JP2015504960A - Dispersed phase polymerization of vinyl halide monomers in the presence of living reaction stabilizers. - Google Patents

Abstract

The present invention provides a compound of formula RbRcC = CX1X2 wherein X1 = F or Cl and X2 = H, F or Cl, and each of Rb and Rc is separately: -H, Cl, F; or- A chlorinated and / or fluorinated, more preferably a perchlorinated or perfluorinated alkyl group) and a dispersed phase polymerization process of vinyl halide compounds comprising A monomer is introduced into the aqueous phase together with at least one reaction stabilizer comprising at least one free radical source; and a polymer chain and a thiocarbonylthio group —S (C═S) —, wherein the polymer chain is The present invention relates to a method comprising a step (E1) comprising a non- (N-vinyl lactam) monomer unit.

Description

  The present invention relates to the field of polymerization (dispersed phase polymerization) using monomers in a liquid phase dispersed in a continuous liquid phase, particularly including emulsion polymerization. More precisely, the present invention relates to this type of polymerization using specific stabilizers for the dispersed phase, known as “reaction stabilizers”.

  Various polymerization reactions using monomers in the form of droplets dispersed in a continuous phase (generally an aqueous phase) using a reaction stabilizer type stabilizer are known.

  In general, the reaction stabilizers used in these reactions are first molecules that can stabilize the droplets of the dispersed phase containing the monomer and also participate in the polymerization reaction. Such reaction stabilizers have, inter alia, the advantage of replacing, in whole or in part, additional surfactants that would otherwise be used to stabilize the dispersed phase, Thus, polymer dispersions (latexes) are obtained which are advantageous in the sense that they do not contain such surfactants or that they have such surfactants with a reduced content at a minimum.

  Such reaction stabilizers have been proposed especially for carrying out emulsion polymerization of vinyl type hydrophobic monomers, for example, having a xanthate type group at the end of the chain (-S (C = S) having an O-functional group), capable of inducing a controlled radical polymerization reaction of the monomer, for example ATRP (atom transfer radical polymerization) or NMP (nitroxide mediated polymerization), or RAFT or MADIIX in the presence of free radicals A hydrophilic or amphiphilic molecule that typically contains a hydrophilic polymer chain and a reactive group that can be typed. These reaction stabilizers firstly ensure stabilization of the emulsion of the dispersed phase oil droplets because of their hydrophilicity, and they secondly typically have a reversible addition-cleavage chain. By the transfer process, it acts as a polymerization control agent so that each step of incorporation of the monomer unit into the chain is a reactive chain end for subsequent incorporation of another monomer unit by the same addition-cleavage process. The polymer chain grows from this control agent by gradual consumption of the monomer contained in each droplet by a process known per se, in which the polymer chain has a “living” property, in the sense that it results in a polymer still having (For more details on controlled or “living” radical polymerization and chain generation from chain transfer agents, see, inter alia, Ha. dbbook of RAFT polymerisation, Barner-Kowollik C. edited by Wiley-VCH 2008, or alternatively, WO 96/30421, WO 98/01478, WO 99/35178, WO No. 98/58974 pamphlet, WO 00/75207 pamphlet and WO 01/42312 pamphlet, WO 99/35177 pamphlet, WO 99/31144 pamphlet, French Patent No. 2 794 464. Or the process described in WO 02/26836).

  Using reaction stabilizers of the type described above that induce controlled radical polymerization, with the incorporation of stabilizers into these polymer chains from the beginning of the polymerization, but nevertheless necessarily using additional surfactants Without having to do so, the hydrophilic chains stay schematically around the droplets as illustrated in the attached FIG. 1, while maintaining the stabilization of the emulsion throughout the polymerization, and the living polymer chains in the dispersed droplets Formation is obtained.

Reaction stabilizers of the type described above have been proposed inter alia in the process described in the following publications:
Nitroxide-Mediated Controlled / Living Free-Radical Surfactant-Free Emulsion Polymerization of Methyl Physiological Using a Poly (Methacrylic Acid).
C. Dire, S.M. Magnet, L.M. Couvreur, B.M. Charleux
Macromolecules 42 (1), 95-103 (2009)
PEO-based Block Copolymers and Homopolymers as Reactive Surfactants for AGET ATRP of Butyl Acrylate in Minimulation.
W. Li, K .; Min, K .; Matyjaszewski, F.M. Stoffelbach, B.M. Charleux
Macromolecules 41, 6387-6392 (2008)
Effective ab Initio Emulsion Polymerization under RAFT Control
Christopher J. et al. Ferguson, Robert J. et al. Hughes, Binh T .; T.A. Pham, Brian S .; Hawkett, Robert G. et al. Gilbert, Algirdas K. et al. Serelis, and Christopher H. Such
Macromolecules (2002)
Surfactant-free controlled / living radical emulsification (co) polymerization of n-buty acrylated and methy thy te ly th e s s s s s e n a n s ti s e n a ti s e n a n s e n s e n ti n s e n a n s e n a ti s e n a n s e n a n a s e n a ti a n e n a s e n a n a s e n a i n a n a n a n a s e n i n a n a n a s e n i n a n e n a n i n e n b ur ent e n a s e n i n e n e n
J. et al. Rieger, G. et al. Osterwinter, C.I. Bui, F .; Stoffelbach, B.M. Charleux
Macromolecules (2009)

  Although absolutely advantageous, one of the limitations of the reaction stabilizers described so far is that they are only suitable for the polymerization of certain vinyl monomers, essentially of the methacrylate and alkyl acrylate type. That is.

  One object of the present invention is to provide a dispersed phase polymerization process suitable for the use of a large number of hydrophobic monomers and particularly suitable for the dispersed phase polymerization of hydrophobic N-vinyl monomers.

  For this purpose, the inventors have shown the advantage of using a new type of reaction stabilizer, ie a living polymer chain derived from RAFT or MADIX controlled radical polymerization of N- (vinyl lactam) monomers. did.

More precisely, we are a method for producing a polymer comprising the step of disperse phase polymerization in the presence of a reaction stabilizer, in which step:
At least one ethylenically unsaturated monomer, generally in dispersed form;
A reaction stabilizer comprising at least one free radical source; and-a polymer chain comprising (or even consisting of) N- (vinyl lactam) monomer units and a thiocarbonylthio group -S (C = S)-. Contacted in the aqueous phase,
A method wherein the step is preferably carried out at a temperature below the decomposition temperature of the thiocarbonylthio group —S (C═S) — of the reaction stabilizer, preferably at a temperature below 40 ° C., for example at a temperature below 30 ° C. The method can be advantageously performed, for example, at room temperature).

According to one embodiment, the hydrophobic monomer used is of the formula R _b R _c C═CX ¹ X ²
(Wherein X ¹ = F or Cl;
X ² = H, F or Cl,
Each of R _b and R _c is independently:
-H, Cl, F; or
-Preferably represents a chlorinated and / or fluorinated, more advantageously a perchlorinated or perfluorinated alkyl group)
It may contain a halogenated vinyl compound such as chloride, vinyl fluoride or vinylidene.

  The inventors further have that the dispersed phase polymerization of the vinyl halide compounds described above more generally contain thiocarbonylthio groups -S (C = S)-, similar to those of the present invention, but with monomer units. What can be obtained with reaction stabilizers containing polymer chains other than those containing (N-vinyl lactam), or alternatively chains containing less than 50% or even less than 30% monomer units (N-vinyl lactam) Proved.

More precisely, the inventors include step (E1),
Wherein ^{_{R b R c C = CX 1}} X 2
(Wherein X ¹ = F or Cl;
X ² = H, F or Cl,
Each of R _b and R _c is independently:
-H, Cl, F; or
-Preferably represents a chlorinated and / or fluorinated, more advantageously a perchlorinated or perfluorinated alkyl group)
An advantageous process for the disperse phase polymerization of vinyl halide compounds corresponding to
-At least one free radical source; and-a polymer chain and a thiocarbonylthio group -S (C = S)-, the polymer chain comprising non- (N-vinyllactam) monomer units, ,
Acrylate-type hydrophilic monomers, such as acrylic acid and its salts such as sodium acrylate, and also water-soluble acrylic esters, such as 2-hydroxyethyl acrylate or oligo or polyethylene glycol acrylate;
Acrylamide-type hydrophilic monomers such as acrylamide, dimethylacrylamide, 2-acrylamido-2-methyl-1-propanesulfonic acid and its salts, acrylamidopropyltrimethylammonium chloride (APTAC), dimethylaminopropylacrylamide, N, N-diethyl Acrylamide, N-isopropylacrylamide, N-morpholine acrylamide or N-hydroxyethylacrylamide;
-Methacrylate-type hydrophilic monomers, for example methacrylic acid and its salts such as sodium methacrylate and also oligo or polyethylene glycol methacrylate, 3- [N- (3-propyl methacrylate) -N, N-dimethyl] ammoniopropane sulfonate) Hydroxyethyl methacrylate;
Methacrylamide-type hydrophilic monomers such as methacrylamide, 3- [N- (3-methacrylamideamidopropyl) -N, N-dimethyl] ammoniopropanesulfonate (SPP), [(3-methacrylamideamidopropyl) -N , N-trimethylammonium chloride (MAPTAC);
-Hydrophilic monomers of the vinyl type, such as vinyl phosphonic acid, sodium vinyl sulfonate, 2-vinyl pyridine, 4-vinyl pyridine and their quaternized versions, and vinyl imidazole;
-Allyl type hydrophilic monomers such as diallyldimethylammonium chloride (DADMAC), diallyldimethylammonium methylphosphonate (DALP)
Revealing a process comprising step (E1), preferably selected from, introduced into the aqueous phase, generally in dispersed form, together with at least one reaction stabilizer referred to herein below as “RS2” did.

  Polymer chains comprising non-N-vinyl lactam monomer units may optionally contain N-vinyl lactam monomer units in an amount of less than 50%, or even less than 30%.

  The method constitutes the subject of the present invention.

  With the halogenated monomers described above, it can be seen that one of the advantages of this method is the particular advantage, i.e. the possibility of replacing the surfactants required in the dispersed phase polymerization with the reagents of the present invention. Specifically, conventionally, dispersed phase polymerization of halogenated monomers of the type described above is perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA), or perfluorononanoic acid (PFNA). With the use of halogenated surfactants, which are usually fluorinated, such as fluoroamphiphiles of the type such as ammonium salts, their use is due to their toxicity profile (toxicity related to persistence) However, it is increasingly opposed.

  The present invention makes it possible to provide a fluorinated latex in which this type of surfactant is at least partly and preferably totally replaced with the reaction stabilizer according to the invention. In this context, the reaction stabilizer used may be halogenated or fluorinated (for example, a reaction stabilizer having a fluorinated or chlorinated group may be used). Unlike conventional dispersed phase polymerization methods, the method of the present invention, which uses a reaction stabilizer, results in the immobilization of the stabilizer on the polymer particles and is therefore observed with conventional fluorinated latex Does not provide a possible surfactant leaching effect. The present invention thus allows the use of fluorinated stabilizers with a reduced impact from this point of view.

  Furthermore, the process of the present invention is particularly efficient in the case of the halogenated monomers described above and provides unprecedented access to the controlled polymerization of the monomers described above.

Dispersed phase polymerization is shown.

  The free radical source used in the step (E1) is preferably a redox type polymerization initiator. More generally, it is any initiator capable of generating free radicals under the conditions of step (E1), preferably at temperatures below 40 ° C., more advantageously at temperatures below 30 ° C. May be.

  Dispersed phase polymerization conducted in the context of the present invention is generally a polymerization that results in an emulsion or dispersion of the synthetic polymer in the aqueous phase at the end of the reaction.

  To do this, according to the first embodiment, the monomers are typically used in dispersed form in the aqueous phase (eg emulsion polymerization).

  Alternatively, the monomer may be used without forming any dispersion of the monomer in the aqueous phase. In this case, the polymer will gradually precipitate and be dispersed in the form of particles (typically dispersion polymerization). For example, monomers may be gradually introduced during the polymerization while maintaining the monomer concentration below their solubility limit.

  According to certain embodiments, the monomer may be introduced continuously or semi-continuously into the aqueous phase initially containing only a portion of the monomer at an initial concentration below the solubility limit.

  In any case, the reaction stabilizer used according to the present invention can stabilize the polymer emulsion or dispersion obtained at the end of the reaction. In certain embodiments (especially emulsion polymerization), it can also stabilize the initial monomer dispersion.

The reaction stabilizer used in step (E1) is typically
A monomer of (and usually consisting of) the same or different (generally identical) non-N-vinyl lactam monomer of the type described above;
-A radical polymerization control agent comprising, for example, a thiocarbonylthio group -S (C = S)-; and-a controlled radical polymerization step (E0) of a composition comprising a radical polymerization initiator which is typically a redox system A derivatized polymer.

  According to a particular embodiment of the invention, the radical polymerization initiator used may be a thermal system.

  Studies conducted by the researchers on this subject have shown that radical polymerization is carried out both in aqueous media and in an efficiently controlled manner, provided that this radical reaction is initiated using a redox system. Now it is possible to demonstrate that it can be done.

  According to another embodiment, the reaction stabilizer used in step (E1) is produced in an organic solvent medium or without solvent. If necessary, it is replaced in water before step (E1).

  After step (E1), a stable polymer dispersion (latex) of polymer particles of controlled mass and size, which constitutes another particular subject of the invention, is generally obtained. The present invention in particular provides access to latexes of fluorinated polyolefins (especially fluorovinyl polymers) that do not contain fluorinated surfactants or have at least a much lower surfactant content than commonly used. obtain.

  Various advantageous features and embodiments of the inventive method are described in more detail below.

Reaction stabilizer The reaction stabilizer used in step (E1) may be used alone or in combination with other stabilizers. Thus, according to an advantageous embodiment, step (E1) is carried out in the absence of other stabilizers, in particular in the absence of surfactants. Nevertheless, according to another foreseeable embodiment, step (E1) may be carried out using the reaction stabilizer of the present invention together with other co-stabilizers such as surfactants.

  The reaction stabilizer used in step (E1) may typically be used at a mass concentration ranging from 0.01% to 50%.

  The polymer / stabilizer mass ratio generally remains greater than 0.005, preferably greater than 0.01, for example greater than 0.02, in particular to ensure a sufficient stabilizing effect. This polymer / stabilizer mass ratio generally need not be greater than 400, which is typically 100 or less, or even 50 or less. This ratio may therefore be, inter alia, 0.005-400, such as 0.05-300, especially 0.02-50.

The thiocarbonylthio group of the reaction stabilizer This group is typically introduced by a control agent used in the controlled radical polymerization performed in step (E0), which is typically a RAFT or MADIX control agent. It is. According to certain embodiments, the control agent used in step (E0) may have several thiocarbonylthio groups.

The thiocarbonylthio group present on the reaction stabilizer typically corresponds to the formula —S (C═S) —Z, where Z is as defined below, and this group is typically Specifically, the following formula (A):
(Where:
-Z is
・ Hydrogen atom,
・ Chlorine atom,
An optionally substituted alkyl or an optionally substituted aryl radical,
An optionally substituted heterocycle,
An optionally substituted alkylthio radical,
An optionally substituted arylthio radical,
An optionally substituted alkoxy radical,
An optionally substituted aryloxythio radical,
An optionally substituted amino radical,
An optionally substituted hydrozine radical,
An optionally substituted alkoxycarbonyl radical,
An optionally substituted aryloxycarbonyl radical,
An optionally substituted carboxyl radical,
An optionally substituted aroyloxy radical,
An optionally substituted carbamoyl radical,
・ Cyano radical,
A dialkyl- or diaryl-phosphonate radical,
A dialkyl-phosphinate or diaryl-phosphinate radical,
Or represents a polymer chain,
And -R ₁ is
An optionally substituted alkyl, acyl, aryl, aralkyl, alkene or alkyne group,
(Saturated or unsaturated, aromatic, optionally substituted carbocyclic or heterocyclic ring, or represents a polymer chain)
Is obtained by using a control agent corresponding to the above in step (E0).

The groups R ₁ or Z, when they are substituted, are optionally substituted phenyl groups, optionally substituted aromatic groups, saturated or unsaturated carbocycles, saturated or unsaturated A heterocycle, or the following: R represents an alkyl or aryl group, or a polymer chain, alkoxycarbonyl or aryloxycarbonyl (—COOR), carboxyl (—COOH), acyloxy (—O ₂ CR), carbamoyl (— CONR ₂ ), cyano (—CN), alkylcarbonyl, alkylarylcarbonyl, arylcarbonyl, arylalkylcarbonyl, phthalimide, maleimide, succinimide, amidino, guanidino, hydroxyl (—OH), amino (—NR ₂ ), halogen, per Fluoroalkyl C _n F _{2n +1} , allyl, epoxy, alkoxy (—OR), S-alkyl, S-aryl, alkali metal salt of carboxylic acid, alkali metal salt of sulfonic acid, polyalkylene oxide chain (PEO, PPO), cationic substituent (primary It may be substituted with a group selected from hydrophilic or ionic groups such as quaternary ammonium salts.

According to certain embodiments, R ₁ is a substituted or unsubstituted, preferably substituted alkyl group.

  The optionally substituted alkyl, acyl, aryl, aralkyl or alkyne groups referred to in this description are generally 1-20 carbon atoms, preferably 1-12, more preferentially 1-9. Contains carbon atoms. They may be linear or branched. They may also be substituted with oxygen atoms or sulfur or nitrogen atoms, especially in the form of esters.

  Among the alkyl radicals, mention may in particular be made of methyl, ethyl, propyl, butyl, pentyl, isopropyl, tert-butyl, pentyl, hexyl, octyl, decyl or dodecyl radicals.

  For purposes of this description, an alkyne group is a radical generally containing 2 to 10 carbon atoms and contains at least one acetylenic unsaturation, such as an acetylenyl radical.

  For the purposes of this description, an acyl group is a radical that generally contains from 1 to 20 carbon atoms with a carbonyl group.

  Among the aryl radicals that may be used according to the invention, mention may be made in particular of phenyl radicals, optionally substituted with nitro or hydroxyl functions.

  Among the aralkyl radicals, mention may be made in particular of benzyl or phenethyl radicals, which are optionally substituted, in particular with nitro or hydroxyl functions.

When R ₁ or Z is a polymer chain, this polymer chain may be derived from radical or ionic polymerization or from polycondensation.

  In the context of the present invention, it is particularly advantageous to use xanthates, dithiocarbamates or dithiocarbazates as control agents.

Advantageously, as a control agent in step (E0), xanthate compounds, for example, the formula _{(CH 3 CH (CO 2 CH} 3)) S (C = S) O- ethyl _OCH 2 CH ₃ -S- (1 -Methoxycarbonylethyl) xanthate is used, and more generally the reaction stabilizer of step (E1) preferably has such a group.

  A particularly suitable control agent for the implementation of step (E0) is a compound sold by the company Rhodia under the name Rhodixan A1.

Free radical sources that may be used in steps (E0) and (E1) The free radical sources used in steps (E0) and (E1) may be the same or different and are typical for practical reasons. Are identical.

  A free radical source that is suitable both in step (E0) and in step (E1) may be introduced simultaneously or sequentially in a redox type comprising two reagents, namely an oxidizing agent and a reducing agent. It is a polymerization initiator.

  According to an advantageous embodiment, the reducing agent and the oxidizing agent are introduced separately, which makes it possible to delay the start of the polymerization until the second reagent has been introduced. Advantageously, the step of using such a redox agent comprises (i) mixing a mixture comprising one of an oxidizing or reducing agent with a monomer and a control agent, which is a reactive chain transfer agent in step (E1). This is done by first forming as a mixture and then (ii) adding other reagents (reducing agent or oxidizing agent, respectively) to the mixture.

The advantageous effects revealed by the inventors in the context of the present invention are generally more pronounced the greater the difference between the standard redox potential of the oxidant and the reductant (E _ox −E _red ). is there. It is recommended in this connection with the present invention that the difference between the standard redox potential of the oxidant and the reducing agent (E _ox -E _red ) is 1-2V. Furthermore, the standard redox potential E _ox of the oxidation of the oxidant (Ox) used in step (E0) is greater than that of the monomers used (preferably at least 0.2 V, more preferentially at least about 0.1. It may be advantageous to be 5V, or even at least 1V) low.

  A particularly suitable oxidizing agent in this connection is hydroperoxide, in particular tert-butyl hydroperoxide (t-BuOOH). Hydrogen peroxide is another possible oxidant.

  In addition, it is more common for agents present in redox systems to contain no acids that are of the nature of inducing monomeric pseudo-reactions, which tend to lead to undesirable by-products, more commonly they trigger such reactions. Preferably, it does not contain a sufficiently low pKa compound. Thus, preferably, it is generally possible to reduce the content of by-products in the synthetic polymer by at most a few percent, greater than 4, more preferentially 6, or even 6.5. It is particularly recommended to use a reducing agent (Red) and an oxidizing agent (Ox) having a pKa of greater than and preferably at least 7. In this connection, a particularly preferred reducing agent is sodium sulfite (pKa = 7.2).

  A redox system that is particularly suitable for carrying out steps (E0) and (E1) of the process of the invention is tert-butyl hydroperoxide (t-BuOOH) in combination with a reducing agent selected from ascorbic acid and sodium sulfite. ) As an oxidizing agent.

  A tertiary butyl hydroperoxide / sodium sulfite redox system has proven particularly advantageous. The use of this system in step (E0) makes it possible to polymerize at room temperature and in water, with by-products of very low content, typically well below 5%.

Conditions for performing steps (E0) and (E1) Given the use of a redox system in step (E0), this step is advantageously used in an aqueous medium, typically water as the sole solvent Done. It thus makes it possible to obtain the polymer directly in an aqueous medium without the need to use organic solvents, which makes the process particularly suitable for use on an industrial scale.

  Furthermore, steps (E0) and (E1) are advantageously carried out at low temperatures, preferably below 40 ° C., more advantageously at temperatures below 30 ° C., in particular between 5 and 25 ° C. These two steps may therefore be performed, for example, at room temperature, which is another advantage of the method of the present invention in terms of energy costs.

  The block polymer produced in steps (E0) and (E1) may be a random (or gradient, in particular in step (E0)) homopolymer or copolymer.

Monomers that may be used in (E1) Examples of halogenated monomers that may be used in step (E1) include vinyl chloride H2C = CHCl (VC), vinylidene chloride H2C = CCl2 (VC2), vinyl fluoride ( VF), vinylidene fluoride (VDF), hexafluoropropene (HFP), 3,3,3-trifluoropropene (TFP), tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE), or perfluorovinyl ether ( PFVE), for example perfluoromethyl vinyl ether (PFMVE). These monomers may be combined with each other or with other ethylenically unsaturated, halogenated or non-halogenated monomers (optionally typically less than 50 mol% of non-halogenated monomers) in step (E1). It may be homopolymerized or copolymerized.

Polymer Dispersion Synthesized According to the Invention Regardless of the nature of the monomers used, step (E1) provides access to the polymer dispersion. Typically, it is a latex comprising dispersed particles formed with block polymers derived from controlled radical polymerization, as obtained after step (E1), which is from the controlled radical polymerization performed in this step. Containing dispersed particles formed of derivatized block polymers, each of these block polymers
A first block, generally hydrophilic or optionally amphiphilic, corresponding to the polymer chain of the reaction stabilizer used in step (E1);
The ethylene used in step (E1), generally terminated with a thiocarbonylthio reactive group (eg xanthate) originally present on the reaction stabilizer used in step (E1), covalently bonded to this first block. And a second block that is hydrophobic and includes a polymer chain resulting from the polymerization of the unsaturated monomer.

  Considering the operating conditions of step (E1), the block polymer derived from this step is initially present on the particle “core” based on the hydrophobic block and on the reaction stabilizer covalently bonded to the core chain Will be placed schematically in each particle to form an outer “shell” based on the polymer chains.

  The latex thus obtained has the advantage that it is stable without the need for the presence of a surfactant. Although the use of additional surfactants is not excluded, it is usually advantageous that no additional surfactants are used at all in or subsequent to step (E1) to obtain a surfactant-free latex. . The immobilization of the stabilizer on the particles by covalent grafting, inherent in the use of step (E1), is the desorption observed when conventional surfactants are used in place of the reaction stabilizers of the present invention. Involves towards stabilizing the latex by preventing the phenomenon.

Furthermore, the use of step (E1) makes it possible to obtain a controlled surface chemistry at the surface of the latex particles, which can be adjusted depending on the nature of the polymer chain of the reaction stabilizer, and reacting onto this polymer chain. The group is
Before step (E1): inter alia by introducing functionalized or unfunctionalized monomers in step (E0); and / or after step (E1): eg immobilized on the surface of latex particles It may also be introduced by a grafting reaction with groups present on the polymer chain.

  The use of controlled radical polymerization in step (E1) furthermore allows very fine control of the number average molecular weight Mn of the synthetic polymer very easily and directly. As a result, step (E1) allows a very easy fine-grained control of the size of the particles formed, which may be used inter alia to optimize colloidal stability. Furthermore, likewise, polymer particles tending to have a homogeneous and narrow diameter around the mean value are obtained.

  The polymer obtained by step (E1) in the form of particles has a living character and can therefore be used absolutely as a living polymer for the subsequent synthesis of the block copolymer. The third block will be grafted. In this connection, the polymer obtained in step (E1) may be used as a control agent in the polymerization step following step (E1).

Usually, however, these polymers are used in latex form. In this case, it may be desirable to deactivate the reactive end of the polymer obtained after step (E1). This deactivation may take place after step (E1), alternatively it may terminate this step (eg it is performed when the desired molecular weight or the expected diameter of the latex particles has been reached). You may) In this connection, the method then comprises a chain end chemical treatment step (E2) after step (E1). For example, if the reaction stabilizer used in step (E1) is xanthate, the xanthate reactive end obtained on the polymer can be oxidized, for example, by oxidizing the xanthate reactive end to various oxidized species (especially thioesters). Deactivated in order to deprive the polymer of its living properties by the action of hydrogen peroxide or by the action of organic peroxides or or by ozone, of the form —S (C═O) — and —SO ₃ H). May be.

  The latex obtained after step (E1) is used for a great number of applications, in particular for producing paints, coatings and adhesives, for producing building materials, or alternatively in cosmetic or body care compositions, It may be used in plant protection formulations or for the agricultural sector, or alternatively in petroleum extraction fluids.

  According to a particular embodiment, a block polymer derived from controlled radical polymerization as obtained after step (E1), organized in the form of micelles, which may be used as a polymerization site for controlled radical polymerization A polymer dispersion obtained from step (E1) comprising:

  The invention and its advantages are further illustrated by the examples set forth below.

Example 1: Emulsion polymerization of vinylidene chloride (VDC) in the presence of polyacrylamide-Xa 10 g VDC, 59 g distilled water, 0.47 g polyacrylamide-Xa (Xa = Rhodixan A1, Mn = 3000 g / mol, Taton et al., Macromol. Rapid Commun. 2001, 22, 18, 1497) and 0.26 g of tert-butyl hydroperoxide solution (70% by weight in water) at room temperature (20 ° C.) in a 250 ml round bottom flask Put it in.

  The reaction mixture was cooled to 10 ° C. and degassed by gentle sparging with pure nitrogen for 5 minutes with stirring (magnetic bar). Next, 0.26 g of sodium sulfite was added all at once under a stream of nitrogen.

  The reaction medium was then allowed to stir at 10 ° C. (± 5 ° C.) for 3 hours.

  After the reaction, a conversion of 91% was measured by gravimetry.

  Analysis by static light scattering (Malvern Zetasizer) gives a particle size value Dz of 241 nm and a particle polydispersity value of 0.04.

Example 2: Emulsion polymerization of vinylidene chloride (VDC) in the presence of poly (acrylic acid) -Xa 10 g VDC, 59 g distilled water, 0.47 g polyacrylic acid-Xa (Xa = Rhodixan A1, Mn = 3200 g / mol, synthesized according to Taton et al. Macromol. Rapid Commun. 2001, 22, 18, 1497) and 0.26 g of tert-butyl hydroperoxide solution (70% by weight in water) at room temperature (20 ° C.) In a round bottom flask.

  The reaction mixture was cooled to 10 ° C. and degassed by gentle sparging with pure nitrogen for 5 minutes with stirring (magnetic bar). Next, 0.26 g of sodium sulfite was added all at once under a stream of nitrogen.

  The reaction medium was then allowed to stir at 10 ° C. (± 5 ° C.) for 3 hours.

  After the reaction, a conversion of 89% was measured by gravimetry.

  Analysis by static light scattering (Malvern Zetasizer) gives a particle size value Dz of 195 nm and a particle polydispersity value of 0.03.

Claims (11)

Wherein ^{_{R b R c C = CX 1}} X 2
(Wherein X ¹ = F or Cl;
X ² = H, F or Cl,
Each of R _b and R _c is independently:
-H, Cl, F; or
-Preferably represents a chlorinated and / or fluorinated, more advantageously a perchlorinated or perfluorinated alkyl group)
A dispersion phase polymerization method of a halogenated vinyl compound corresponding to
These monomers are
At least one free radical source; and at least one reaction stabilizer comprising a polymer chain and a thiocarbonylthio group —S (C═S) —, wherein the polymer chain comprises non-N- (vinyl lactam) monomer units. A process comprising step (E1), introduced into the aqueous phase together. In the step (E1), the non-N-vinyl lactam monomer unit is
Acrylate-type hydrophilic monomers, such as acrylic acid and its salts such as sodium acrylate, and also water-soluble acrylic esters, such as 2-hydroxyethyl acrylate or oligo or polyethylene glycol acrylate;
Acrylamide-type hydrophilic monomers such as acrylamide, dimethylacrylamide, 2-acrylamido-2-methyl-1-propanesulfonic acid and its salts, acrylamidopropyltrimethylammonium chloride (APTAC), dimethylaminopropylacrylamide, N, N-diethyl Acrylamide, N-isopropylacrylamide, N-morpholine acrylamide or N-hydroxyethylacrylamide;
-Methacrylate-type hydrophilic monomers, for example methacrylic acid and its salts such as sodium methacrylate and also oligo or polyethylene glycol methacrylate, 3- [N- (3-propyl methacrylate) -N, N-dimethyl] ammoniopropane sulfonate) Hydroxyethyl methacrylate;
Methacrylamide-type hydrophilic monomers such as methacrylamide, 3- [N- (3-methacrylamideamidopropyl) -N, N-dimethyl] ammoniopropanesulfonate (SPP), [(3-methacrylamideamidopropyl) -N , N-trimethylammonium chloride (MAPTAC);
-Hydrophilic monomers of the vinyl type, such as vinyl phosphonic acid, sodium vinyl sulfonate, 2-vinyl pyridine, 4-vinyl pyridine and their quaternized versions, and vinyl imidazole;
-Allyl type hydrophilic monomers such as diallyldimethylammonium chloride (DADMAC), diallyldimethylammonium methylphosphonate (DALP)
The method of claim 1, which may be selected from:   The method according to claim 1, wherein in step (E1), the vinyl halide monomer is in a dispersed form.   The process according to claim 1, wherein step (E1) is carried out at a temperature below 40 ° C, preferably below 30 ° C.   The method according to claim 4, wherein the free radical source used in step (E1) is a redox polymerization initiator.   6. The method of claim 5, wherein the redox initiator comprises tert-butyl hydroperoxide (t-BuOOH) as an oxidizing agent in combination with a reducing agent selected from ascorbic acid and sodium sulfite.   The process according to any one of claims 1 to 6, wherein the thiocarbonylthio group present on the reaction stabilizer is xanthate or dithiocarbamate, preferably xanthate.   A polymer dispersion obtainable by the method according to claim 1.   9. The dispersion of claim 8, which is a latex comprising dispersed particles formed of block polymer derived from controlled radical polymerization as obtained after step (E1) of claim 1.   Claims for manufacturing paints, coatings and adhesives, for manufacturing building materials, in cosmetic or body care compositions, in plant protection formulations or for the agricultural sector, or in petroleum extraction fluids Use of the dispersion according to 9.   A block polymer derived from controlled radical polymerization as obtained after step (E1) according to claim 1, organized in the form of micelles, which may be used as a site of polymerization for controlled radical polymerization The dispersion according to claim 10.