WO2015121225A1 - Polymer bearing phosphorus functional groups and at least one azide functional group, method for the synthesis thereof and use of same - Google Patents

Abstract

The invention relates to a novel polymer bearing phosphonate and/or phosphonic pendant functional groups along the length of the chain, as well as at least one azide functional group. The invention also relates to the method for the synthesis thereof, in particular by means of RAFT/MADIX radical polymerisation, and to the use thereof for the synthesis of block copolymers by means of 1,3-dipolar cycloaddition reaction with at least one polymer bearing an alkyne functional group at one or each of its chain ends.

Description

 Polymer carrying phosphorus functional groups and at least one azide function, its synthesis process and its use.

The present invention relates to a polymer carrying phosphonate and / or phosphonic functions pendant along the chain, as well as at least one azide function. The present invention also relates to a process for synthesizing such a polymer.

In order to improve the properties of the materials contained in the tire rubber compositions, different strategies are possible. Of these, the structural modification of diene elastomers is one of the methods employed.

The Applicants are particularly interested in the context of the invention to elastomers having phosphorus functions. (phosphonate and / or phosphonic). Indeed, phosphorus polymers have recently gained increasing interest because of their utility in a wide range of applications such as for example fuel cells (J. Fuel Cells, 2005, 5, (3), 355), membranes electrolytes (cation exchange membranes) (J. App .. Poly Sci, 1999, 74, 83, Macromol Rapid Commun 2006, 20, 1719), flame retardants (Polymer Degradation and Stability, 2012, 97, 2428) dental additives (J. Dent Res, 1974, 53, (4), 867, J. Mater Sci Lett, 1990, 9, 1058), the solubilization of drugs (hydrogels for the release of drugs). (J. Sci Polym., 1998, 70, 1947), Cell Proliferation Promoters (Fuji Photo Film Co. US 6,218,075, Biomaterials, 2005, 26, 3663) and Corrosion Inhibitors and Promoters adhesion for coatings (Rhodia Chimie WO 2003076531).

The phosphonate or phosphonic function of these polymers can be either present in a monomer involved in the copolymerization with the other or the other monomers constituting the polymer, is obtained by the post-polymerization modification of the polymer.

The preparation of phosphorus diene polymers by copolymerization with a monomer carrying a phosphonate function in its ester form was written by Carpentier et al. (Ajellal N., C.M. Thomas, Carpentier J.F., Polymer, 2008, 49, 4344-4349). These authors reported the preparation of new random polydienes containing phosphonate groups by radical copolymerization of dimethyl 1,3-butadiene-1-phosphonate (BPMe) with chloroprene (CP) or isoprene (IP) in the presence of (2, 2,6,6-tetramethylpiperidin-1-yl) oxy (TEMPO). However, this approach may have several drawbacks such as reactivity ratios that are incompatible with those of the comonomers of the elastomer composition or simply the need to synthesize the appropriate phosphonate monomer in the event of industrial unavailability. In addition, the microstructure of the polydiene obtained by radical polymerization is difficult to control, with visible branching phenomena or the formation of insoluble fraction.

The preparation of phosphoric diene polymers by postpolymerization modification of the polymer by radical grafting of functionalized thiols carrying a phosphorus functional group was also studied. The group of Pr. Boutevin (Polym Bull, 1998, 41, 145-151) describes the radical grafting of a thiol, diethyl 3-mercaptopropyl phosphonate (HS- (CH ₂ ) 3 -PO ₃ (Et) 2 ), on a hydroxy-telechelic polybutadiene (M _n = 1200 g / mol and 20% or 80% butadiene-1, 2) in THF with azobisisobutyronitrile (AIBN) as a radical initiator. To have a real benefit related to the reactivity of the phosphonate functions of a phosphoric diene polymer in order to significantly modify the properties of the polymer in its most diverse applications, it is necessary to use a polymer having phosphonate function levels. high.

In view of the existing post-radical polymerization modification methods, an increase in the level of functions on the polymer involves the use of a greater proportion of functionalized thiols carrying a phosphorus function. However, the use of small functionalized thiol molecules carrying a phosphorus function to achieve high levels of graft functions leads to a significant change in the macrostructure of the resulting modified polymer. This macrostructure evolution observed in the context of radical grafting is generally due to secondary reactions (radical -radical bimolecular coupling, transfer reaction, ...); the proportion of these side reactions increasing with the molar level of targeted graft functions.

The technical problem that arises with respect to the state of the art is to have a polymer having a high molar ratio of phosphonate and / or phosphonic functions whose synthesis process is simple and reproducible and overcomes the disadvantages of the processes. earlier.

The present invention proposes to contribute to answering this problem and to overcoming the disadvantages encountered in the preparation of elastomers with a high content of phosphorus functional groups.

Indeed, the inventors have now developed a new polymer carrying phosphonate and / or phosphonic functions pendant along the chain and bearing at least one azide function. These polymers are of particular interest because it becomes possible to couple poly (phosphorus) polymers by a 1,3-dipolar type reaction to a diene elastomer bearing an alkyne function at one or both of its chain ends, in order to form the corresponding block copolymer which has a high molar ratio of phosphonate and / or phosphonic functions.

A first object of the present invention is therefore a poly (phosphorus) polymer, that is to say carrying phosphonate and / or phosphonic functions pendant along the chain, bearing at least one azide function.

The invention also relates to a process for preparing this novel polymer. Another object of the invention is the use of this novel polymer for the synthesis of block copolymers by coupling with a polymer bearing an alkyne function at one or both of its chain ends.

In the present description, the term "phosphorus" is understood to mean either the function carried by a monomer or of a polymer, a polymeric compound or unit, as the case may be, comprising at least one phosphonate function, a phosphonic hemiacide function or a phosphonic diacid function. The term "a phosphonic function" is used to refer to a phosphonic hemiacide function or a phosphonic diacid function. In the polymer, the phosphorus functions are pendent along the chain.

In the present description, the term "unit" of the polymer, any unit derived from a monomer of the polymer backbone.

In the present description, one defines by rate or mass percentage of a unit in a polymer, the total mass of these units in the polymer relative to the total mass of the polymer.

On the other hand, any range of values designated by the expression "between a and b" represents the range of values from more than a to less than b (i.e. terminals a and b excluded) while any range of values designated by the expression "from a to b" means the range of values from a to b (i.e. including the strict limits a and b). values referred to as "between a and b" represents the range of values from more than a to less than b (i.e., limits a and b excluded) while any range of values designated by the expression "from a to b" means the range of values from a to b (i.e., including the strict limits a and b). Thus a first object of the invention is a poly (phosphorus) polymer bearing at least one azide function. By poly (phosphorus) polymer is meant according to the invention, a polymer whose phosphonate and / or phosphonic functions are pendent along the main chain

According to the invention, the poly (phosphorus) polymer can be written: P - (N ₃ ) q

P poly (phosphorus) being a polymer chain comprising phosphorus units and q an integer ranging from 1 to 1 5, or even 1 to 1 2, preferably 1 to 8. According to the invention, the polymer chain P can be any homopolymer chain obtained by polymerization of a monomer carrying at least one phosphonate and / or phosphonic function, or of any copolymer chain of one or more monomers bearing at least one phosphonate and / or phosphonic function between them or with a or several comonomers. According to a variant of the invention, the poly (phosphorus) polymer chain P corresponds to the following general formula (I):

(I)

 with

 m denoting an integer greater than or equal to 2 and n denoting an integer greater than or equal to 0, provided that when n is not 0, n and m may be identical or different, preferably greater than 2 and preferably less than 2500; .

X, X ', which may be identical or different, represent H, a halogen or a group R _1; OR _1; OCORi, NHCOH, OH, NH _2, NHR-ι, N {Rfe (Ri) ₂ N ⁺ O ^", NHCOR ^1, CO ₂ H, CO ₂ R, CN, CONH _2, CONHR-ι or COI ^ R ^, wherein R 1 is selected 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 groups.

Y, Y ', which may be identical or different, are such that either Y, Y' or both comprise at least one phosphorus functional group -P (O) (OR ₂ ) (OR ₃ ), R 2 and R ₃ , which are identical or different, representing a hydrogen atom or an alkyl radical, optionally haloalkyl. According to variants of the invention, the poly (phosphorus) polymer bearing at least one azide function may consist of a type of monomeric unit comprising Y and Y '. The poly (phosphorus) polymer bearing at least one azide function is then an azide derivative of a homopolymer of a monomer carrying at least one phosphorus functional group.

According to variants of the invention, the poly (phosphorus) polymer bearing at least one azide function may consist of several types of monomeric units comprising Y and Y ', Y and Y' then being different from a type of unit. to the other. The poly (phosphorus) polymer bearing at least one azide function is then an azide derivative of a copolymer of several monomers carrying at least one phosphorus functional group. The sequence of the different monomer units comprising Y and Y 'may be random or sequenced.

According to variants of the invention, the poly (phosphorus) polymer bearing at least one azide function may consist of one or more types of monomer units comprising Y and Y ', and one or more types of monomeric units comprising X and X ', Y and Y' on the one hand, and X and X 'on the other hand, then being different from one type of unit to another. The poly (phosphorus) polymer bearing at least one azide function is then an azide derivative of a copolymer of one or more monomers carrying at least one phosphorus functional group and one or more comonomers comprising X, X '. The sequence of the different monomeric units, comprising X, X 'on the one hand, and on the other hand Y and Y', can be statistical or sequenced.

The mole fraction of monomer units with X and X 'may be zero, and is generally from 0 to 0.5, preferably from 0 to 0.25, more preferably from 0 to 0.1.

Among the monomers from which the units carrying phosphorus functional groups Y and Y 'that are useful in the present invention are vinyl phosphonic acid, vinyl phosphonic acid dimethyl ester, bis (2-chloroethyl) ester, and the like. vinyl phosphonic acid, vinylidene diphosphonic acid, tetraisopropyl ester of vinylidene diphosphonic acid, alpha-styrene phosphonic acid, dimethyl-p-vinylbenzylphosphonate, diethyl-p-vinylbenzylphosphonate, dimethyl (methacryloyloxy) methylphosphonate, diethyl (methacryloyloxy) methylphosphonate, diethyl-2- (acrylamido) ethylphosphonate or a mixture of these monomers, more generally, any unsaturated styrene monomer, acrylate or methacrylate, acrylamido or methacrylamido, vinyl or allylic bearing at least one dialkylphosphonate, phosphonic acid or hemiacide - P (OH) (OR) group, or a mixture of these monomers. Preferably, the dimethyl ester of vinylphosphonic acid and dimethyl-p-vinylbenzylphosphonate will be used.

Among the monomers from which the units substituted by X and X 'that are useful for the present invention are the hydrophilic (h) or hydrophobic (H) monomers chosen from the following monomers.

Among the hydrophilic monomers (h), mention may be made of:

vinyl alcohol resulting from the hydrolysis of vinyl acetate, for example.

 neutral acrylamido monomers, such as acrylamide, N, N-dimethylacrylamide and N-isopropylacrylamide.

 the cyclic amides of vinylamine, such as N-vinylpyrrolidone and vinylcaprolactam.

ethylenically unsaturated mono- and di-carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, or fumaric acid.

 ethylenic monomers comprising a sulphonic acid group or an alkali metal or ammonium salt thereof, for example vinylsulfonic acid, vinylbenzene sulphonic acid, alpha-acrylamidomethylpropanesulphonic acid or 2-sulphoethylene methacrylate; , or

monomers chosen from aminoalkyl (meth) acrylates and aminoalkyl (meth) acrylamides; monomers comprising at least one secondary, tertiary or quaternary amine function, diallyl dialkyl ammonium salts such as dimethylaminoethyl (meth) acrylate, dimethylamino propyl (meth) acrylate, dimethylamino propyl (meth) acrylamide, 2-vinylpyridine, 4-vinylpyridine, diallyldimethylammonium chloride.

Preferably, the hydrophilic monomeric units (h) are chosen from acrylic acid (AA), dimethylaminopropyl acrylamide, and N-vinylpyrrolidone.

Among the hydrophobic monomers (H), mention may be made of:

 styrenic derived monomers such as styrene, alphamethylstyrene, paramethylstyrene or paratertiobutylstyrene, or

the esters of acrylic acid or of methacrylic acid with C 1 -C 12 alcohols, preferably C ₁ -C ₈ alcohols, which are optionally fluorinated, such as, for example, methyl acrylate or ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, t-butyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylate n-butyl, isobutyl methacrylate,

 vinyl nitriles containing from 3 to 12 carbon atoms, and in particular acrylonitrile or methacrylonitrile,

 vinyl esters of carboxylic acids, such as vinyl acetate (VAc), vinyl versatate, or vinyl propionate,

 vinyl or vinylidene halides, for example vinyl chloride, vinylidene chloride and vinylidene fluoride, and

 diene monomers, for example butadiene or isoprene.

Preferably, the hydrophobic monomer units (H) of the copolymers of the invention are butadiene, isoprene, butyl acrylate and styrene.

The poly (phosphorus) polymer bearing at least one azide function as defined previously has an average number of units of at least 2 and at most equal to 5000.

Another subject of the invention is a process for synthesizing the poly (phosphorus) polymer bearing pendant phosphonate and / or phosphonic functions along the chain, bearing at least one azide function. The poly (phosphorus) polymer bearing at least one azide function may be obtained by any process allowing the functionalization by an azide function of any poly (phosphorus) polymer obtained by homopolymerization of a monomer carrying at least one phosphorus functional group, or by copolymerization of one or more monomers carrying at least one phosphorus functional group with one another or with one or more comonomers Depending on the processes, the functionalization by introduction of at least one azide function may be concomitant with the polymerization or may be subsequent thereto.

This polymer can be obtained by any appropriate means depending on the type of phosphorus monomers used. It is possible to mention chain polymerization such as anionic or cationic polymerization, in solution or in emulsion, radical polymerization, Ziegler-Natta catalytic polymerization, or stepwise polymerization (polycondensation). The choice of polymerization is within the reach of those skilled in the art. However, radical polymerization has several advantages within the scope of the invention, particularly as regards the introduction of the azide function in the polymer chain. Various radical polymerization techniques are known to those skilled in the art, namely conventional atomic transfer controlled polymerization (ATRP) (ACS Symp Ser 1998). , 685, 258-283, ACS Symp Ser 2000, 768, 2-26, Polymer Prog 2001, 26, 2083-2134, Chem Rev 2001, 101, 2921-2990, Advances in Polymer Science. 2002, 159, 2-166), controlled by nitroxides (NMP) (Chem Rev. 2001, 101, 3661 -3688) or controlled by addition-fragmentation-transfer (RAFT or MADIX) (Macromolecules 1998, 31, 5559 -5562, Handbook of Radical Polymerization, Wiley-Interscience, 2002, pp. 629-690). Controlled radical polymerization techniques are preferably used in the context of the invention, these allowing the synthesis of polymers whose molecular weight, polydispersity, topology, composition and functionalization are well controlled. The addition-fragmentation-transfer controlled radical polymerization (RAFT or MADIX) is used as a preferential treatment, this polymerization process allowing the introduction in the polymer of a group bearing at least one azide function included in the structure of the transfer agent and consequently the introduction of this group at the end of the polymer chain.

Thus, according to particularly preferred variants of the process of the invention, a mode of synthesis of the poly (phosphorus) polymer bearing at least one azide function comprises the RAFT or MADIX polymerization of at least one monomer carrying at least one phosphorus functional group. in the presence of the transfer agent RAFT or MADIX functionalized azide and a polymerization initiator.

According to these variants, the method may also comprise the synthesis of the transfer agent RAFT or MADIX carrying an azide group.

According to variants of the invention, the transfer agent is a thiocarbonylthio compound carrying an azide group. More particularly, the thiocarbonylthio transfer agent has the general formula (II)

R-S- (C = S) -Z. (He) in which,

- R represents:

 a group (i) alkyl, acyl, aryl, alkenyl or alkynyl,

 a carbon cycle (ii), saturated or non-saturated, optionally aromatic;

- heterocycle (iii), saturated or unsaturated, optionally aromatic; or wherein said groups and rings (i), (ii) and (iii) may be substituted by substituted phenyl groups, substituted aromatic groups or: alkoxycarbonyl or aryloxycarbonyl (-COOR '), carboxy (-COOH), acyloxy ( - ₂ CR '), carbamoyl (-CONR' ₂ ), cyano (-CN), alkylcarbonyl, alkylarylcarbonyl, arylcarbonyl, arylalkylcarbonyl, phthalimido, maleimido, succinimido, amidino, guanidimo, hydroxy (-OH), amino (-NR ' ₂ ), halogen, allyl, epoxy, alkoxy (-OR '), S-alkyl, S-aryl, groups having a hydrophilic or ionic character such as the alkaline salts of carboxylic acids, the alkaline salts of sulfonic acid, polyalkylene oxide chains (POE, POP), cationic substituents (quaternary ammonium salts), R 'representing an alkyl or aryl group,

 a polymer chain,

 with the proviso that R contains an azide group;

Z is an oxygen atom, a carbon atom, a sulfur atom, a nitrogen atom or a phosphorus atom, these atoms being substituted with one, two or three hydrocarbon radicals R ", so as to have a an appropriate valence, which may comprise at least one heteroatom, such that R "represents:

 a group (i) alkyl, acyl, aryl, alkenyl or alkynyl,

 a carbon cycle (ii), saturated or non-saturated, optionally aromatic;

- heterocycle (iii), saturated or unsaturated, optionally aromatic; or wherein said groups and rings (i), (ii) and (iii) may be substituted by substituted phenyl groups, substituted aromatic groups or: alkoxycarbonyl or aryloxycarbonyl (-COOR '), carboxy (-COOH), acyloxy ( - ₂ CR '), carbamoyl (-CONR' ₂ ), cyano (-CN), alkylcarbonyl, alkylarylcarbonyl, arylcarbonyl, arylalkylcarbonyl, phthalimido, maleimido, succinimido, amidino, guanidimo, hydroxy (-OH), amino (-NR ' ₂ ), halogen (Cl, Br, I or F), allyl, epoxy, alkoxy (-OR '), S-alkyl, S-aryl, groups having a hydrophilic or ionic character such as the alkaline salts of carboxylic acids alkali metal salts of sulfonic acid, polyalkylene oxide chains (POE, POP), cationic substituents (quaternary ammonium salts), R 'representing an alkyl or aryl group,

 a polymer chain.

According to variants of the invention, thiocarbonylthio agents bearing an azide group of general formula (II) may be obtained in a manner known to those skilled in the art from the transfer agents described in the following documents, the descriptions of which are integrated by reference: the applications WO 98/58974, WO 00/75207 and WO 01/421312 which implement a controlled radical polymerization by xanthate control agents (group -S- (C = S) -O-), the agents of controlled radical polymerization of dithioester type (-S- (C = S) -S-carbon group) or trithiocarbonates (-S- (C = S) -S-) group of the application WO 98/01478, radical polymerization agents controlled dithiocarbamates (-S- (C = S) -Azote group) of the application WO 99/31144, the controlled radical polymerization agents of the dithiocarbazate type (group -S- (C = S) -Azote) of the WO 02/26836, the agents of xanthates, dithiocarbonates and / or trithiocarbonates type described in WO 02070571; WO 2001060792; WO 2004037780; WO 20040831 69; WO 2003066685; WO 2005068419; WO2003062280; WO 2003055919; WO 2006023790. Particular designations of R and R "can be extracted from these documents set forth below.

Thus, preferably, R is a group N ₃ -CH ₂ -CH ₂ -CH ₂ -O (C = O) - (CH ₃ ) CH-.

More preferably, Z denotes a group OR "with R" denoting a C ₁ -C ₅ alkyl radical, more preferably a C ₁ -C ₂ alkyl radical.

As particularly useful transfer agents according to the invention, there may be mentioned the xanthate of formula N3- (CH ₂ ) 3 -O (C = O) - (CH ₃ ) CH-S- (C = S) - EtO.

The above preferred and variant aspects are combinable with one another.

The synthesis of a thiocarbonylthio agent bearing an azide group corresponding to the general formula RS- (C = S) -Z can be carried out in a manner known to those skilled in the art. The RAFT or MADIX polymerization is carried out in a manner known per se. In the context of initiating the RAFT or MADIX controlled radical polymerization of the monomer carrying the phosphorus functional group, the source of free radicals employed is generally a radical polymerization initiator.

The radical polymerization initiator may be chosen to be chosen from the initiators conventionally used in radical polymerization. It can be for example one of the following initiators:

hydrogen peroxides such as tertiary butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyacetate, t-butylperoxybenzoate, t-butylperoxyoctoate, t-butylperoxynéodécanoate, t-butylperoxyisobutarate, lauroyl peroxide, t-amylperoxypivalte, t-butylperoxypivalate, dicumyl peroxide, benzoyl peroxide, potassium persulfate, ammonium persulfate,

azo compounds such as: 2-2'-azobis (isobutyronitrile), 2,2'-azobis (2-butanenitrile), 4,4'-azobis (4-pentanoic acid), 1,1 ' azobis (cyclohexane-carbonitrile), 2- (t-butylazo) -2-cyanopropane, 2,2'-azobis [2-methyl-N- (1,1) -bis (hydroxymethyl) -2-hydroxyethyl] propionamide, 2,2'-azobis (2-methyl-N-hydroxyethyl) -propionamide, 2,2'-azobis (N, N'-dimethyleneisobutyramidine) dichloride, 2,2'-azobis dichloride (2 -amidinopropane), 2,2'-azobis (Ν, Ν'-dimethyleneisobutyramide), 2,2'-azobis (2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide) 2,2'-azobis (2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propionamide) 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] 2,2'-azobis (isobutyramide) dihydrate,

- redox systems with combinations such as:

. mixtures of hydrogen peroxide, alkyl, peresters, percarbonates and the like and any of the iron salts, titanium salts, zinc formaldehyde sulfoxylate or sodium formaldehyde sulfoxylate, and reducing sugars, . persulfates, perborate or perchlorate of alkali metals or ammonium in combination with an alkali metal bisulfite, such as sodium metabisulphite, and reducing sugars,

The amount of initiator to be used is generally determined so that the amount of radicals generated is at most 20 mol% relative to the amount of the RAFT or MADIX transfer agent, preferably at most 5% in mole.

RAFT or MADIX polymerization processes are described in particular in documents WO 98/58974, WO 00/75207 and WO 01/42312, WO 98/01478, WO 99/31144, WO 02/26836,

According to certain variants of the invention, the monomers bearing at least one phosphorus functional group are unsaturated monomers of the styrene, acrylate or methacrylate, acrylamido or methacrylamido, vinylic or allylic type bearing at least one dialkylphosphonate, phosphonic acid or hemiacide group. -P (OH) (OR), or a mixture of these monomers. Among these monomers carrying phosphorus functional groups, there may be mentioned in particular vinyl phosphonic acid, vinyl phosphonic acid dimethyl ester, vinyl phosphonic acid bis (2-chloroethyl) ester, vinylidene diphosphonic acid, tetraisopropyl ester of vinylidene diphosphonic acid, alpha-styrene phosphonic acid, dimethyl-p-vinylbenzylphosphonate, diethyl-p-vinylbenzylphosphonate, dimethyl (methacryloyloxy) methylphosphonate, diethyl (methacryloyloxy) methylphosphonate, diethyl-2 - (acrylamido) ethylphosphonate or a mixture of these monomers. Preferably, the dimethyl ester of vinyl phosphonic acid and dimethyl-p-vinylbenzylphosphonate will be used.

According to certain variants of the invention, the non-phosphorus comonomers useful for the present invention are the hydrophilic (h) or hydrophobic (H) monomers mentioned above.

The polymerization can be carried out in bulk or in solution, depending on the case. When carried out in solution, is preferably carried out known per se, in the presence of a solvent inert with respect to the radical polymerization which may be for example water, an aliphatic or alicyclic hydrocarbon such as pentane, hexane, heptane, iso- octane, cyclohexane, methylcyclohexane or an aromatic hydrocarbon such as benzene, toluene, xylene or in a more polar solvent such as dichloromethane, THF, DMF, etc.

The polymerization is carried out generally at a temperature of between 10 ° C. and 120 ° C. and preferably in the region of 20 ° C. to 90 ° C.

The invention also relates to the use for the synthesis of block copolymer of a polymer carrying phosphonate and / or phosphonic functions pendant along the chain, and bearing at least one azide function, as described above. by its structure or its method of synthesis.

Indeed, because of the presence of at least one azide function in the poly (phosphorus) polymer, this polymer is particularly suitable for the synthesis of Huisgen cycloaddition cycloaddition block copolymers with a at least one polymer carrying an alkyne function at one or each of its chain ends in accordance with the method described in application WO 2013057083 A2 in the name of the Applicants, the description of which is incorporated by reference. This application describes a process for the synthesis of diene copolymers with at least two blocks, which implements the reaction of the polymer blocks with each other, each being obtained separately according to a polymerization mode perfectly adapted to the nature of each of the monomers. In addition, this synthesis method makes it possible to obtain block copolymers whose macrostructure is controlled while achieving high yields. The polymer blocks are, on the one hand, a diene elastomer carrying an alkyne function at one or each of its chain ends and, on the other hand, a polymer bearing at least one azide function. This reaction also has the advantage of a high yield of up to 90% or even 100%. . This reaction has many additional benefits. It is carried out under mild operating conditions, such as at low temperatures, without secondary products or else harmless by-products, without the influence of impurities, in the absence of solvents or with the use of non-toxic solvents. Which from an industrial point of view represents significant economic, energy and environmental benefits.

The implementation of this process with the poly (phosphorus) polymer according to the invention and a diene elastomer carrying an alkyne function at one or each of its chain ends makes it possible to obtain a diene block copolymer with a high level of phosphonate and / or phosphonic functions under optimal conditions, in a simple, controllable and reproducible manner.

By diene elastomer is meant according to the invention, any elastomer in the sense known to those skilled in the art, derived at least in part (ie, a homopolymer or a copolymer) of at least one conjugated diene monomer having from 4 to 15 carbon atoms, such as 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di (C 1 -C 5) -alkyl-1,3-butadienes, such as, for example, 2-butadiene; 3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3-isopropyl-1, 3-butadiene, aryl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene. The aforementioned features of the present invention, as well as others, will be better understood on reading the following description of several embodiments of the invention, given for illustrative and non-limiting in connection with the attached annexes.

EXAMPLE OF CARRYING OUT THE INVENTION

Measurements and tests used

The elastomers are characterized, before cooking, as indicated below. Stereo Excluder The number-average molar masses M n of the polymers as well as their dispersions were obtained by size exclusion chromatography (CES) with tetrahydrofuran (THF) as eluent at 1 ml / min. Calibration is carried out with polystyrene (PS) standards having molar masses of between 1200 and 512800 g mol-1. The CES chain is equipped with a Waters 2414 RI detector and a set of 2 columns (Shodex KF-802.5 and KF-804) thermostatically controlled at 35 ° C.

Tem perterre of vitreous transitio

The glass transition temperature determination analyzes were carried out with a Netzsch DSC (Phoenix) apparatus.

An aluminum crucible comprising 5 to 10 mg of sample is deposited on a platinum boat. The rate of temperature rise used for all the samples is 10 ° C.min-1. The analyzes were conducted under nitrogen.

Nucleic Magnetic Resonance Spectroscopy

The ¹ H NMR, ³¹ P NMR and ¹³ C NMR analyzes are recorded on a 300 MHz Bruker spectrometer at room temperature and using CDCl ³ as the solvent. The chemical shifts are indicated in ppm. The conversions to monomers are determined by ¹ H NMR and ³¹ P NMR.

Synthesis Example of a Block Copolymer According to the Invention

Examples of the implementation of the invention

 Example 1 Synthesis of an X1-N3 Azide Xanthate

- Reaction scheme

 X1-N3 Scheme 1: Synthesis of xanthate X1 -N3.

In a 500 ml flask, 7.45 g (5.36 × 10 ^-2 mol) of 3-bromo-1-propanol are solubilized in a mixture of 90 ml of acetone and 15 ml of water The reaction mixture is refluxed After 15 hours of evaporation of the acetone, the residue is purified by extraction with diethyl ether / water (1: 1) The organic phase is dried over MgSO ₄ after evaporation of the solvent under reduced pressure 3-azido-1-propanol is isolated as a colorless oil (4.9 g, 90%).

¹ H NMR (300 MHz, CDCl ₃ , δ = ppm): 3.67 (2H, t, -CH ₂ -OH), 3.38 (2H, t, -CH ₂ -N 3), 1.76 (2H, quint, -CH ₂ -CH ₂ -CH ₂ -), 1.68 (1H, s, -CH ₂ -OH).

¹³ C NMR (300 MHz, CDCl ₃ , δ = ppm): 59.48 (-CH ₂ -OH), 48.27 (-CH ₂ -N ₃ ), 31.32 (-CH ₂ -CH ₂ -CH) ₂ -).

A solution of 2-bromopropionyl bromide (19.44 g, 90 mmol) in 65 mL of THF is added dropwise to a solution of 3-azido-1-propanol (6.07 g, 60 mmol) and triethylamine. (12.55 mL, 9.1 g, 90 mmol) in 95 mL of THF at 0 ° C. The reaction is stirred for 2 hours at room temperature. Then the triethylammonium bromide formed is filtered and the THF is evaporated under reduced pressure. The reaction crude is solubilized in chloroform, washed three times with a saturated solution of ammonium chloride and then three times with distilled water. The organic phase is dried over MgSO ₄ after evaporation of the solvent under reduced pressure. 3-Azidopropyl-2-bromopropanoate is isolated as a yellowish oil (18.22 g, 90%). This product is dissolved in 190 mL of ethanol for direct use in the next step. To this solution, 18.56 g (1 16 mmol) potassium ethylxanthogenate are added slowly at 0 ° C. The reaction is stirred for 15 hours at room temperature. The potassium bromide and the excess potassium ethylxanthogenate are filtered and the ethanol is evaporated under reduced pressure. The reaction crude is solubilized in chloroform and washed three times with distilled water. The organic phase is dried over MgSO ₄ after evaporation under reduced pressure of chloroform. After purification on a chromatographic column (eluent: petroleum ether / ethyl acetate, 95/5), the product X1-N3 is obtained in the form of a yellow oil (9.15 g, 55%) after having been dried under reduced pressure.

¹ H NMR (300 MHz, CDCl ₃ , δ = ppm): 4.63 (2H, q, -O-CH ₂ -CH ₃ ), 4.38 (1H, q, O (O) C-CH ( CH ₃ ) -SC (S) -), 4.22 (2H, t, -CH ₂ -CH ₂ -OC (O) -), 3.40 (2H, t, -CH ₂ -N ₃ ), 1 , 92 (2H, quint, -CH ₂ -CH ₂ -CH ₂ -), 1. 57 (3H, d, O (O) C-CH (CH ₃ ) -SC (S) -), 4.63 ( 2H, t, -O-CH ₂ CH ₃ ).

¹³ C NMR (300 MHz, CDCl ₃ , δ = ppm): 212.0 (-SC (S) -CH-), 171, 1 (CH ₂ -OC (O) -CH-), 70.3 (0); -CH ₂ -CH ₃ ), 62.4 (-CH ₂ -CH ₂ -OC (O) -), 48.0 (-CH ₂ -CH ₂ -CH ₂ -), 47.0 (0 (0) C-CH (CH ₃ ) -SC (S) -), 28.0 (-CH ₂ -N ₃ ), 1 6.7 (0 (C) CH (CH ₃ ) -SC (S) -) , 13.6 (O-CH ₂ -CH ₃ ).

Example 2 Synthesis of poly (dimethyl vinylphosphonate): PDMVP-N3

- Reaction scheme

Scheme 2: MADIX polymerization of DMVP in the presence of X1 -N3

The polymerization is carried out according to the following protocol: X1-N3 xanthate (383 mg, 1.38 × 10 ^-3 mol), dimethyl vinylphosphonate (1 g, 7.34 × 10 ^-3 mol), ΓΑΙΒΝ (24 mg, 1.46x10 ^"4 mol) and 1.54 g of 1,4-dioxane are placed in a Schlenk tube, the solution is degassed with argon for 15 minutes and then placed in a bath previously heated to 70 ° C. C. The reaction mixture is left stirring for 24 hours and the reaction mixture is purified by drying under reduced pressure at 80 ° C. and washing with dichloromethane to remove the residual monomer and dioxane.The conversion obtained is 80% and the molar mass, determined by ³¹ P NMR, is 820 g mol ^-1 (M _n , _he = 800 g mol ^-1 ).

Example 3 Synthesis of Poly (Dimethyl Vinylbenzylphosphonate): PDMVBP-N3

 - Reaction scheme

Scheme 3: MADIX polymerization of DMVBP in the presence of X1 -N3

The polymerization is carried out according to the following protocol: xanthate X1 - N3 (28.1 mg, 1.11 .10 ^-4 mol), dimethyl p-vinylbenzylphosphonate (DMVBP) (2 g, 8.85 × 10 ^-3 mol) ΙΆΙΒΝ (14.5 mg, 8.85 × 10 ^-5 mol) and 3.1 g of 1,4-dioxane are placed in a Schlenk tube, the solution is degassed with argon for 15 minutes and then placed in a bath. preheated to 70 ° C. The reaction is left stirring for 24 hours The reaction mixture is purified by precipitation in pentane and then drying under reduced pressure at 80 ° C. The conversion obtained is 70% and the average molar mass in number, determined by CES-RI, is 13250 g mol ^-1 (M _n , _he = 14000 g mol ^-1 ). Example 4 Synthesis of the polybutadiene-b-poly (dimethyl vinylbenzylphosphonate) block copolymer

- Reaction scheme

Scheme 4: Synthesis of polybutadiene-b-poly (vinylbenzylphosphonate dimethyl) block copolymer 500 mg of polybutadiene functionalized acetylene (Mn = 93000 g mol- ¹ , 5.37 × 10 ^-6 mol), 85.3 mg (Mn = 13250 g) mol ^"1 , 6,44.10 ^{" 6} mol) of polyvinylvinyl dimethyl phosphonate functionalized azide and 4 mL of THF are introduced into a Schlenk tube which is then degassed by 3 cycles freeze / thaw. A second solution contained 7.9 mg (6,44.10 ^"5 mol) of CuOAc in 10 mL of THF. This solution was degassed with argon for 15 minutes and then 1 mL of this solution was cannulated into the solution containing the polymers. The reaction medium is heated in an oil bath at 40 ° C. and then left stirring for 48 hours, after which the reaction medium is passed through an alumina column in order to remove the copper residues and then purified by dialysis via membranes with a threshold of cut at 14000 g mol ^-1 to remove unreacted PDMVBP-N3. The diblock polymer is then subjected to an antioxidant treatment by adding 0.2 parts per hundred parts of 4,4'-methylene-bis-2,6-tert-butylphenol elastomers and then dried under reduced pressure at 80 ° C. . The molar mass, determined by CES-RI, is 105300 g mol ^-1 .

Example 5 Synthesis of the polybutadiene-b-poly (dimethyl vinylphosphonate) block copolymer

Reaction scheme

 Scheme 5: Synthesis of polybutadiene-b-poly (dimethyl vinylphosphonate) block copolymer

500 mg of polybutadiene functionalized with acetylene (Mn = 93000 g / mol, 5.37 × 10 ^-6 mol), 7 mg (Mn = 1080 g mol- ¹ , 6.44 × 10 ^-6 mol) of dimethyl poly (vinylphosphonate) functionalized with azide and 4 mL of THF are introduced into a Schlenk tube which is then degassed by 3 freeze / thaw cycles. a second solution contained 7.9 mg (6,44.10 ^"5 mol) of CuOAc in 10 mL of THF. This solution is degassed with argon for 15 minutes then 1 ml of this solution is cannulated in the solution containing the polymers. The reaction medium is heated in an oil bath at 40 ° C. and then left stirring for 48 hours. The reaction medium is then passed through a column of alumina to remove the copper residues and then purified by dialysis via 14000 g mol- ¹ cut-off membranes to remove the unreacted PDMVP-N3. an antioxidant treatment by addition of 0.2 parts per hundred parts of elastomers, 4,4'-methylene-bis-2,6-tert-butylphenol and then dried under reduced pressure at 80 ° C. The molar mass, determined by CES-RI is 95200 g mol ^-1 .

Claims

Poly (phosphorus) polymer carrying phosphonate and / or phosphonic functions pendant along the chain, as well as at least one azide function. Polymer according to Claim 1, characterized in that it corresponds to the formula: P - (N ₃ ) _q  P poly (phosphorus) being a polymeric chain comprising units bearing phosphonate and / or phosphonic functions pendant along the chain and q an integer ranging from 1 to 15, or even from 1 to 12, preferably 1 to 8. Polymer according to Claim 1 or 2, characterized in that the poly (phosphorus) polymer chain P corresponds to the following general formula (I):

 (I)  with  m denoting an integer greater than or equal to 2 and n denoting an integer greater than or equal to 0, provided that when n is not 0, n and m may be identical or different, preferably greater than 2 and preferably less than 2500; . X, X ', which may be identical or different, represent H, a halogen or a group R 1, OR 1, OCOR 1, NHCOH, OH, NH ₂ , NHR-1, N (R 1) ₂ ,

NHCOR1, CO ₂ H, CO2R1, CN, CONH2, CONHR1 or COISKR1, wherein R1 is selected from alkyl, aryl, aralkyl, alkylaryl, alkene or organosilyl groups, optionally perfluorinated and optionally substituted by one or more carboxyl groups, epoxy , hydroxyl, alkoxy, amino, halogen or sulfonic acid. Υ, Υ ', which may be identical or different, are such that either Y, Y' or both comprise at least one phosphorus functional group -P (O) (OR ₂ ) (OR ₃ ), R 2 and R ₃ , which are identical or different, representing a hydrogen atom or an alkyl radical, optionally haloalkyl,  the monomeric units comprising Y and Y 'consist of monomer units comprising Y and Y' of the same nature or a mixture of monomer units comprising Y and Y 'of different nature,  the monomeric units comprising X and X 'are constituted by monomer units comprising X and X' of the same nature or a mixture of monomeric units containing X and X 'of different nature,  the sequence of monomer units is statistical or sequenced. Polymer according to Claim 3, characterized in that the molar fraction of monomer units of the poly (phosphorus) polymer containing X and X 'ranges from 0 to 0.5, preferably from 0 to 0.25, more preferably from 0 to 0.1. Polymer according to any one of the preceding claims, characterized in that the poly (phosphorus) polymer bearing an azide function at the chain end has a number of units of at least 2 and at most equal to 5000. Process for the synthesis of a poly (phosphorus) polymer bearing at least one azide function, characterized in that it comprises firstly the homopolymerization of a monomer carrying at least one phosphonate and / or phosphonic function or the copolymerization of one or more monomers carrying at least one phosphonate and / or phosphonic function between them or with one or more comonomers, and, on the other hand, concomitantly or successively, functionalization by introduction of at least one an azide function. Process according to Claim 6, characterized in that the polymerization is a RAFT or MADIX polymerization of at least one monomer bearing from minus a phosphonate and / or phosphonic function in the presence of a transfer agent RAFT or MADIX carrying at least one azide group and a polymerization initiator. 8. Process according to claim 7, characterized in that it comprises the synthesis of the transfer agent carrying at least one azide group. 9. The method of claim 8, characterized in that the transfer agent is a thiocarbonylthio compound bearing at least one azide group. 10. Process according to claim 9, characterized in that the thiocarbonylthio transfer agent corresponds to the general formula:  R-S- (C = S) -Z  in which,  R represents:  a group (i) alkyl, acyl, aryl, alkenyl or alkynyl,  a carbon cycle (ii), saturated or non-saturated, optionally aromatic; - heterocycle (iii), saturated or unsaturated, optionally aromatic; or wherein said groups and rings (i), (ii) and (iii) may be substituted by substituted phenyl groups, substituted aromatic groups or: alkoxycarbonyl or aryloxycarbonyl (-COOR '), carboxy (-COOH), acyloxy ( - ₂ CR '), carbamoyl (-CONR' ₂ ), cyano (-CN), alkylcarbonyl, alkylarylcarbonyl, arylcarbonyl, arylalkylcarbonyl, phthalimido, maleimido, succinimido, amidino, guanidimo, hydroxy (-OH), amino (-NR ' ₂ ), halogen, allyl, epoxy, alkoxy (-OR '), S-alkyl, S-aryl, groups having a hydrophilic or ionic character such as the alkaline salts of carboxylic acids, the alkaline salts of sulfonic acid, polyalkylene oxide chains (POE, POP), cationic substituents (quaternary ammonium salts), R 'representing an alkyl or aryl group,  a polymer chain, with the proviso that R contains an azide group; Z is an oxygen atom, a carbon atom, a sulfur atom, a nitrogen atom, or a phosphorus atom, these atoms being substituted with one, two or three hydrocarbon radicals R ", so as to have an appropriate valence, which may include a heteroatom, such that R "represents:  a group (i) alkyl, acyl, aryl, alkenyl or alkynyl,  a carbon cycle (ii), saturated or non-saturated, optionally aromatic; - heterocycle (iii), saturated or unsaturated, optionally aromatic; or wherein said groups and rings (i), (ii) and (iii) may be substituted by substituted phenyl groups, substituted aromatic groups or: alkoxycarbonyl or aryloxycarbonyl (-COOR '), carboxy (-COOH), acyloxy ( - ₂ CR '), carbamoyl (-CONR' ₂ ), cyano (-CN), alkylcarbonyl, alkylarylcarbonyl, arylcarbonyl, arylalkylcarbonyl, phthalimido, maleimido, succinimido, amidino, guanidimo, hydroxy (-OH), amino (-NR ' ₂ ), halogen (Cl, Br, I or F), allyl, epoxy, alkoxy (-OR '), S-alkyl, S-aryl, groups having a hydrophilic or ionic character such as the alkaline salts of carboxylic acids alkali metal salts of sulfonic acid, polyalkylene oxide chains (POE, POP), cationic substituents (quaternary ammonium salts), R 'representing an alkyl or aryl group,  a polymer chain, 1 1. Process according to claim 10, characterized in that the transfer agent corresponds to the structural formula: N3- (CH ₂ ) ₃ -O (C = O) - (CH ₃ ) CH-S- (C = S) -OEt 12. Process according to any one of Claims 6 to 11, characterized in that the monomer carrying at least one phosphonate and / or phosphonic function is vinylphosphonic acid, the dimethyl ester of vinylphosphonic acid, vinylphosphonic acid bis (2-chloroethyl) ester, vinylidene diphosphonic acid, vinylidene diphosphonic acid tetraisopropyl ester, alpha-styrene phosphonic acid, dimethyl-p- vinylbenzylphosphonate, diethyl-p-vinylbenzylphosphonate, dimethyl (methacryloyloxy) methylphosphonate, diethyl (methacryloyloxy) methylphosphonate, diethyl-2- (acrylamido) ethylphosphonate, any styrene unsaturated monomer, acrylate or methacrylate, acrylamido or methacrylamido, vinyl or allylic bearing at least one dialkylphosphonate, phosphonic acid diacid or hemiacide-P (OH) (OR) group, or a mixture of these monomers. 13. Process according to any one of claims 6 to 12, characterized in that the comonomer is a hydrophilic monomer (h) or a hydrophobic monomer (H),  The hydrophilic monomer (h) being  the vinyl alcohol resulting from the hydrolysis of vinyl acetate, a neutral acrylamido monomer,  a cyclic amide of vinylamine,  an ethylenically unsaturated mono- and dicarboxylic acid, an ethylenic monomer comprising a sulphonic acid group or one of its alkaline or ammonium salts, or  a monomer chosen from aminoalkyl (meth) acrylates and aminoalkyl (meth) acrylamides; monomers comprising at least one secondary, tertiary or quaternary amine functional group, diallyldialkyl ammonium salts such as dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, 2-vinylpyridine, 4-vinylpyridine, diallyldimethyl ammonium chloride.  The hydrophobic monomer (H) being  a styrene monomer, an ester of acrylic acid or of methacrylic acid with C ₁ -C ₂ , preferably C ₁ -C ₈ , alcohols which may be fluorinated, a vinyl nitrile containing from 3 to 12 carbon atoms,  a vinyl ester of a carboxylic acid, a vinyl or vinylidene halide, or a diene monomer. 14. Use of a poly (phosphorus) polymer defined according to any one of claims 1 to 5 for the synthesis of block copolymers by reaction of 1,3-dipolar cycloaddition with at least one polymer bearing an alkyne function to one or both of its chain ends. 15. Use according to claim 14 characterized in that the poly (phosphorus) polymer is obtainable by the process defined according to any one of claims 6 to 13. 16. Use according to claim 14 or 15, characterized in that the polymer bearing an alkyne function at one or each of its chain ends is a diene elastomer.