WO2003002614A2 - Synthese de polymeres par voie radicalaire controlee en miniemulsion - Google Patents
Synthese de polymeres par voie radicalaire controlee en miniemulsion Download PDFInfo
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- WO2003002614A2 WO2003002614A2 PCT/FR2002/002219 FR0202219W WO03002614A2 WO 2003002614 A2 WO2003002614 A2 WO 2003002614A2 FR 0202219 W FR0202219 W FR 0202219W WO 03002614 A2 WO03002614 A2 WO 03002614A2
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- Prior art keywords
- polystyrene
- ethylenically unsaturated
- chosen
- polymers
- surfactant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
-
- 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
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
-
- 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
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
Definitions
- the present invention relates to a new radical polymerization process in miniemulsion giving access to polymers with reactivable chain ends, usable in particular for the preparation of block copolymers.
- Emulsion polymerization is the most developed polymerization process at present on an industrial scale.
- the best known products are styrene-butadiene copolymers, acrylic latexes, and vinyl acetate.
- a standard process for radical emulsion polymerization involves the following compounds: water, a monomer or a mixture of monomers, at least one surfactant, an initiator and optionally polymerization additives (transfer agents, salts).
- the monomers are distributed as follows:
- the reaction begins with the creation of radicals in the aqueous phase, resulting from the decomposition of the water-soluble initiator. These radicals initiate chains which propagate in the aqueous phase, until reaching a critical size at which these chains precipitate and nucleate a particle.
- the very low specific surface area of the droplets combined with their number makes their nucleation improbable compared to that of the micelles. Most of the nucleation takes place in swollen micelles of monomers, which are nucleated into polymer particles. The supply of particles with monomers is therefore ensured by the droplets, which act as a reservoir of monomers which diffuses towards the polymerization sites.
- the particle size distributions are generally wide, which makes it possible to envisage the preparation of latex with very high solids content (superior to the conventional emulsion process - Masa et al. J. Appl. Polym. Sci. 48, 205 (1993)). It has also been shown that the miniemulsion has a clear advantage for controlling the particle size during polymerization processes in CSTR (Continuous Stirred Tank Reactors) reactors (Aizpurua et al. Macromol. Symp. 111, 121 (1996)).
- CSTR Continuous Stirred Tank Reactors
- Specific radical polymerization processes have recently been developed, in which the polymer chains produced are functionalized by terminal groups capable of being able to be reactivated in the form of free radicals by means of reversible termination or transfer reactions.
- This specific type of radical polymerization is generally designated by the term of "controlled” or "living” radical polymerization.
- These names come from the fact that the presence of the reactivable end groups described above induces the existence of equilibria between functionalized species (called “dormant” species) and active species (free radicals), which allows both controlling the growth of polymer chains (obtaining tight mass distributions and controlling the average molecular mass, in particular by playing on the molar ratio of monomer / precursor of active chains) and of obtaining functionalized polymers, known as "living” polymers, capable of 'be used as reactivatable species in subsequent radical polymerization reactions, which is particularly advantageous in the context of the preparation of block copolymers.
- Controlled radical polymerization can make it possible to present the following distinctive aspects:
- the average molecular weight is controlled by the monomer / chain precursor molar ratio
- control agents via a reversible termination reaction such as nitroxide precursors according to the teaching of patent application WO 99/03894 or the organometallic complex in the oxidized state in ATRP technology (Radical Polymerization by Transfer atom) according to the teaching of application WO 96/30421, can be distributed between the organic phase and the aqueous medium. If too large a proportion of deactivator is present in the aqueous phase, reversible termination reactions take place there. The main consequence is the decrease in the rate of polymerization. A lack of control agent in the effective place of polymerization, namely the particles, causes a loss of control of the reaction. The main result is a widening of the molecular weight distribution. In addition, from a kinetic point of view, the nitroxide and ATRP technologies are penalized in an approach in a dispersed medium. This results in very slow polymerizations. Nitroxide technology has been implemented in conventional emulsion
- the distribution of the catalyst between the aqueous phase and the organic phase is mainly determined by the nature of the ligand. It has been demonstrated that the ligand must be sufficiently hydrophobic to provide a minimum of catalyst in the organic phase. On the contrary, if the complex becomes too hydrophobic, the diffusion of the catalyst through the aqueous phase becomes too slow, which has the effect of altering the quality of the polymerization control. To maintain the copper catalyst in the particles, Matyjaszewski et al. (Journal of Polymer Science, vol. 38, 4724 (2000) had a miniemulsion approach.
- a major drawback of this system is the fact that it can use only nonionic surfactants, more and more in very large quantities (more than 10% compared to the monomers in conventional procedures).
- Reversible transfer systems are more favorable, kinetically on the one hand, but especially due to the creation of macro-control agents (polymer chains), once the first transfer reaction has been carried out between the control agent initial and a growing radical in the organic phase. This situation prevents any exit of the control agent thus created from the particle.
- An object of the present invention is therefore to propose a new process implemented in a miniemulsion making it possible to obtain high polymer yields.
- a second object of the invention is to propose a process for the synthesis by radical polymerization of block polymers, in particular triblocks, with lower polydispersity index than for a standard emulsion process using the same reagents.
- a third aim is to propose a radical polymerization process which is easy to carry out and of low cost.
- the process according to the invention has the advantage of being able to prepare triblock polymers in a dispersed medium easily and efficiently.
- polymer in the broad sense, both homopolymers as well as copolymers.
- block copolymer (or “block copolymer”) a copolymer comprising at least two successive sequences (blocks) of monomer units of different chemical constitutions.
- Each of the blocks present can consist of a homopolymer or a copolymer obtained from a mixture of ethylenically unsaturated monomers.
- the block can in particular be a random copolymer.
- Block copolymers within the meaning of the invention can thus comprising two blocks each made up of random copolymers.
- the ethylenically unsaturated monomers are such that the blocks obtained are of different natures.
- blocks of different natures is meant either blocks made up of monomers of different types, or blocks made up of monomers of the same type but in different quantities.
- control agents which can therefore be used for preparing the polymer (s)
- R 2 and R 3 identical or different, represent:
- . -S-R ⁇ an optionally substituted alkyl, acyl, aryl, aralkyl or alkyne radical, . a carbonaceous cycie or a heterocycle, saturated or not, aromatic, optionally substituted,
- R 2 and R 3 together can represent the atoms necessary to form a carbon ring or a heterocycle, saturated or not, aromatic, optionally substituted, and p is between 2 and 10.
- the groups Ri, R 2 and R 3 when substituted, may be substituted by substituted phenyl groups, substituted aromatic groups, saturated or unsaturated carbon rings, saturated or unsaturated heterocycles, or groups: aikoxycarbonyl or aryloxycarbonyl (-COOR), carboxy (- COOH), acyloxy (-O2CR), carbamoyl (-CONR2), cyano (-CN), alkylcarbonyl, alkylarylcarbonyl, arylcarbonyl, arylalkylcarbonyl, phthalimido, maleimido, succinimido, amidino, guanidimo, hydroxy (- OH), amino (-NR2), halogen, perfluoroalkyl C n F 2n + ⁇ , allyl, epoxy, alkoxy (-OR), S-alkyl, S-aryl, groups having a hydrophilic or ionic character such as alkali salts carboxylic acids, alkali salts,
- R 1 is a substituted or unsubstituted alkyl group, preferably substituted.
- the compounds of formulas (B) useful, as control agents for preparing the first generation polymers are for example the compounds in which Ri is chosen from: - CH (CH3) (C02Et)
- the compounds of formula (B) are easily accessible. They can in particular be obtained by reaction between P S ⁇ 0 , K 2 C0 3 and a halogen derivative
- the optionally substituted alkyl, acyl, aryl, aralkyl or alkyne groups generally have 1 to 20 carbon atoms, preferably 1 to 12, and more preferably 1 to 9 carbon atoms. They can be linear or branched. They can also be substituted by oxygen atoms, in the form in particular of esters, sulfur or nitrogen atoms.
- alkyl radicals mention may in particular be made of the methyl, ethyl, propyl, butyl, pentyl, isopropyl, tert-butyl, pentyl, hexyl, octyl, decyl or dodecyl radical.
- the alkyne groups are radicals generally of 2 to 10 carbon atoms, they exhibit at least one acetylenic unsaturation, such as the acetylenyl radical.
- the acyl group is a radical generally having from 1 to 20 carbon atoms with a carbonyl group.
- aryl radicals mention may in particular be made of the phenyl radical, optionally substituted in particular by a nitro or hydroxyl function.
- aralkyl radicals mention may in particular be made of the benzyl or phenethyl radical, optionally substituted in particular by a nitro or hydroxyl function.
- control agents are preferred: xanthates, dithiocarbamates and those of general formula
- xanthates are used as the control agent.
- the process of the invention is carried out in the presence of a source of free radicals (initiator), however, for certain monomers, such as styrene, the free radicals making it possible to initiate the polymerization can be generated by the monomer to ethylenically unsaturated itself at sufficiently high temperatures generally above 100 C C. It is not, in this case necessary to add a source of additional free radicals.
- a source of free radicals initiator
- the source of free radicals can be introduced into the mini-emulsion or before the formation of the mini-emulsion.
- the source of free radicals useful in the process of the present invention is generally a radical polymerization initiator.
- the radical polymerization initiator can be chosen from the initiators conventionally used in radical polymerization. It can for example be one of the following initiators:
- - hydrogen peroxides such as in particular: tertiary butyl hydroperoxide, cumene hydroperoxide, t-butyl-peroxyacetate, t-butyl-peroxybenzoate, t-butylperoxyoctoate, t-butylperoxyneodecanoate, t - butylperoxyisobutarate, lauroyl peroxide, t-amylperoxypivalte, t-butylperoxypivalate, dicumyl peroxide, benzoyl peroxide, potassium persulfate, ammonium persulfate, azo compounds, such as in particular: 2- 2'- azobis (isobutyronitrile), 2,2'-azobis (2-butanenitrile), 4,4'-azobis (4-pentanoic acid), 1, 1'-azobis (cyclohexane-carbonitrile), 2 - (t-butylazo) -2-
- persulfates, perborate or perchlorate of alkali metals or ammonium in combination with an bisulfite of alkali metal, such as sodium metabisulfite, and reducing sugars alkali metal persulfate in combination with an arylphosphinic acid, such as benzene phosphonic acid and the like, and reducing sugars.
- the amount of initiator to be used is determined so that the amount of radicals generated is at most 50% by mole, preferably at most 20% by mole, relative to the quantity of the control agent.
- the screening officer corresponds to a functional definition.
- the ethylenically unsaturated monomers useful in the process of the present invention are advantageously monomers substantially insoluble in water and generally have the following general formula (I):
- - X, X ′ identical or different, represent H, a halogen or a group R, OR, 0 2 COR, NHCOH, OH, NH2, NHR, N (R) 2, (R) 2N + 0 " , NHCOR, CO2H, CO2R, CN, CONH2, CONHR or CON (R) 2, in which R is chosen from alkyl, aryl, aralkyl, alkylaryl, alkene or organosilyl groups, optionally perfluorinated and optionally substituted by one or more carboxyl, epoxy, hydroxyl, alkoxy, amino, halogen or sulfonic, and
- - b is 0 or 1.
- the monomers which are substantially insoluble in water are preferably monomers which have a solubility in water of 0 to 5% by weight, advantageously from 0 to 3% by weight.
- the ethylenically unsaturated monomers can in particular be chosen from:
- vinyl aromatic monomers such as styrene, and styrene derivatives, such as alpha methylstyrene or vinyltoluene, - ethylenic monomers such as ethylene, alpha-olefins, vinyl chloride
- - dienics such as butadiene, isoprene or chloroprene
- alkyl acrylates and methacrylates in which the alkyl group contains from 1 to 10 carbon atoms such as methyl, ethyl, n-butyl, 2-ethylhexyl acrylates and methacrylates, t-butyl, isobornyl, phenyl, benzyl and monomers fluorinated
- vinyl monomers such as vinyl acetate, vinyl versatate®, vinyl propionate and nitriles, more particularly those comprising from 3 to 12 carbon atoms, such as acrylonitrile and methacrylonitrile.
- styrene and styrene derivatives such as alphamethylstyrene or vinyltoluene, - vinyl nitriles,
- - dienes for example butadiene or isoprene.
- (meth) acrylic esters is meant the esters of acrylic acid or methacrylic acid with hydrogenated or fluorinated CjC ⁇ alcohols, preferably Ci-C ⁇ .
- CjC ⁇ alcohols preferably Ci-C ⁇ .
- Vinyl nitriles more particularly include those having 3 to 12 carbon atoms, such as in particular acrylonitrile and methacrylonitrile.
- vinyl esters of carboxylic acid such as, for example, vinyl acetate, are preferably used as ethylenically unsaturated monomers.
- the polymer obtained is hydrolyzed at acidic or basic pH.
- the types and quantities of polymerizable monomers used according to the present invention vary depending on the particular final application for which the polymer is intended. These variations are well known and can be easily determined by those skilled in the art.
- ethylenically unsaturated monomers can be used alone or as a mixture.
- the polymer of first generation obtained includes n times the unit of formula (II):
- n being greater than or equal to 1, preferably greater than 6, - V, V, X, X 'and b being as defined above.
- Surfactants which can be used in the context of the present invention include the anionic, cationic, amphoteric and nonionic emulsifiers commonly used in emulsion polymerization processes. They can be used alone or as a mixture. A list of surfactants usable in the context of the present invention can be found in "McCutcheon's Emulsifiers and Detergents 1981 Annuals”.
- anionic surfactants such as sodium dodecylbenzene sulfonate, alkali metal alkylsulfates, such as sodium dodecylsulfate
- SDS sulfonated alkyl esters
- fatty acid esters or salts of fatty acids such as sodium stearate.
- the surfactants can be used in variable amounts which make it possible to obtain a mini-emulsification.
- the surfactants can be present in an amount of between approximately 0.02 and 8.0% by weight, preferably between 0.3 and 5% by weight, relative to the total weight of ethylenically unsaturated monomers present.
- Co-surfactants increase the stability of the mini-emulsion while minimizing the effects of Ostwald ripening.
- These co-surfactants are generally compounds that are substantially insoluble in water, such as long-chain C 10 -C 40 hydrocarbon compounds chosen from alcohols, alkanes, mercaptans, carboxylic acids, ketones, amines and mixtures thereof. . Mention may thus be made of hexadecane or cetyl alcohol. It is also possible to use polymeric co-surfactants, and more specifically polymers (homopolymers, random copolymers, blocks or grafts) substantially insoluble in water, but soluble in the monomer or the mixture of monomers used in the process according to the invention. .
- block copolymers mention may in particular be made of polystyrene-polybutadiene-polystyrene and polystyrene-polyisoprene.
- the number-average molecular mass (Mn) of the co-surfactant when the latter is a polymer, is preferably between 10,000 and 1,000,000, preferably between 50,000 and 250,000 g / mol.
- the molar ratio of co-surfactants to surfactant is advantageously between 0.001 and 10, preferably between 0.5 and 5.
- the amount of surfactants and optionally of co-surfactants is between 0.4 and 2% by weight relative to the total weight of ethylenically unsaturated monomers present.
- the aqueous solution of the process according to the invention therefore comprises generally demineralized water.
- the amount of water introduced can advantageously be relatively small. It can thus be such that the quantity of dry extract at the end of the process according to the invention is between 10 and 65% by weight, preferably between 30 and 55%, relative to the total weight of the miniemulsion.
- a mini-emulsion is therefore an oil in water finely divided emulsion. More specifically, the average diameter of the droplets corresponding to the dispersed phase is between 10 and 500 nm. It can be prepared in many ways. Preferably, it is obtained by ultrasonication or by shearing of the emulsion comprising the compounds specified according to the present invention.
- the method is implemented semi-continuously.
- the instantaneous polymer content relative to the instantaneous amount of monomer and polymer is between 50 and 99% by weight, preferably between 75 and 99%, even more preferably between 90 and 99% .
- This content is maintained, in known manner, by controlling the temperature, the rate of addition of the reagents and optionally the polymerization initiator.
- the method is implemented in the absence of UV source, by thermal ignition.
- the temperature of reaction (ii) can vary between 40 ° C and 200 ° C depending on the nature of the monomers used. Preferably, it is between 60 and 120 ° C.
- the pressure is conveniently atmospheric pressure, but can be higher.
- the mini-emulsion is cooled to room temperature, (iv) optionally the polymer obtained is isolated and (v) optionally washed and / or dried.
- the determination of the end of reaction (ii) can be done by determining the level of solid or by gas chromatography.
- the process of the invention can be carried out using a mixture of ethylenically unsaturated monomers.
- a first generation statistical polymer is obtained.
- a block having particular properties is obtained. This procedure is particularly advantageous when the first generation polymer thus obtained is an intermediate in the preparation of a block copolymer.
- the present invention also relates to a process for the preparation of a Nth generation block copolymer, by radical polymerization, N being greater than or equal to 2, which comprises:
- a first radical polymerization step as described above to form the first generation polymer followed by - N-1 radical polymerization steps, each of these steps being carried out using a miniemulsion, as described above, comprising: at least one ethylenically unsaturated monomer, the polymer obtained in the preceding radical polymerization step, optionally an aqueous solution, - optionally a surfactant, preferably in small quantity, and (ii) the reaction of said emulsion, presence of a source of free radicals, at sufficient temperature and / or for a time sufficient to form polymers, the ethylenically unsaturated monomer (s) being such that the block formed in this step is different in nature from the block formed in the previous step.
- a first generation polymer is synthesized from a miniemulsion and then (2) the first generation polymer obtained in step (1) is used to prepare a copolymer diblocks (second generation) by contacting in a miniemulsion of this first generation polymer with one or more ethylenically unsaturated monomers and a source of free radicals, the block obtained in step (2) being different in nature from the polymer of first generation of step (1).
- This step (2) can be repeated with new monomers and the diblock copolymers obtained to synthesize a new block and obtain a triblock copolymer.
- the polymerization step can thus be repeated as many times as necessary from a block copolymer to obtain a copolymer with an additional block.
- Formula (III) from a miniemulsion comprising:
- n and n ', identical or different, are greater than or equal to 1 , V, V, W and, identical or different, represent: H, an alkyl group or a halogen, X, X ', Y and Y', identical or different, represent H, a halogen or a group R, OR, O2COR, NHCOH, OH, NH 2 , NHR, N (R), (R) 2N + 0 " , NHCOR, C0 2 H, C0 2 R, CN, CONH 2 , CONHR or CON (R) 2 , in which R is chosen from alkyl, aryl, aralkyl, alkaryl, alkene or organosilyl groups, optionally perfluorinated and optionally substituted with a or more carboxyl,
- the polymerization step is carried out with a composition containing a mixture of ethylenically unsaturated monomers.
- the present invention also relates to the first generation polymers and the block polymers which can be obtained according to any one of the methods of the invention. These polymers have a controlled molecular weight.
- the block polymers comprise at least three polymer blocks chosen from the following associations:
- Block copolymer 100 1 17 200 115 000 6.7 97
- a solution of sodium dodecyl sulfate (1.56 g; 0.5% by weight relative to butyl acrylate), sodium hydrogen carbonate (0.2 g) and initiator 4,4'-azo- (4-cyanopentanoic acid) (0.45 g; 50 mol% relative to xanthate) in water (540.0 g) is mixed with a solution of diethyl meso-2,5-di (0-ethyi xanthate) adipate (1.43 g; 0.00323 mole) and hexadecane (4.88 g) in n-butyl acrylate (315.0 g).
- the mixture is then homogenized for 5 minutes by mixing at 24,000 rpm and by ultrasound for 5 minutes using equipment of the Branso ⁇ 1200 type.
- the pre-miniemulsion prepared according to the method described above is introduced in a pentacol reactor equipped with a condenser, a thermocouple and mechanical stirring.
- the temperature is set at 70 ° C.
- the reaction mixture is stirred at the rate of 2.50 rpm at for 4 hours.
- a 40 g sample is taken from the reaction medium (first Poly block (n-butyl acrylate)).
- 0.23 g of 4,4'-azo- (4-cyanopentanoic acid) in 10 g of water are introduced at the same time as 0.03 g of soda.
- 53 g of styrene are then added continuously for 30 minutes. 5 hours after the end of introduction of the styrene, the reaction is stopped by cooling to room temperature.
- the particle size distribution is very narrow: less than 0.01 for the first polybutylacrylate block in miniemulsion, 0.03 for the triblock.
- the medium is then homogenized for 5 minutes by stirring at 9500 rpm and then by ultrasound for 5 minutes using equipment of the Branson 1200 type.
- the pre-miniemulsion prepared as described above is charged.
- the reaction mixture is then degassed at room temperature with a stream of nitrogen with stirring (250 rpm), then the temperature is brought to 70 ° C. The mixture is kept at this temperature for 6 hours.
- a sample of 40 g is collected (first block Poly (n-butyl acrylate)), followed by the addition of an initiator solution (0.20 g) in water (40.0 g). At this time, 110 g of styrene are added in ten minutes. After this addition, the reaction is extended for 5 hours, then cooled to room temperature.
- the medium is then homogenized for 5 minutes by stirring at 24,000 rpm and then by asonification for 5 minutes with equipment of the Branson 1200 type.
- the pre-miniemulsion prepared as described above is charged.
- the reaction mixture is then degassed at room temperature with a stream of nitrogen with stirring (250 rpm), then the temperature is brought to 70 ° C.
- the mixture is kept at this temperature for 6 hours.
- a 5 g sample is taken (first Poly block (n-butyl acrylate)), this being followed by the addition of an initiator solution (0.42 g) in water (40.0 g).
- an initiator solution (0.42 g) in water (40.0 g).
- 115 g of styrene are added over ten minutes.
- the temperature is brought to 80 ° C. and the reaction is prolonged for 5 hours, then cooled to ambient temperature.
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Abstract
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Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP02762496A EP1409555A2 (fr) | 2001-06-29 | 2002-06-26 | Synthese de polymeres par voie radicalaire controlee en miniemulsion |
AU2002328349A AU2002328349A1 (en) | 2001-06-29 | 2002-06-26 | Controlled mini-emulsion free radical polymerisation |
US10/482,330 US7317050B2 (en) | 2001-06-29 | 2002-06-26 | Controlled mini-emulsion free radical polymerization |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR0108683A FR2826658B1 (fr) | 2001-06-29 | 2001-06-29 | Synthese de polymeres par voie radicalaire controlee en miniemulsion |
FR01/08683 | 2001-06-29 |
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WO2003002614A2 true WO2003002614A2 (fr) | 2003-01-09 |
WO2003002614A3 WO2003002614A3 (fr) | 2003-10-30 |
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US (1) | US7317050B2 (fr) |
EP (1) | EP1409555A2 (fr) |
AU (1) | AU2002328349A1 (fr) |
FR (1) | FR2826658B1 (fr) |
WO (1) | WO2003002614A2 (fr) |
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WO2003075968A2 (fr) * | 2002-03-04 | 2003-09-18 | Georgia Tech Research Corporation | Films hydrophiles biocompatibles produits a partir de mini-emulsions polymeres destines a etre appliques sur la peau |
AU2005321543A1 (en) * | 2004-12-30 | 2006-07-06 | Cinvention Ag | Combination comprising an agent providing a signal, an implant material and a drug |
BRPI0519754A2 (pt) * | 2005-01-13 | 2009-03-10 | Cinv Ag | materiais compàsitos contendo nanopartÍculas de carbono |
BRPI0617450A2 (pt) * | 2005-10-18 | 2011-07-26 | Cinv Ag | partÍculas de termocura e mÉtodos para produÇço das mesmas |
FR2903409A1 (fr) * | 2006-07-04 | 2008-01-11 | Solvay | Procede de polymerisation radicalaire en dispersion aqueuse pour la preparation de polymeres |
US9987820B2 (en) | 2009-11-17 | 2018-06-05 | Arkema France | Multilayer structures containing biopolymers |
WO2011062781A1 (fr) * | 2009-11-17 | 2011-05-26 | Arkema France | Alliage acrylique résistant aux chocs |
EP2851377A1 (fr) | 2013-09-19 | 2015-03-25 | Synthomer Deutschland GmbH | Copolymères triséquencés par polymérisation RAFT en miniémulsion |
WO2015173193A1 (fr) * | 2014-05-12 | 2015-11-19 | Solvay Specialty Polymers Italy S.P.A. | Procede de polymerisation regulee de monomeres fluores |
JP6834970B2 (ja) * | 2015-10-28 | 2021-02-24 | テクノUmg株式会社 | グラフト共重合体の製造方法、およびそれを用いた熱可塑性樹脂組成物の製造方法 |
JP6989792B2 (ja) | 2019-12-25 | 2022-01-12 | ダイキン工業株式会社 | フルオロポリマーの製造方法 |
Citations (2)
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WO1998001478A1 (fr) * | 1996-07-10 | 1998-01-15 | E.I. Du Pont De Nemours And Company | Polymerisation presentant des caracteristiques vivantes |
FR2794463A1 (fr) * | 1999-06-04 | 2000-12-08 | Rhodia Chimie Sa | Procede de synthese de polymeres par polymerisation radicalaire controlee a l'aide de xanthates halogenes |
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EP0771848B1 (fr) * | 1995-04-27 | 2004-02-18 | Polyplastics Co. Ltd. | Composition de resine thermoplastique et son procede de fabrication |
CA2309279C (fr) * | 1997-12-18 | 2009-07-14 | E.I. Du Pont De Nemours And Company | Procede de polymerisation presentant des caracteristiques vivantes et polymeres obtenus par ce procede |
WO2000055218A1 (fr) * | 1999-03-18 | 2000-09-21 | California Institute Of Technology | Nouveaux copolymeres a trois sequences et a deux sequences aba, et procedes de preparation correspondant |
DE19920353A1 (de) * | 1999-05-04 | 2000-11-09 | Agfa Gevaert Ag | Farbfotografisches Silberhalogenidmaterial |
FR2802209B1 (fr) * | 1999-12-10 | 2002-03-01 | Rhodia Chimie Sa | Latex a chimie de surface modifiee et poudres redispersables , leur obtention et leurs utilisations |
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2001
- 2001-06-29 FR FR0108683A patent/FR2826658B1/fr not_active Expired - Fee Related
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2002
- 2002-06-26 WO PCT/FR2002/002219 patent/WO2003002614A2/fr not_active Application Discontinuation
- 2002-06-26 EP EP02762496A patent/EP1409555A2/fr not_active Withdrawn
- 2002-06-26 AU AU2002328349A patent/AU2002328349A1/en not_active Abandoned
- 2002-06-26 US US10/482,330 patent/US7317050B2/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998001478A1 (fr) * | 1996-07-10 | 1998-01-15 | E.I. Du Pont De Nemours And Company | Polymerisation presentant des caracteristiques vivantes |
FR2794463A1 (fr) * | 1999-06-04 | 2000-12-08 | Rhodia Chimie Sa | Procede de synthese de polymeres par polymerisation radicalaire controlee a l'aide de xanthates halogenes |
Also Published As
Publication number | Publication date |
---|---|
US7317050B2 (en) | 2008-01-08 |
EP1409555A2 (fr) | 2004-04-21 |
FR2826658B1 (fr) | 2003-09-05 |
AU2002328349A1 (en) | 2003-03-03 |
US20040192838A1 (en) | 2004-09-30 |
WO2003002614A3 (fr) | 2003-10-30 |
FR2826658A1 (fr) | 2003-01-03 |
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