitués par un ou plusieurs substituants sélectionnés parmi les substituants hydroxyl, alkoxy en Ci à Ce, halogène ;Ri, R2, R3, and R, identical or different, are independently selected from the group consisting of - linear or branched al yl having from 1 to 9 carbon atoms, preferably from 1 to 4 carbon atoms, optionally substituted by one or several substituents selected from the hydroxyl, C1 to C6 alkoxy, halogen substituents;
- cycloalkyles en C3 à Cι2, éventuellement substitués par un ou plusieurs substituants sélectionnés parmi les groupes alkyle en Ci à C6, alkoxy en C-i à C6, hydroxy et halogène ;- cycloalkyl, C 3 Cι 2, optionally substituted with one or more substituents selected from alkyl to C 6, alkoxy C 6, hydroxy, and halogen;
- aralkyles éventuellement substitués par un ou plusieurs groupes alkyle en Ci à C6, alkoxy en Ci à C@, hydroxy et halogène ;- aralkyl optionally substituted by one or more alkyl groups -C 6 -alkoxy-C @, hydroxy and halogen;
- aryles éventuellement substitués par un ou plusieurs substituants sélectionnés parmi les groupes alkyle en Ci à Ce, alkoxy en Ci à CQ hydroxy et halogène ; avec au moins une des combinaisons Rι-R2 et R3-R pouvant éventuellement former un cycle aliphatique ; R" et R' sont identiques ou différents l'un de l'autre et sont sélectionnés indépendamment dans le groupe consistant en radicaux aliphatiques linéaires ou ramifiés en Ci à C10, de préférence en Ci à C . L'avantage de ces esters d'acides azocarboxyliques est leur basse température de fusion, généralement inférieure à 27°C. Les esters d'acides azocarboxyliques préférés sont ceux dans lesquels R" et R' représentent le méthyle ou l'éthyle et dans lesquels Ri, R2, R3, et R4 représentent avantageusement les groupes alkyles de Ci à C4. De plus, ils ne génèrent ni des sous produits toxiques, ni même des composés cyanés.- aryls optionally substituted with one or more substituents selected from C1 to C6 alkyl, C1 to C6 alkoxy, hydroxy and halogen; with at least one of the combinations Rι-R 2 and R 3 -R which may optionally form an aliphatic cycle; R "and R 'are the same or different from each other and are selected independently from the group consisting of linear or branched aliphatic radicals in Ci to C1 0 , preferably in Ci to C. The advantage of these esters d azocarboxylic acids is their low melting point, generally below 27 ° C. The preferred azocarboxylic acid esters are those in which R "and R 'represent methyl or ethyl and in which Ri, R 2 , R 3 , and R 4 advantageously represent the alkyl groups of Ci to C 4 . In addition, they generate neither toxic byproducts, nor even cyan compounds.
L'ester d'acide azocarboxylique particulièrement préféré est le diéthyl 2, 2'-azobisisobutyrate, c'est-à-dire avec R^ R2, R3, et R4 représentant le méthyle et R' et R" représentant l'éthyle. Un mélange de diéthyl 2, 2'-azobisisobutyrate (DEAB) et de diméthyl 2,2'- azobisisobutyrate (DMAB) avec un taux massique en DEAB, de préférence supérieur à 50 % a donné des résultats très intéressants. Des mélanges de DEAB, DMAB et de méthyl 2, éthyl 2' -azobisisobutyrate avec de préférence un rapport molaire COOMe/COOEt≤10 peuvent convenir. Les esters d'acides azocarboxyliques de formule (I) peuvent être préparés par un procédé classique en deux étapes comprenant une première étape de conversion de l'azonitrile, par réaction avec un alcool, en présence de HCI, selon la réaction de Pinner, conduisant au chlorhydrate d'azoiminoéther correspondant et une seconde étape d'hydrolyse en présence du chlorhydrate ainsi obtenu. Ils peuvent être également préparés par les procédés améliorés tels que décrits dans les documents DE 2 254 572, EP 80 275 et EP 230 586.The particularly preferred azocarboxylic acid ester is diethyl 2, 2'-azobisisobutyrate, that is to say with R ^ R 2 , R 3 , and R 4 representing methyl and R 'and R "representing A mixture of diethyl 2, 2'-azobisisobutyrate (DEAB) and of dimethyl 2,2'-azobisisobutyrate (DMAB) with a mass content of DEAB, preferably greater than 50%, has given very interesting results. Mixtures of DEAB, DMAB and methyl 2, ethyl 2 '-azobisisobutyrate with preferably a COOMe / COOEt≤10 molar ratio may be suitable. The azocarboxylic acid esters of formula (I) can be prepared by a conventional two-step process comprising a first step of conversion of the azonitrile, by reaction with an alcohol, in the presence of HCl, according to the Pinner reaction, leading with the corresponding azoiminoether hydrochloride and a second hydrolysis step in the presence of the hydrochloride thus obtained. They can also be prepared by improved methods as described in documents DE 2 254 572, EP 80 275 and EP 230 586.
En outre, ces esters peuvent être préparés par réaction d'un azonitrile avec un alcool et de l'acide chlorhydrique dans un solvant aromatique, avec un rapport molaire HCI/azonitrile > 2 lorsque l'alcool est le méthanol et > 3 lorsque l'alcool est l'éthanol ou un alcool supérieur.In addition, these esters can be prepared by reacting an azonitrile with an alcohol and hydrochloric acid in an aromatic solvent, with an HCl / azonitrile molar ratio> 2 when the alcohol is methanol and> 3 when the alcohol is ethanol or higher alcohol.
Avantageusement, l'ester d'acide azocarboxylique est utilisé en association avec les initiateurs usuels dans la polymérisation en émulsion, tels que les hydroperoxydes, notamment l'hydroperoxyde de tertiobutyl ou de di- isopropylbenzène, et les persulfates de sodium, de potassium ou d'ammonium. La quantité d'ester d'acide azocarboxylique est de préférence comprise entre 5 et 95 % en poids par rapport au poids total des initiateurs et mieux encore entre 30 et 70 %.Advantageously, the azocarboxylic acid ester is used in combination with the usual initiators in emulsion polymerization, such as hydroperoxides, in particular tert-butyl or di-isopropylbenzene hydroperoxide, and sodium, potassium or sodium persulfates. 'ammonium. The amount of azocarboxylic acid ester is preferably between 5 and 95% by weight relative to the total weight of the initiators and better still between 30 and 70%.
La quantité totale d'initiateurs mise en jeu est comprise entre 0,05 et 4 % en poids par rapport au poids des monomères mis en oeuvre. Les initiateurs peuvent être introduits en batch, continu, semi-batch ou semi-continu.The total amount of initiators involved is between 0.05 and 4% by weight relative to the weight of the monomers used. The initiators can be introduced in batch, continuous, semi-batch or semi-continuous.
Ces initiateurs peuvent être associés à un réducteur comme par exemple le bisulfite ou metabisulfite.These initiators can be associated with a reducing agent such as, for example, bisulfite or metabisulfite.
Par esters acryliques, on désigne les esters de l'acide acrylique et de l'acide méthacrylique avec les alcanols en Cι-Cι2, de préférence Cι-C8, tels que l'acrylate de méthyle, l'acrylate d'éthyle, l'acrylate de propyle, l'acrylate de n-butyle, l'acrylate d'isobutyle, l'acrylate de 2-éthylhexyle, le méthacrylate de méthyle, le méthacrylate d'éthyle, le méthacrylate de n-butyle, le méthacrylate d'isobutyle. Les nitriles vinyliques incluent ceux ayant de 3 à 12 atomes de carbone, en particulier l'acrylonitrile et le méthacrylonitrile.The term “acrylic esters” denotes the esters of acrylic acid and of methacrylic acid with the alkanols in Cι-Cι 2 , preferably Cι-C 8 , such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, methacrylate d isobutyl. Vinyl nitriles include those having 3 to 12 carbon atoms, in particular acrylonitrile and methacrylonitrile.
Le styrène peut être remplacé en totalité ou en partie par l'αméthylstyrène ou le vinyltoluène. Parmi les monomères éthyléniquement insaturés polymérisables avec les monomères ci-dessus, et dont la quantité peut aller jusqu'à 40 % en poids du total des monomères on peut citer :Styrene can be replaced in whole or in part by αmethylstyrene or vinyltoluene. Among the ethylenically unsaturated monomers which can be polymerized with the above monomers, and the amount of which can range up to 40% by weight of the total of the monomers, mention may be made of:
- les esters vinyliques d'acide carboxylique comme l'acétate de vinyle, le versatate de vinyle, le propionate de vinyle,- vinyl esters of carboxylic acid such as vinyl acetate, vinyl versatate, vinyl propionate,
- les acides mono et di carboxyliques insaturés éthylèniques comme l'acide acrylique, l'acide méthacrylique, l'acide itaconique, l'acide maléique, l'acide fumarique et les mono-alkylesters des acides dicarboxyliques du type cité avec les alcanols ayant de préférence 1 à 4 atomes de carbone et leurs dérivés N- substitués,- ethylenically unsaturated mono and di carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and the mono-alkyl esters of dicarboxylic acids of the type mentioned with alkanols having preferably 1 to 4 carbon atoms and their N-substituted derivatives,
- les amides des acides carboxyliques insaturés comme l'acrylamide, le méthacrylamide, le N-méthylolacrylamide ou méthacrylamide,- the amides of unsaturated carboxylic acids such as acrylamide, methacrylamide, N-methylolacrylamide or methacrylamide,
- les monomères éthylèniques comportant un groupe acide sulfonique et ses sels alcalins ou d'ammonium par exemple l'acide vinylsulfonique, l'acide vinylbenzène sulfonique, l'acide α-acrylamido méthylpropane-sulfonique, leethylene monomers comprising a sulfonic acid group and its alkali or ammonium salts, for example vinylsulfonic acid, vinylbenzene sulfonic acid, α-acrylamido methylpropane-sulfonic acid,
2-sulfoéthylèneméthacrylate,2-sulfoéthylèneméthacrylate,
- les monomères éthylèniques insaturés comportant un groupe amino secondaire, tertiaire ou quaternaire ou un groupe hétérocyclique contenant de l'azote par exemple les vinylpyridines, le vinylimidazole, les (meth)acrylates d'aminoalkyle et les (meth)acrylamides d'aminoalkyle comme le diméthylaminoéthylacrylate ou- unsaturated ethylene monomers comprising a secondary, tertiary or quaternary amino group or a heterocyclic group containing nitrogen, for example vinylpyridines, vinylimidazole, aminoalkyl (meth) acrylates and aminoalkyl (meth) acrylamides such as dimethylaminoethylacrylate or
-méthacrylate, le ditertiobutylaminoéthylacrylate ou -méthacrylate, le diméthyl amino éthylacrylamide ou -méthacrylamide, et les monomères zwitterioniques comme l'acrylate du sulfopropyl (diméthyl) aminopropyle,-methacrylate, ditertiobutylaminoethylacrylate or -methacrylate, dimethyl amino ethylacrylamide or -methacrylamide, and zwitterionic monomers such as sulfopropyl (dimethyl) aminopropyl acrylate,
- les esters des acides (meth)acryliques avec des alcanediols contenant de préférence 2-8 atomes de carbone tels que le mono (meth)acrylate de glycol, le mono (meth)acrylate d'hydroxypropyle, le mono (meth)acrylate de 1-4 butanediol ainsi que les monomères comportant deux doubles liaisons polymérisables comme le diméthacrylate d'éthylène-glycol.- esters of (meth) acrylic acids with alkanediols preferably containing 2-8 carbon atoms such as glycol mono (meth) acrylate, hydroxypropyl mono (meth) acrylate, mono (meth) acrylate of 1 -4 butanediol as well as the monomers comprising two polymerizable double bonds such as ethylene glycol dimethacrylate.
En plus des monomères cités, on peut encore mettre en oeuvre, en quantités mineures, comprises généralement entre 0,1 et 5 % des monomères éthylèniques insaturés ayant un caractère réticulable tels que le (meth)acrylate de glycidyle ou les silanes vinyliques et acryliques.In addition to the mentioned monomers, it is also possible to use, in minor amounts, generally between 0.1 and 5% of the unsaturated ethylene monomers having a crosslinkable nature such as glycidyl (meth) acrylate or vinyl and acrylic silanes.
Bien qu'il ne soit pas nécessaire, la polymérisation peut être effectuée en présence d'un agent de transfert tel que les mercaptans notamment le t-dodecyl mercaptan, les disulfures de diphényle substitué notamment le bis methoxyphényldisulfure. La quantité d'agent de transfert mise en jeu est de préférence comprise entre 0,05 et 5 % en poids par rapport au poids des monomères. La température de polymérisation, fonction de l'initiateur mis en œuvre, est généralement comprise entre 40°C et 100°C, de préférence entre 50 et 90°C. La stabilisation des particules est assurée, si nécessaire, par tout système de stabilisation colloïdale connu comme les émulsifiants anioniques, cationiques, amphotères et non-ioniques.Although it is not necessary, the polymerization can be carried out in the presence of a transfer agent such as mercaptans, in particular t-dodecyl mercaptan, substituted diphenyl disulfides, in particular bis methoxyphenyldisulfide. The amount of transfer agent used is preferably between 0.05 and 5% by weight relative to the weight of the monomers. The polymerization temperature, depending on the initiator used, is generally between 40 ° C and 100 ° C, preferably between 50 and 90 ° C. Stabilization of the particles is ensured, if necessary, by any colloidal stabilization system known as anionic, cationic, amphoteric and non-ionic emulsifiers.
Les émulsifiants anioniques sont par exemple les alkylsulfates, les alkylsulfonates, les alkylarylsulfonates et les alkylphosphates alcalins ; les dialkylsufosuccinates ; les sels de sodium, potassium ou ammonium des acides gras saturés ou non. Des exemples d'émulsifiants cationiques sont les sels d'alkylpyridinium ou d'alkylammonium comme le chlorure ou le bromure de N-éthyl dodecylammonium, le chlorure ou le bromure de cetylammonium. Comme émulsifiants non-ioniques on cite en particulier les dérivés polyoxyéthylènés et/ou polyoxypropylénés des alcools gras, des acides gras ou des alkylphénols.Anionic emulsifiers are, for example, alkyl sulfates, alkyl sulfonates, alkylarylsulfonates and alkaline alkylphosphates; dialkylsufosuccinates; sodium, potassium or ammonium salts of saturated and unsaturated fatty acids. Examples of cationic emulsifiers are the alkylpyridinium or alkylammonium salts such as N-ethyl dodecylammonium chloride or bromide, cetylammonium chloride or bromide. As nonionic emulsifiers, mention is made in particular of polyoxyethylene and / or polyoxypropylene derivatives of fatty alcohols, fatty acids or alkylphenols.
La polymérisation peut être réalisée en continu, en discontinu ou semi-continu avec introduction d'une partie des monomères en continu et être du type "ensemencé" ou "incrémental" selon toute variante connue pour l'obtention des particules de structure homogène et hétérogène.The polymerization can be carried out continuously, batchwise or semi-continuously with the introduction of a portion of the monomers continuously and be of the "seeded" or "incremental" type according to any known variant for obtaining particles of homogeneous and heterogeneous structure .
Le procédé, selon la présente invention, permet à taux de réticulation identique d'opérer en l'absence d'agent de transfert ou en présence d'une quantité réduite d'agent de transfert ou de poursuivre la polymérisation à une conversion plus élevée par rapport aux procédés de l'état de technique.The method according to the present invention allows the same crosslinking rate to operate in the absence of transfer agent or in the presence of a reduced amount of transfer agent or to continue the polymerization at a higher conversion by compared to state of the art processes.
Les dispersions aqueuses ainsi obtenues peuvent être avantageusement utilisées comme liants dans les compositions de revêtement pour le couchage du papier dans l'industrie textile en particulier pour la fabrication de non-tissés, comme additif dans les peintures et les formulations adhésives.The aqueous dispersions thus obtained can advantageously be used as binders in coating compositions for coating paper in the textile industry, in particular for the manufacture of nonwovens, as an additive in paints and adhesive formulations.
PARTIE EXPERIMENTALEEXPERIMENTAL PART
Dans ce qui suit, sauf indication contraire, les réactifs sont indiqués en partie en poids etIn the following, unless otherwise indicated, the reagents are indicated in part by weight and
DEAB signifie diéthyl 2,2' -azobisisobutyrateDEAB stands for diethyl 2,2 '-azobisisobutyrate
AZOCARBOXY signifie acide 2,2' azobis cyanopentanoïqueAZOCARBOXY stands for 2,2 'azobis cyanopentanoic acid
TDM signifie t-dodécyl mercaptanCT means t-dodecyl mercaptan
KPS signifie persulfate de potassium NaPS signifie persulfate de sodium Préparation des semencesKPS stands for potassium persulfate NaPS stands for sodium persulfate Seed preparation
Dans un réacteur de 3 litres, on charge :In a 3 liter reactor, we load:
PartiesParts
Eau 96 NaPS 0,45Water 96 NaPS 0.45
Metailyl sulfonate de sodium 1Sodium metailyl sulfonate 1
Pyrophosphate de sodium 1Sodium pyrophosphate 1
Sodium dodecyl sulfate 1Sodium dodecyl sulfate 1
On chauffe le mélange à 75 ° C puis on introduit rapidementThe mixture is heated to 75 ° C. and then introduced quickly
PartiesParts
Styrène 5Styrene 5
Acrylate de butyle 4,8 Acide acrylique 0,2Butyl acrylate 4.8 Acrylic acid 0.2
Cinq minutes après introduction des monomères, on observe une exothermie à 82°C puis on laisse la polymérisation se poursuivre à 82°C pendant 1 heure.Five minutes after introduction of the monomers, an exotherm is observed at 82 ° C. and then the polymerization is allowed to continue at 82 ° C. for 1 hour.
La semence non-cuite ainsi obtenue a un extrait sec de 11 ,6 % en poids et le diamètre moyen des particules est de 58,3 mm.The uncooked seed thus obtained has a dry extract of 11.6% by weight and the average particle diameter is 58.3 mm.
On opère comme décrit précédemment sauf qu'au bout d'une heure à 82°C, le mélange est porté à 90°C pendant 14 heures afin d'éliminer l'excès du NaPS. On obtient une semence cuite avec un extrait sec de 13,4 % en poids et un diamètre moyen des particules de 58,7 mm.The procedure is as described above except that after one hour at 82 ° C, the mixture is brought to 90 ° C for 14 hours in order to remove the excess of NaPS. A cooked seed is obtained with a dry extract of 13.4% by weight and an average particle diameter of 58.7 mm.
Mode opératoire général de la préparation des latexGeneral procedure for preparing latex
On charge la semence préalablement préparée dans un réacteur de trois litres auquel on ajoute l'initiateur, puis on porte la température du milieu réactionnel à 30°C et la pression à 12 bars et on attend la stabilité de la pression afin de vérifier qu'il n'y a pas de fuite pouvant provoquer une perte de pression. On ramène le réacteur à la pression atmosphérique en 15 minutes et on porte la température à 75°C. On effectue un vide de -1 bar dans le ciel du réacteur pendant 3 minutes suivi de la coulée du mélange styrène/butadiène/acide acrylique/TDM contenu dans la nourrice en 5 heures. On laisse ensuite la polymérisation se faire pendant 20 heures suivi d'un refroidissement à 30°C et d'un dégazage de 30 secondes à pression atmosphérique. Le latex est récupéré et analysé en terme d'extrait-sec, taux d'insoluble, indice de gonflement et taille de particules. Détermination de l'indice de gonflement et du pourcentage d'insolubles des latex.The seed previously prepared is loaded into a three-liter reactor to which the initiator is added, then the temperature of the reaction medium is brought to 30 ° C. and the pressure to 12 bars and the pressure is waited for stability in order to verify that there is no leak that could cause a loss of pressure. The reactor is brought to atmospheric pressure in 15 minutes and the temperature is brought to 75 ° C. A vacuum of -1 bar is made in the overhead space of the reactor for 3 minutes followed by the pouring of the styrene / butadiene / acrylic acid / TDM mixture contained in the manifold in 5 hours. The polymerization is then left to take place for 20 hours followed by cooling to 30 ° C. and degassing for 30 seconds at atmospheric pressure. The latex is recovered and analyzed in terms of dry extract, insoluble rate, swelling index and particle size. Determination of the swelling index and the percentage of insoluble latex.
Dans un récipient en Téflon, une quantité de latex est déposée afin d'obtenir un film sec de 2 mm d'épaisseur que l'on fera sécher pendant 24 heures au moins à température ambiante puis à l'étuve entre 50 et 60°C pendant 24 à 48 h, jusqu'à ce que le film soit décollable du récipient Téflon.In a Teflon container, a quantity of latex is deposited in order to obtain a dry film 2 mm thick which will be dried for at least 24 hours at room temperature and then in an oven between 50 and 60 ° C. for 24 to 48 hours, until the film is peelable from the Teflon container.
Deux éprouvettes de 10 x 25 mm sont découpées à l'aide d'un emporte pièce dans ce film, soit PO, le poids de l'éprouvette. L'éprouvette est introduite dans un flacon de 60 ml contenant 50 g de solvant THF, pour l'immerger complètement. Les résultats obtenus avec les essais 1 à 8 sont reportés dans le Tableau I.Two 10 x 25 mm test pieces are cut using a cookie cutter in this film, that is PO, the weight of the test piece. The test tube is introduced into a 60 ml bottle containing 50 g of THF solvent, to immerse it completely. The results obtained with tests 1 to 8 are reported in Table I.
Le flacon contenant l'éprouvette et le solvant est posé sur un agitateur à rouleau muni également d'un mouvement de bascule (vitesse d'agitation des rouleaux ~ 50 t/mn).The bottle containing the test tube and the solvent is placed on a roller shaker also provided with a rocking movement (roller shaking speed ~ 50 rpm).
Après 24 heures d'immersion, l'éprouvette est extraite du flacon et séchée superficiellement sur un filtre et pesée le plus rapidement possible, soit P1 l'éprouvette gonflée de solvant.After 24 hours of immersion, the test piece is extracted from the bottle and dried superficially on a filter and weighed as quickly as possible, ie P1 the test piece swollen with solvent.
Celle-ci est déposée dans un cristallisoir préalablement taré avec le filtre puis elle est séchée 24 heures à 60°C.This is placed in a crystallizer previously tared with the filter and then it is dried for 24 hours at 60 ° C.
L'ensemble est ensuite pesé. La tare du cristallisoir et du filtre est soustraite au poids de l'ensemble pour obtenir P2, le poids de l'éprouvette.The assembly is then weighed. The tare of the crystallizer and of the filter is subtracted from the weight of the assembly to obtain P2, the weight of the test piece.
Expression des résultatsExpression of results
Indice de gonflement = Poids de l'éprouvette gonflée = PI Poids de l'éprouvette re-séchée P2Swelling index = Weight of swollen test piece = PI Weight of re-dried test piece P2
% d'insolubles = Poids de l'éprouvette re-séchée x 100 = P2% of insolubles = Weight of re-dried test piece x 100 = P2
Poids initial de l'éprouvette POInitial weight of PO specimen
Une augmentation du taux de réticulation a pour conséquence une augmentation du taux d'insolubles et une diminution du taux de gonflement.An increase in the rate of crosslinking results in an increase in the rate of insolubles and a decrease in the rate of swelling.
L'extrait sec est déterminé selon une méthode gravimétrique consistant à sécher dans une étuve pendant une heure, 1 gramme de latex.The dry extract is determined according to a gravimetric method consisting in drying in an oven for one hour, 1 gram of latex.
La taille des particules est mesurée par diffusion de la lumière avec un appareil COULTER LS 230. The particle size is measured by light scattering with a COULTER LS 230 device.
Tableau Board

Claims

REVENDICATIONS
1. Procédé d'obtention de dispersions aqueuses de copolymères consistant à polymériser un mélange de monomères contenant au moins 60 % en poids de butadiène et d'au moins un monomère choisi parmi le styrène, les esters acryliques, les nitriles vinyliques avec éventuellement jusqu'à 40 % en poids d'un ou plusieurs autres monomères insaturés copolymérisables, en émulsion aqueuse en présence d'un ou de plusieurs initiateur(s) ou amorceur(s) de radicaux libres est caractérisé en ce qu'au moins un des initiateurs ou amorceurs ou que l'initiateur ou l'amorceur est un ester d'acide azocarboxylique de formule (I) :1. Process for obtaining aqueous dispersions of copolymers consisting in polymerizing a mixture of monomers containing at least 60% by weight of butadiene and at least one monomer chosen from styrene, acrylic esters, vinyl nitriles with optionally up to at 40% by weight of one or more other copolymerizable unsaturated monomers, in aqueous emulsion in the presence of one or more initiator (s) or initiator (s) of free radicals is characterized in that at least one of the initiators or initiators or that the initiator or initiator is an azocarboxylic acid ester of formula (I):
/ \/ \
R"O R2 R4 OR'R "OR 2 R 4 OR '
dans laquelle :in which :
Ri, R2, R3, et R4, identiques ou différents sont sélectionnés indépendamment dans le groupe consistant enRi, R2, R 3 , and R 4 , identical or different, are independently selected from the group consisting of
- alkyles linéaires ou ramifiés ayant de 1 à 9 atomes de carbone, de préférence de 1 à 4 atomes de carbone, éventuellement substitués par un ou plusieurs substituants sélectionnés parmi les substituants hydroxyl, alkoxy en C^ à C6, halogène ;- linear or branched alkyls having from 1 to 9 carbon atoms, preferably from 1 to 4 carbon atoms, optionally substituted by one or more substituents selected from the hydroxyl, C 1 -C 6 alkoxy, halogen substituents;
- cycloalkyles en C3 à Cι2, éventuellement substitués par un ou plusieurs substituants sélectionnés parmi les groupes alkyle en Ci à C6, alkoxy en C^ à C6, hydroxy et halogène ;- cycloalkyl, C 3 Cι 2, optionally substituted with one or more substituents selected from alkyl to C 6 alkoxy, C ^ to C 6, hydroxy, and halogen;
- aralkyles éventuellement substitués par un ou plusieurs groupes alkyle en C<\ à Ce, alkoxy en Ci à C6, hydroxy et halogène ;- aralkyls optionally substituted with one or more C 1 -C 6 alkyl, C 1 -C 6 alkoxy, hydroxy and halogen;
- aryles éventuellement substitués par un ou plusieurs substituants sélectionnés parmi les groupes alkyle en Ci à Ce, alkoxy en Ci à C6, hydroxy et halogène ; avec au moins une des combinaisons Rι-R2 et R3-R pouvant éventuellement former un cycle aliphatique ; R" et R' sont identiques ou différents l'un de l'autre et sont sélectionnés indépendamment dans le groupe consistant en radicaux aliphatiques linéaires ou ramifiés en Ci à C10, de préférence en Ci à C . - aryl optionally substituted by one or more substituents selected from alkyl Cl-Ce, -alkoxy-C 6, hydroxy, and halogen; with at least one of the combinations Rι-R 2 and R 3 -R which may optionally form an aliphatic cycle; R "and R 'are the same or different from each other and are independently selected from the group consisting of linear aliphatic or branched C l -C 10, preferably C -C.
2. Procédé selon la revendication 1 caractérisé en ce que l'initiateur est le diéthyl 2,2'-azobisisobutyrate ou un mélange de diéthyl 2,2'-azobisisobutyrate (DEAB) et le diméthyl 2,2'-azobisisobutyrate (DMAB) avec un taux massique en DEAB de préférence supérieur à 50 %.2. Method according to claim 1 characterized in that the initiator is diethyl 2,2'-azobisisobutyrate or a mixture of diethyl 2,2'-azobisisobutyrate (DEAB) and dimethyl 2,2'-azobisisobutyrate (DMAB) with a mass rate of DEAB preferably greater than 50%.
3. Procédé selon la revendication 1 caractérisé en ce que l'initiateur est un mélange de diéthyl 2,2'-azobisisobutyrate, de diméthyl 2,2'-azobisisobutyrate et de méthyl 2, éthyl 2'-azobisisobutyrate avec de préférence un rapport molaire COOMe/COOEt ≤10.3. Method according to claim 1 characterized in that the initiator is a mixture of diethyl 2,2'-azobisisobutyrate, dimethyl 2,2'-azobisisobutyrate and methyl 2, ethyl 2'-azobisisobutyrate with preferably a molar ratio COOMe / COOEt ≤10.
4. Procédé selon l'une quelconque des revendications précédentes caractérisé en ce que l'ester d'acide azocarboxylique est utilisé en association avec les initiateurs usuels de polymérisation en émulsion tels que les persulfates et les hydroperoxydes.4. Method according to any one of the preceding claims, characterized in that the azocarboxylic acid ester is used in combination with the usual emulsion polymerization initiators such as persulfates and hydroperoxides.
5. Procédé selon la revendication 4 caractérisé en ce que la quantité d'ester d'acide azocarboxylique est comprise entre 5 et 95 % en poids par rapport au poids total des initiateurs, de préférence entre 30 et 70 %.5. Method according to claim 4 characterized in that the amount of azocarboxylic acid ester is between 5 and 95% by weight relative to the total weight of the initiators, preferably between 30 and 70%.
6. Procédé selon l'une quelconque des revendications précédentes caractérisé en ce que la quantité totale d'initiateurs est comprise entre 0,05 et 4 % en poids par rapport au poids des monomères.6. Method according to any one of the preceding claims, characterized in that the total quantity of initiators is between 0.05 and 4% by weight relative to the weight of the monomers.
7. Procédé selon l'une quelconque des revendications précédentes caractérisé en ce que la polymérisation est effectuée en présence d'un agent de transfert.7. Method according to any one of the preceding claims, characterized in that the polymerization is carried out in the presence of a transfer agent.
8. Procédé selon l'une quelconque des revendications précédentes caractérisé en ce que la température de polymérisation est comprise entre 40 et 100°C, de préférence entre 50 et 90°C. 8. Method according to any one of the preceding claims, characterized in that the polymerization temperature is between 40 and 100 ° C, preferably between 50 and 90 ° C.
EP02704849A 2001-03-08 2002-02-15 Method for obtaining polybutadiene-based aqueous dispersions Ceased EP1373326A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0103149 2001-03-08
FR0103149A FR2821847B1 (en) 2001-03-08 2001-03-08 PROCESS FOR OBTAINING AQUEOUS BUTADIENE-BASED DISPERSIONS
PCT/FR2002/000593 WO2002070566A1 (en) 2001-03-08 2002-02-15 Method for obtaining polybutadiene-based aqueous dispersions

Publications (1)

Publication Number Publication Date
EP1373326A1 true EP1373326A1 (en) 2004-01-02

Family

ID=8860876

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02704849A Ceased EP1373326A1 (en) 2001-03-08 2002-02-15 Method for obtaining polybutadiene-based aqueous dispersions

Country Status (6)

Country Link
US (1) US7071270B2 (en)
EP (1) EP1373326A1 (en)
JP (1) JP2004528419A (en)
CA (1) CA2439046C (en)
FR (1) FR2821847B1 (en)
WO (1) WO2002070566A1 (en)

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE254572C (en)
FR13438E (en) 1910-09-03 1911-04-07 Leonce Girardot Detachable wheel for automobiles
US3296226A (en) * 1964-08-28 1967-01-03 Us Rubber Co Process for preparing acrylonitrile/butadiene/unsaturated acid terpolymer with an azobisbutyronitrile/ferric salt catalyst
DE2254572C3 (en) * 1972-11-08 1979-01-11 Bayer Ag, 5090 Leverkusen Azo diisobutyric acid ester
GB2039497B (en) * 1979-11-20 1983-01-26 Ici Ltd Manufacture of polymer dispersions and coating compositions derived from them
DE2900880A1 (en) * 1979-01-11 1980-07-24 Bayer Ag METHOD FOR THE PRODUCTION OF TELECHELEN DIENPOLYMERISAT
EP0080275A1 (en) 1981-11-19 1983-06-01 Imperial Chemical Industries Plc Preparation of azoiminoether hydrochlorides from azonitriles and their hydrolysis to azocarboxylic esters
EP0094739A1 (en) * 1982-05-13 1983-11-23 Imperial Chemical Industries Plc Novel azocarboxylic esters useful as polymerisation initiators and process for their manufacture
JPH0625100B2 (en) 1986-01-14 1994-04-06 和光純薬工業株式会社 Method for producing azoimino ether

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO02070566A1 *

Also Published As

Publication number Publication date
FR2821847B1 (en) 2004-06-18
WO2002070566A1 (en) 2002-09-12
FR2821847A1 (en) 2002-09-13
CA2439046A1 (en) 2002-09-12
JP2004528419A (en) 2004-09-16
CA2439046C (en) 2010-09-28
US20040106727A1 (en) 2004-06-03
US7071270B2 (en) 2006-07-04

Similar Documents

Publication Publication Date Title
EP0469954B1 (en) Process for preparing aqueous dispersion of copolymers
EP1711536B1 (en) Method for radical emulsion polymerisation using hydrosoluble alkoxyamines
JP3696203B2 (en) Living type free radical polymerization control agent, polymerization method, emulsion and polymer using the same
EP0597747B1 (en) Use of dienes as transfer agent during the preparation of polymers
FR2983484A1 (en) Preparing copolymer used to produce membrane for fuel cell device, comprises copolymerizing vinylidene fluoride monomer with monomer of alpha-trifluoromethacrylic acid or its derivative in presence of xanthate or trithiocarbonate compound
WO2002022688A2 (en) Method for block polymer synthesis by controlled radical polymerisation in the presence of a disulphide compound
FR2965564A1 (en) PREPARATION OF HIGH-MASS HYDROPHILIC POLYMERS BY CONTROLLED RADICAL POLYMERIZATION
EP1373326A1 (en) Method for obtaining polybutadiene-based aqueous dispersions
CA1326932C (en) Process for the fabrication of polychloroprene
EP0000462A1 (en) Process for preparing graft copolymers by emulsion suspension graft polymerisation
EP0192508B1 (en) Curable polymers based on unsaturated esters of furoic acid, method for their preparation and their use in the preparation of coatings
EP0150640B1 (en) Process for the polymerisation of chloroprene
FR3041963B1 (en) PROCESS FOR THE SYNTHESIS OF ACRYLIC (CO) POLYMERS FROM OLIGOMERS OF ACRYLIC ACID
CA1335467C (en) Process for the polymerization in an emulsion of vinylic monomers
FR2724658A1 (en) PROCESS FOR THE PREPARATION OF (CO) POLYCHLOROPROPENE RUBBER.
EP0277671B1 (en) Plastisols based on polymers of vinyl chloride, and the use of these plastisols in the coating of cataphoretically treated plates
WO1999033890A1 (en) Diol associative alkaline soluble copolymer and its use as thickening agent for paper coating
WO2019022227A1 (en) Polymer manufacturing method
EP0685501A1 (en) Graft polyolefinic copolymer
BE899982A (en) WEATHER AND SHOCK RESISTANT COMPOSITION AND PROCESS FOR PREPARING THE SAME.
WO2004078793A1 (en) Method for synthesis of branched copolymers by controlled radical polymerisation
WO1997026282A1 (en) Macromonomeres compounds, their preparation from dienic compounds and use thereof
FR2813607A1 (en) Aqueous dispersions based on acrylic polymers and copolymers with high molecular weight, are obtained using organic hydroperoxide salt as initiator, in presence of organic, mineral or mixed type reducing agent
BE601244A (en)
EP1040142A1 (en) Method for preparing an aqueous pressure sensitive adhesive (psa) emulsion, with high shearing resistance

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20030725

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO SI

RIN1 Information on inventor provided before grant (corrected)

Inventor name: TEMBOU N'ZUDIE, DENIS

Inventor name: LEMAHIEU, FREDERIC

Inventor name: COLOMBIE, DAMIEN

17Q First examination report despatched

Effective date: 20040514

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: ARKEMA

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: ARKEMA FRANCE

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: ARKEMA FRANCE

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED

18R Application refused

Effective date: 20090920