CA2275736C - Polymers derived from block polymerization monomers and their uses, especially for the preparation of ionic conductors - Google Patents

Abstract

The present invention relates to polymers obtained by anionic initiation and carrying functions that can be activated by cationic initiation which are not reactive in the presence of reagents initiating anionic polymerizations. The presence of such functions with cationic primer allow effective crosslinking of the polymer after shaping, or in particular in the form of a thin film. It is thus possible to obtain polymers having very well-defined properties, in terms of molecular weight and crosslinking density. The polymers of the invention are capable of dissolving ionic conductivity inducing compounds for the preparation of electrolytes.

Description

TITLE

Polymers obtained from monomers allowing their polymerization sequence, and their uses, in particular for the preparation of ionic conductors.
FIELD OF THE INVENTION

The present invention relates to polymers obtained by anionic initiation and carrying functions that can be activated by cationic priming which does not are not reactive in the presence of reagents initiating anionic polymerizations. The presence such functions with cationic primer allow effective crosslinking of the polymer after shaping, or in particular in the form of thin film. It is thus possible to obtain polymers with very well-defined properties, in terms of mass molecular and crosslinking density.

PRIOR ART

Three types of polymerization mechanism are mainly known the anionic, cationic and radical occurrence. Generally, the monomers wearing conjugate or activated double link functions allowing the spread radical species are the most used. On the other hand, it is difficult to control molecular masses obtained, especially since the radicals are inactivated by oxygen.

More recently, monomers carrying vinyl ether type functions CH2 = CHO- having a high reactivity in cationic polymerization have been marketed. Cationic polymerization, although very fast, gives with difficulty high molecular weights mainly because carbocations allowing the propagation of polymerization are sensitive to water or other nucleophiles present In the reaction medium.

-2-The most used compositions for the manufacture of films, varnishes or inks generally combine epoxy monomers with monomers carrying one or more vinyl ether functions and which are polymerized by of the cationic catalysts. Polymerization of epoxides and that of ethers vinyl CH2 = CHO- propagating at very different speeds, solids macromolecular obtained usually consist of corresponding interpenetrating networks every type of monomers. The degree of polymerization and the crosslinking density effective such systems are therefore difficult to control. Mechanical properties are more depending on the rigidity of the chains or the presence of OH functions giving strong hydrogen bonds. These compositions, in particular those to which are added the vinyl diethers of glycols or triols, nevertheless allow minimize the consumption of volatile solvents due to the low viscosity of the monomers corresponding (called "reactive diluents"). Vinyl ethers present That much low toxicity.

The concept of "reactive diluent" is also used for monomer mixtures of acrylic (radical) type with monomers of vinyl ether type, in the presence radical initiators added to cationic initiators. It is nevertheless just as 2o difficult by this technique to ensure a regular control of the rate of polymerisation tion / crosslinking due to the sensitivity to oxygen of the polymerization radical. This problem arises especially for thin films exposing a surface of contact important to the air. Polyfunctional monomers containing a function ether vinylic have been described in US 5,605,941. These compounds are intended for get some cross-linked resins having a high glass transition temperature by a process in

-3-a single step involving interpenetrating networks of the type (cationic +
cationic) or (cationic + radical).

Anionic polymerization has many advantages in terms of precise control of the molecular mass, in particular a distribution of masses M, / M ,, narrow. This method remains the one of choice for the preparation of polymers massive predetermined and for the elaboration of block polymers, type AB, ABA, or branched.
However, the initiators as well as the anionic species allowing the spread are very reactive. These species are either organometallic or alkoxides of metals lo alkalis that react on most organic functions carried by the monomers, especially those that would allow easy subsequent crosslinking, such as functions containing epoxides, alcohols or amines, or double bonds activated by one or more conjugated double bonds, an aromatic ring or group attractor of electrons such that C = O, C = N. Conditions of exclusion of water or other nucleophile when 1.5 of the polymerization make that this type of polymer is prepared in dedicated units, and not at the time of use or formatting.

Polymers possessing ether functional groups are also known high concentration, usually 40 to 100 mol%, especially containing the units - [(CH 2 H (R) O] .- where 4 <n <2 x 104 and R is H or a single alkyl group from 1 to 4 carbon atoms, or a polymerizable group such as the group allyloxy methyl CH = CHCH2OCH2-. Copolymers, in particular those in which R is mainly H, have the property of dissolving certain salts, metallic or of onium (ammonium, amidinium, guanidinium) to form solid solutions 25 conductors. Lithium salts are particularly useful for forming electrolytes

-4-usable in primary or secondary batteries, super-capacitors where the so-called "electrochromic" light modulation devices. The environment in which these materials work, in particular in contact with elements very Reducers, such as metallic lithium, its alloys or solutions solids of this metal in different forms of carbon, including graphite and cokes, requires a big stability of the constituent bonds of the polymer, mainly limited to CH links and CO ether functions. The low intrinsic conductivity of these materials leads to put them into thin films with good outfits mechanical. This is obtained by the use of high molecular weights or even more conveniently lo by a process of crosslinking. This last method has the opposite disadvantage to increase the glass transition temperature (Tg) of the network, which is the parameter the more important to determine the conductivity. In addition, the functions allyloxymethyl introducing functions allowing crosslinking, in particular with the monomer allyl-glycidyl ether (AGE), which are resistant to the action of catalysts allowing the anionic polymerization, are only slightly active for the subsequent formation of knots crosslinking, and it is impossible to exactly control the density of crosslinking materials containing this monomer. It is difficult to involve more than 50% of double bonds to crosslinking.

Polymers prepared from vinyl ethers of oligo (ethylene oxide) have been proposed as solid electrolytes, for example in US 4,886,716, US 5,064,548, US 5,173,205, US 5,264,307, US 5,411,819 and US 5,501,920 and show acceptable conductivity properties. The preparation of the monomers corresponding is delicate. These materials before crosslinking are low molecular weight, as for most cationic polymerizations.
Indeed,

-5-the monomers are very hygroscopic, and therefore difficult to purify. In In addition, mechanical properties of polymers are poor due to the lack of entanglement, a phenomenon peculiar to side chain polymers. By use polyfunctional monomers of the vinyl diether type, it is possible to to obtain crosslinked products, but it is impossible to separate the step from polymerization of cationic crosslinking, which makes it possible to practically no control over the process of obtaining the crosslinked polymer.

SUMMARY OF THE INVENTION

The present invention relates to a crosslinkable polymer prepared by priming anionic polymerization followed by cationic crosslinking, the polymer responding to the general formula:

(A) .Q (Y) p in which Q represents a bond, -CO-, SO2, or an organic radical of valence n + p no reactive with agents initiating the anionic polymerization or cationic comprising an alkyl, alkylearyl or arylalkyl radical optionally comprising substituents oxa or aza, and comprising from 1 to 30 carbon atoms;

A represents a reactive radical in anionic polymerization;

Y represents a reactive radical in cationic and non-reactive polymerization vis-a-vis an agent initiating the anionic polymerization;

n varies between 1 and 3; and p varies between 1 and 6.

In a preferred embodiment, A comprises

-6-GOLD
z Includes O /
R

wherein Z represents O or CH2;

R represents H, an alkyl or oxa-alkyl radical of 1 to 12 carbon atoms, CN or CH2000R 'wherein R' is H or an alkyl or oxa-alkyl radical of 1 to 12 atoms of carbon;

R 'represents H or an alkyl radical of 1 to 12 carbon atoms; and r varies between 1 and 6.

The present invention also relates to an ionically conductive material constituted by at least one polymer and at least one ionic compound, characterized in that than:

the polymer is a crosslinked polymer prepared by anionic polymerization followed by crosslinking by cationic polymerization of a monomer corresponding to the formula (A) õQ (Y) p optionally with one or more other monomers, in which -6a-Q represents a bond, CO, SO2, or an organic radical of valence n + p non-reactive with initiators of the anionic polymerization or a cationic polymerization, the organic radical is chosen from a radical alkyl, alkylaryl and arylalkyl optionally having oxa substituents or aza, and having 1 to 30 carbon atoms;

* A is a reactive radical in anionic polymerization;

Y is a reactive radical in cationic polymerization and non-reactive vis-à-vis screw an agent initiating the anionic polymerization and represents the function crosslinkable crosslinked polymer, * n varies between 1 and 3;

* p varies between 1 and 6; and the ionic compound is constituted by at least one salt M "+ Xj, in which M" +
represents an inorganic, organic or any organometallic cation of load n, and X is a monovalent anion, two or more X- anions are linked together by covalent chains or belonging to the chain of a polymer.

The polymers of the invention are capable of dissolving ionic compounds inducing conductivity, for the preparation of electrolytes.

DETAILED DESCRIPTION OF THE INVENTION

The subject of the present invention is polymers obtained by priming anionic and carrying functions that can be activated by priming cationic, and allowing effective cross-linking of the polymer after shaping, or particular in the form of a thin film. Active functions in cationic polymerization thereby are -6b-chosen for their stability vis-à-vis the reagents allowing the anionic polymerization.
It is thus possible to obtain polymers having very high properties.
well defined,

-7-terms of molecular weight and crosslinking density, making use of the cumulative benefits of these two types of polymerization. Crosslinking is realized from efficient way, and totally independent in particular from the action of oxygen.

Integral part and are an important aspect of the invention, polymers anionically prepared and cationically cross-linked, capable of dissolve ionic compounds inducing conductivity for the preparation solid electrolytes.
As mentioned earlier, the need to be able to introduce grounds allowing crosslinking without compromising chemical stability or electrochemical lo system and without significant increase of the transition temperature glassy, is decisive. The polymers of the invention meet these criteria by the choice of active groups in cationic polymerization and allowing crosslinking effective and controlled.

The monomers used to obtain a polymer according to the invention are defined by the general formula:

(A) .Q (Y) p in which Q represents a bond, -CO- or -SOZ, an organic radical of valence n + p no 2o reagent vis-à-vis agents initiating the anionic polymerization or cationic, and type alkyl, alkylearyl or arylalkyl, optionally having substituents oxa or aza, and comprising from 1 to 30 carbon atoms;

A represents a reactive radical in anionic polymerization;

Y represents a reactive radical in cationic and non-reactive polymerization vis-à-vis Initiators of anionic polymerization;

-8-n varies between 1 and 3; and p varies between 1 and 6.

Preferably, n is equal to 1 except in the case where it is advantageous of directly dispose of a crosslinked material and it is desirable to continue the cationic mode crosslinking. When n is 2, two functions carried by the same monomer polymerise in a concerted manner, as for those formation of cycles without creating crosslinking. It can also be interesting to mix monomers for which n = 1 to a small fraction, for example from 0.1 to 10%, of the polyfunctional monomer so as to increase the molecular weight by creation of connections compensating for the natural termination of the strings.

The polymers of the invention are prepared by anionic polymerization, and contain monomers as defined above in which A comprises preferably:

R

Z
wherein Z = O or CH2; and R represents H, an alkyl or oxa-alkyl radical of 1 to 12 carbon atoms, CN or CH 2 COOR 'in which R' is H or an alkyl or oxa-alkyl radical of 1 to 12 atoms of carbon.

In these same monomers, Y preferably comprises:

-9 R ~ / OO and N
wherein R 'represents H or an alkyl radical of 1 to 12 carbon atoms; and r varies between 1 and 6.

The lifetime of cationic species allowing the propagation of the polymerization / crosslinking being particularly long compared to the species radicals, the reaction may continue after initiation by an initiator of cationic polymerization until complete consumption of the Y groups.
particular, a very short exposure to heat or radiation actinic enough to initiate the reactive species, and the polymerization can continue even in the absence of activating agent, especially due to the absence of a termination reaction by the oxygen of the air.

The present invention extends to a material for which the polymerization cationic Y groups is made in the presence of other monomers, oligomers or polymers carrying functions that are activated by agents initiating the cationic, radical polymerizations, or both.

The present invention aims at a material for which the polymerization cationic groups Y and any optional additive in the form of monomer, oligomer or polymer, is made thermally, by radiation action actinic, or both, with or without an initiator.

- 9a-The present invention is directed to a material further containing a plasticizer.

The present invention is directed to a material in which an additive is incorporated in the form of powders, fibers or both, optionally treated, so that its surface has increased compatibility and adhesion to the polymer or of the polymer blends.

The present invention is directed to a material in which the additive is organic or inorganic, and optionally has ionic conduction properties or intrinsic electronic, optical properties, a dielectric constant high, piezoelectric properties, or a combination thereof.

The present invention extends to a material for which the polymer is a homopolymer of a monomer (A) nQ (Y) p wherein A is a group O
or a copolymer of the monomer (A) nQ (Y) p and an epoxide. In a mode of use preferred, the epoxide is ethylene oxide.

The present invention extends to a material for which at least one co-monomer is used in addition to ethylene oxide, the comonomer is chosen among one propylene oxide, a butylene oxide, a diene monoepoxide of 4 to 10 carbon of carbon and ethers of glycidol with methyl, ethyl or allyl.

- 9b-The present invention aims at a material for which the crosslinked polymer is a homopolymer of a monomer (A) õQ (Y) p wherein A is a group or a copolymer of the monomer (A) õQ (Y) p and a styrenic monomer.

The initiators of anionic type which can be used preferably comprise organometallics, amides, alkoxides, strong bases derived dialkyl aminophosphines. Preferred organometallics include aikyllithium, such than butyllithium (primary, secondary or tertiary), hexyllithium, derivatives, lithium, sodium or potassium of 1,1'-diphenylethylene, tetraphenylethylene, of naphthalene, biphenyl and benzophenone. Preferred amides include NaNH2, Ca (NH2) 2, their adducts with epoxides, dialkylamides as lithium di-isopropylamide. Preferential alkoxides include methoxides, ethoxides, butoxides (primary, secondary, tertiary) or amyloxide alkali metals, the alkoxides of linear alcohols with 8 to 18 carbon, monohydric polyethylenes with a mass of between 400 and 800, the alkoxides of alcohols

-10-polyhydric compounds, such as glycol, glycerol, oligoethylene glycol, sorbitol, the pentaerythritol, trimethylolpropane, bis-trimethyloldiethylether, bisphenol A and their polyethoxylated derivatives. Preferential strong bases include derived from dialkylaminophosphines such as 1-tert-butyl-4,4,4, -tris [dimethylamino-2,2-bis (trisdiméthylamino) phosphoranylideneamino] -2X5-4? 5-catenadi (phosphazene), commonly called "phosphazene base P4-t-bu". In general, derivatives organometallic compounds and dialkylamides, in particular derivatives of lithium, are preferred for initiating the polymerization of the double bonds activated by other doubles conjugated C = C or C = O bonds, such as butadiene derivatives, styrene, acid lo acrylic or methacrylic. For the polymerization of epoxides, the metal derivatives alkalis such as sodium and more particularly the potassium of alcohols mono- or polyhydroxylates leading to the formation of linear or branched chains, are preferred.
On the other hand, the dialkylaminophosphines are reactive for acrylates or the epoxides. The activity of organometallic derivatives, amides or alkoxides, may be increased in the presence of molecules likely to strongly solvate the ions alkali, for example THF, the di-alkyl ethers of oligoethylenes glycols having from 2 to 16 carbon atoms and can also be used as a solvent. The peralkyl (polyethyleneimines) of 2 to 8 nitrogen atoms, in particular the tetramethylethylenediamine (TMDA), pentamethyldiethylenediamine, and tris (2-2-dimethylaminoethylamine) have particularly activating properties marked.

The polymers of the invention obtained after the anionic polymerization step initially are cross-linked by a cationic process using the groups of monomers provided for this purpose. In general, the catalysts allowing the propagation of the polymerization / crosslinking reaction are acids of Lewis or

-11-Bronsted. Lewis acids among the most reactive include derivatives of aluminum, boron, zinc type B (Hal) 3, Al (Hal) 3, Zn (Hal) 2, in which Hal is a halogen or pseudohalogen, an alkyl, aryl, or halide group of zinc.
Bronsted acids are on their side likely to give a cation of which load surface area is greater than 3 x 10-19 coulombs / R2. The other cations that correspond to load criterion may in an unrestricted manner include Li +, Mg2 +, Cal +, Zn 2+, Sn 2+, A13 + etc. The most reactive derivatives are strong acids whose anions X-are weakly basic or weakly nucleophilic. Examples of such anions X are A1C14, BF4, PF6, AsF6, SbF6, TeOFS, R2SO3 or B (R2) 4 wherein R2 is the fluorine, a the organic group alkyl or aryl, halogenated or not; the imidures (R2SO2) 2N; the methylides (R2SO2) 2C (R3) -, (R2SO2) 3C- where R3 is H or R2. Acids can to be directly added to the polymer or be in latent form. Base salts low such as nitrogenous bases or ethers, are suitable for this purpose, and the acid form is released by heating, preferably at temperatures between 40 and 180 C. He It is also possible to release the acid thermally from a salt of diazonium RN = N + X- decomposing to give HX acid and nitrogen by tearing of protons to the solvent or monomer.

The acid esters corresponding to non-nucleophilic anions are Effective cationic initiators. These include toluene, fluoro, methane- and trifluoromethanesulfonates of methyl, ethyl, benzyl, diesters of the tetramethylene - (CH2) 4-.

In a very advantageous manner, the acids can be released by actinic radiation on labile compounds. By actinic radiation, hear them

-12-visible or UV photons, ionizing radiation, including y-rays and beams P. Cationic photoinitiators, otherwise known as photogenerators acid, include the ionic compounds JX in which X represents an anion such than defined above and J + represents a cation of diaryliodionium type, diarylbromonium, triarylsulfonium, phenacyl-dialkylsulfonium, arene-metallocenium arylesdiazonium, the organic groups being optionally substituted.
Two or several J + cations can be connected together or J + can be part of one unit recurrent of a polymer chain. Another family of photoinitiators or initiators advantageously comprises the sulphonic esters of 2-nitro, 2,4-dinitro or 2,6-dinitrobenzyl, especially toluenesulfonates of 2,4-dinitro or 2,6 dinitrobenzyl. These initiators are not ionic, and therefore easily miscible with monomers and polymers with little or no polarity.

There are other cationic initiators, in particular salt derivatives of allyloxypyridinium which, in the presence of free radical generators, is activated thermally or by actinic radiation, release alkyl cations or pyridyl.
N- [2-ethoxycabonylallyloxy] hexafluoroantimonate picolinium.

The technique of the invention is particularly advantageous for the preparation of polymers in the form of films, due to the insensitivity of process of cationic polymerization with oxygen, in particular in comparison with techniques involving radical processes. The scope of the process is however not limited to this type of formatting. The polymers before crosslinking can to be shaped in any shape after adding a latent catalyst of polymerization cationic which is activated either by heat or by actinic radiation penetrating.

-13-It may be interesting to minimize the volume contractions inherent in the most of the polymerization processes, including crosslinking. The process cationic compounds involving oxygenated derivatives of spiro-type dioxolanes orthoformates or spiroorthocarbonates are characterized by an increase of volume.
Monomers and polymers of the invention carrying such functions, which can be used to control volume variations, are exemplified by the formulas following:

M50le O 0> ~ OO
OOO
rr Another advantage that the cationic crosslinking groups of in addition to the controllability and completeness of the crosslinking, is the flexibility of the subnet obtained. The functions resulting from the crosslinking cationic carrying groupings of type:

'- ~ Y 0 / O / OO
`1 ~ 0 41 0 01_ ~ \ __ / N
r N
O

intrinsically flexible, and the corresponding homopolymers have low glass transition temperatures (Tg). For example, Tg = -31 C for the polyvinylmethyl ether, whereas Tg = + 114 C for polymethacrylate methyl. These characteristics can be maintained at the cationic subnetwork of polymer by the choice of flexible links connecting the anionic groups to the

-14-cationic groups. Single alkylene - (CH2) n in which 2 <_ n <_ 12 and oxyalkylene - [CH 2 OCH (R)] n in which 1 <n <6, are particularly favorite to form the divalent organic bonds ensuring the junction between the groups anionic and cationic groups in the monomer and / or the polymer resulting.

The polymers of the present invention may be homo- or random copolymers incorporating monomers with dual functionality and one or several other monomers. For example, we denote Aa-stat-Bb stat-C ,, a terpolymer containing the monomers A, B and C in molar ratios a, b, and c respectively.

They may be block polymers, of the A-block-B or A-block-B-block-A type, A block-B-block C, each segment A, B or C can incorporate at various rates the monomers to double functionality. In a variant, only A, B or C incorporates in form of homopolymer or copolymer at least one monomer with dual functionality.
It is understood that the polymers of the invention are not limited to three monomers and anyone skilled in the art can appreciate the possible variations offered by the character living from anionic polymerization. Another possibility is to train polymers in star or dendrimers from polyfunctional anionic initiators Of type T (Aa-stat-Bb stat-Cc) t, T (A-block-B) t or T (A-block-B-block-A) t or else T (A-block-B-block-C) t, T being a polyfunctional radical of valence t, t <104, of preferably, 2 <_ t <_ 10 for star structures, and may have a value up to 104 for dendrimers.
Branched polymers can be obtained by using low rates a monomer having more than one reactive functionality in polymerization anionic.

The shaping and crosslinking step can be preceded or simultaneous with the addition of various adjuvants, for example a dispersion of solids, under made of

-15-powders, slivers or fibers, intended to change the properties rheological and produced during formatting and / or imparting characteristics mechanical improved to the finished product as well as flame retardant properties. To this end, can quote the dispersions of silica in the form of nanoparticles, carbon black, oxides simple like magnesia, or complexes like LiAlO2, nitrides and carbides lamellar silicates, in particular of the micas type, hectorite montmorillonite, vermiculite, graphite, including expanded form; of the complex fluoroaluminates of KA1F4 type, polyolefin type fibers or polyimides, including aromatic ones, carbon fibers in particular those lo obtained by pyrolysis of organic materials of ceramic fibers including oxides, nitrides or carbides or oxynitrides or oxycarbides, optionally form woven or nonwoven web. Additives conferring other properties specific to polymer may also be added, for example additives having a conductivity ionic or electronic like alumina R or a ", lithium nitride, carbon under all its forms, the conjugated polymers, in particular the derivatives of the benzene, thiophene, pyrrole and fused heteroaromatic rings. Additives structure perovskite can contribute to increasing the dielectric constant in inducing piezoelectric properties for the resulting composite material.

The molar proportion of monomer with dual functionality can be chosen between 0.1 and 100 mol% depending on the desired crosslinking density. The compositions preferred compounds of the invention comprise between 1 and 35 mol% of monomer to double functionality.

-16-Liquids or plasticisers to increase the flexibility of the polymer at the finished state or during its shaping can also be added. Of such liquids or plasticizers are very numerous and known to those skilled in the art. In general, these materials are chosen for their compatibility with the polymer chain and for their weak volatility. It is possible to mention mainly organic polyacid esters, such as phthalates, citrates, α, β-diacids of 3 to 12 carbon atoms of alkyl or alkylene glycols of 2 to 18 carbon atoms, and esters of phosphoric acids or phosphonic compounds which confer flame retardant properties.

The addition of plasticisers also makes it possible to increase if necessary the low temperature conductivity of polymer electrolytes. The plasticizer is then chosen according to its dielectric constant as well as for its stability electrochemical in the conditions where the polymer electrolyte is to be used. The most plasticizers useful for this purpose include plasticizers having polar liquids such as cyclic and acyclic carbonates, particularly ethylene carbonate and carbonate of propylene, dimethyl carbonate, diethyl carbonate, ethyl-methyl methyl-propyl;
γ-butyrolactone; esters of carboxylic acids such as formates, acetates, alkyl propionates of 1 to 6 carbon atoms; tetraalkylsulfamides;
the ethers dialkylated mono, di, tri and tetraethylene glycols comprising alkyl groups of 1 to 8 carbon atoms; the dialkyl ethers of the oligooxyethylenes of masses lower at 2000 g / mol, these alkyl groups possibly having from 1 to 18 atoms of carbon. These Plasticizers can be used alone or in a mixture.

-16a-The plasticizer content may be variable, generally between 0.5 and 90% by weight.
weight, preferably between 3 and 70% by weight. High concentrations of plasticizers

-17-lead to high conductivity materials. The mobility of the chains becoming This, in turn, translates into a significant loss of properties mechanical. The high crosslinking density obtained with the polymers according to the invention is an advantage to keep good mechanical properties.

The added plasticizers can also be reactive in the reaction of cationic crosslinking. The plasticizer (s) added to the polymer must in this case contain at least one reactive function in cationic polymerization. Of numerous plasticizers of this type are known and / or commercially available, in especially those lo carrying vinyl ether functions. There may be mentioned vinyl ethers glycols, in butanediol, di-, tri- and tetraethylene glycol and their monoalkyl ethers, trimethylolpropane. An additive particularly interesting because of its high constant dielectric and its ability to dissolve polar compounds, salts metal or onium, including cationic photoinitiators, is propenyl propylene carbonate ether i5 (PEPC) O
YO

O
Any other dye, anti-oxidant or anti-UV additive known to the person of and compatible with the structures of monomers and polymers in resulting may Be used for the polymers of the invention.

The crosslinking can also be carried out in the presence of reactive cycles in cationic polymerization, such as epoxides, 1,3-dioxolane, 1,3-dioxolane, dioxane, 1,3-

-18-dioxane and their derivatives, orthoformate spiranes or orthocarbonate defined previously, for example the mono- and di-formal pentaerythritol derivatives.
In the where Y is a vinyl ether, it is also possible to incorporate monomers possessing electron-poor double bonds. The most representative are the fumarates, maleates, maleic anhydride, maleimides, and in a lesser measure, acrylates and methacrylates. These compounds form with the ethers vinyl charge transfer complexes whose concerted polymerization leads to the formation of an alternating polymer forming the crosslinking subarray. This type of polymerization is spontaneously activated by heat or sources of free radicals, lo generated thermally or via actinic radiation, even in presence of a photoinitiator. Derivatives of maleimide in particular give spontaneously polymerizable complexes in the presence of UV radiation and little sensitive to oxygen. The compounds can be monofunctional, or bifunctional For example :

OO

wherein R4 is an alkylene radical having 2 to 18 carbon atoms or oxyalkylene -CH2CH2 (OCH2CH2) nOCH2CH2- wherein n ranges from 0 to 60.

The use of the compounds of the invention for the preparation of electrolytes polymers represents a particularly preferred implementation. Of such Polymeric electrolytes have many applications in the field of electrochemistry. They also have antistatic properties that do not require the contribution of

-19-absorbent conductive powders. As mentioned above, polyethers are materials of choice because of their solubilizing power and dissociating metal salts, or protonated nitrogenous bases (ammonium, imidazolium, guanidinium etc). The architecture of the polymer can be linear, star, or Of type s side chain comb. Linear polymers are more easily obtained by copolymerization of one or more solvating epoxides with a monomer of the invention having for group A an epoxide function. Solvent epoxides preferably include ethylene oxide, propylene oxide and the oxide of butylene. Ethylene oxide is particularly preferred because of its high power the complexing agent and its high reactivity in anionic polymerization, allowing a control of molecular weights.

It may be desirable, depending on the conditions of use of the electrolyte polymer, to be able to minimize the degree of crystallinity resulting from the trend of 15 polyethylene oxide segments to form organized domains of which existence is detrimental to conductivity. For this, we choose the preparation of terpolymers between ethylene oxide, the starting monomer and a terpolymer. The terpolymer comprises preferentially propylene oxide, butylene oxide, methylglycidylether, allylglycidyl ether, or a monomer bearing an ionic function such as K + K +
CF3SO2NSO2-CF2CF2-O-CH2-17- / O3S-CF2CF2-O-CH2 \ 7

20 0 or O

in a preferential proportion of 0.5 to 25 mol%. Potassium is advantageous because it does not interfere with cationic polymerization and can be exchange later by other ions, including the lithium cation.

The monomer of the polymer electrolytes according to the invention comprises preferentially the compounds RORO
CH2 R5--7-7 CH2 R5_ O-CH2 - '; ~ -7 F- ~ r- ~ O
O ~ O O_ O

OO
(R5 (RO-CH2 /

CO /> -wherein R5 represents a divalent alkyl or oxa-alkyl radical of 0 to 12 atoms of carbon; and R 'is as defined previously.

R5 is preferably -CH2-, -C2Hg1 -C4Hg, -C6H12-1 -C2H40C2H4- or -C2H40C2H40C2H40-, and R 'preferably comprises H, methyl or ethyl.
When R5 is -CH2-, R 'is preferably CH3- or C2H5-. The corresponding monomers are easily accessible from the commercial allyl glycidyl ether by isomerization of the double bond in the presence of the RuC12 complex with phosphines or iron derivatives pentacarbonyl Fe (COS).

In another embodiment of the polymer electrolytes, the anionic polymerization of styrene is used to form a chain polymer to ethylene oxide side chain. The general formula of these compounds is:

R6- (OCH2CH2) p O- Q R6- (OCH2CH2) p O- (CH2) or

-21-in which p varies between 2 and 60;

R6 is a monovalent alkyl radical having 1 to 18 carbon atoms, or aryl monovalent comprising from 5 to 18 carbon atoms;

Q is (CH2) q, -CO- or -SO2-; and g varies between 0 and 4.

A preferred example of a compound type is when Q is (CH2) q and q is 1, which is readily prepared by reaction of an alkali metal derivative of an alkoxy oligooxyethylene R6 (OCH2CH2) pOM where M is Li, Na, K, on the ortho- or para-chloromethylstyrene.

Monomers making it possible to prepare the preferred polymers of the invention are / -R7-OQ r- ~ M> - ~ \
R p ,, ~ 0 O ~ O
or where R 'and Q are as previously defined, and R7 is R5.

Particularly preferred compounds are those where Q is (-CH 2 -) q, and q is 1.

-21a-One aspect of the invention is a material in which at least one other monomer is copolymerized in addition to the α-alkyl (oligoethoxy) -O-vinylbenzyl.

Another aspect of the invention is a material for which the polymer reticle is a homopolymer of a (A), Q (Y) p monomer in which A is R

O
in which R represents H, an alkyl or oxa-alkyl radical of 1 to 12 atoms of carbon, Wherein R 'is H, an alkyl or oxa-alkyl radical of 1 to 12 carbon carbon, or a copolymer of the monomer (A) õ Q (Y) p and a monomer having a double bond activated by a carbonyl group.

It may be desirable to incorporate a styrenic terpolymer for introduce variations in Tg, adhesion, polarity etc. Drifts of

-22-vinylbenzene having various functionalities represent a good choice, and these latter are numerous and known to the person skilled in the art. Among the features of interest, note those containing polar groupings intended to change the constant local dielectric, for example NO2, RCO and RCOO; surface tensions, by for example, alkyl chains of more than 8 carbons. Halogens act on flammability. It is interesting to incorporate monomers with functions ions to induce ionic conductivity, mainly due to cations which are the most interesting for electrochemical applications. In this case, can quote the monomeric salts:

K +

In another preferred embodiment of the polymer electrolytes, the anionic polymerization of a double bond activated by a group carbonyl is used to form a lateral ethylene oxide chain polymer chain.
The formula The main monomer used to produce these polymers is:

R6 - (OCH2CH2) p- Z
R

in which R 'and R6 are as defined above.

R represents H, an alkyl or oxa-alkyl radical of 1 to 12 carbon atoms, CN or CH2000R 'wherein R' is H or an alkyl or oxa-alkyl radical of 1 to carbon atoms.

Monomers making it possible to prepare the preferred polymers according to the invention comprises:

- 23-CH3 O, O CH3 O CH3 or "CH3 in which R 'is as defined above, and R8 is R.

One aspect of the invention extends to a material in which at least one other monomer selected from an organic acrylate and a metal acrylate is copolymerized in addition to the acrylate, methacrylate or itaconate of c-alkyl (oligoéthoxy) ethyl.

As before, it is interesting to incorporate monomers possessing ionic functions. In this case, mention may be made of the salts monomers:

K +

In the polymer electrolyte preparation modes described above, the conductivity is ensured by a dissolved salt in the chain solvating the segments polyether. In general, the salts are chosen from the salts metal or salts of a protonated nitrogen base, for example ammonium, imidazolium or guanidinium - 23a-which are likely to release the cation MZ + and a chosen anion of preferably from weakly basic and non-nucleophilic anions such as ClO4, BF4, PF6-, AsF6, SbF4, RfS03, CõF2n + IS03 where n varies between 0 and 8, (R ,, SO2NSO2R '.) (RSO2C (SO2R'x) R, ") -, the anion derivatives of cyclopentadiene and its analogues aza carrying groups electroattractants, anions derived from pyrimidine-trione or 1,3-dioxane-4,5-dione wearing. electron-withdrawing groups, in particular of CN type or CF3SO2, and derivatives of malononitrile, in which RX and RX 'are groups identical or different and at least one of which has electronegative atoms such halogen, in

-24-particular such that at least one R ,, and R ,, 'is equal to CJ2n + 1 where n varies between 0 and 8, Rx "being either Rx, or RSO2- or R, SO2-. Preferred anions are C104-, BF4, PF6 , CF3SO3-, (FSO2) 2N (CF3SO2) 2N-, (C2F5SO2) 2N-, [(CF3SO2) 2CH] -, [(CF3SO2) C (CN) 21-, [(CF 3 SO 2) 3 C] -, [(CF 3 SO 2) NSO 2 N (R 9) 2] - where R 9 represents alkyl of 1 to 30 atoms of carbon, anions derived from 4,5-dicyano-1,2,3-triazole, 3,5-bis-1,2,4 triazole or tricyanomethane. The salt concentration is more conveniently expressed in terms of the ratio of the oxygen number of the oxyethylene segments per cation (O / M).
In general, this number is between 0.5 and 1000.

The invention relates to an ionically conductive material as defined previously, characterized in that the salt is selected from the salts of anions C104, BF4 "
, PF6-, AsF6, SbF4, CF3SO3-, [(CF3SO2) 2CH] -, [(CF3SO2) 2CH] -, [(CF3SO2) C (CN) 2] -, (RS02NSO2R'x) -, (RS02C (SO2R'x) Rx ") -, anions derived from cyclopentadiene and of its aza analogues carrying electron-withdrawing groups, derived anions of pyrimidine-trione or 1,3-dioxane-4,5-dione bearing groups electro-attractors, derivatives of malononitrile, [(CF3SO2) NS02N (R9) 2] "where R9 represents alkyl from 1 to 30 carbon atoms, anions derived from 4,5-dicyano-1,2,3-triazole, 3,5-bistrifluoromethyl-1,2,4-triazole and tricyanomethane, Rx and RX being groups same or different selected from halogen and C ,, F2õ + 1 where n varies between 0 and 8 and in which Rx "represents R, RxSO2- or R, t SO2 A large number of cations or cation mixtures give solutions in the polymers of the invention. The cations of lithium, sodium, potassium, calcium, tin, ammonium and imidazolium are preferred. Lithium ion and ion mixtures -24a-lithium and potassium are particularly preferred for applications Electrochemical.

An aspect of the invention is a material having a lithium salt or a mixture of lithium salt and a salt of another cation.

The anionic part or the cationic part of the salt can be part of a macromolecular chain, including the polymer of the invention, by the incorporation of aforementioned termonomers or other ionic type. Polymers in which a part at least negative charges are fixed on the polymer are particularly useful in as solid electrolytes for battery applications and accumulators, supercapacitors or electrochromic systems.

Another aspect of the invention extends to a material for which at least one fraction of X- anions is either carried by the polymer chain, or part of a different polymer chain.

One aspect of the invention extends to a material in which the polymerization cationic form of acetal bonds between groups Y and ends of chains from anionic polymerization.

A further aspect of the invention is a material in which the mass polymers before crosslinking is between 2 x 103 and 60 x 103 glmol.

-24b-As mentioned previously, the polymers according to the invention can be crosslinked to high levels of crosslinking due to the responsiveness of cationic functions of the monomers employed. In the case of electrolytes polymers,

-25-high levels of crosslinking intended to induce good properties mechanical are useful if the glass transition temperatures are not increased by one way notable. As has been exposed, the flexibility of the links connecting the chain anionic to cationic subnetwork as well as the intrinsic flexibility of this subnetwork are assets determinants for polymer electrolytes.

The shaping of polymer electrolytes into thin films is done so conventional spreading from solutions or extrusion. For some reasons and minimizing the impact on the environment, it is desirable to to use the smaller possible amounts of solvents. From this point of view, weak polymers masses are interesting because their formatting can be done from solutions concentrated or pure. In the case of epoxies, the ends of chains are in general hydroxyl functions. Their higher concentration in the case of polymers of small masses is detrimental to the extent that these functions are reactive, in particular with respect to lithium. An advantage of crosslinking cationic is its ability to neutralize hydroxyl functions to form bonds stable acetals potentials close to those of lithium participating in the crosslinking. This possibility is exemplified below in the case where the cationic functions are ethers vinylic:

R 'R' The polymers of the present invention can be used in combination with at least one salt M "+ X" -, M "+ being an inorganic, organic or

-26-any organometallic charge n and X- being a monovalent anion, two or several X- anions which can be linked together by covalent chains or up belong to the chain of a polymer. Such a combination is useful in a system of storage of electrical energy of primary or secondary generator type or Great-capacity comprising at least one negative electrode and at least one electrode positive, the latter comprising at least part of the ionic compound. The electrode positive may further comprise another electrode material such as oxides of vanadium LiyVOX in which (2x-5 <_ ys 2x-3; 2.15 sxs 2.5), LiyNi _ ,, _ ZCo ,, AI, 02 where 0 _ <x + y <1 and 0 <_ y <_ 1, the manganese spinels LiyMn2-xM, 04 where M is Li, Cr, Al, V, Or, 0 5 x: 5 0.5 and 0 5 y 5 2, organic polydisulphides, polyquinones such as rhodizonates, FeS, FeS2, iron sulphate, phosphates and phosphosilicates iron and olivine structure lithium or Nasicon, or the substitute products of the iron by the manganese, used alone or as a mixture.

One aspect of the invention extends to an electrochemical cell comprising a electrolyte, the electrolyte is constituted at least in part by a material as defined previously.

Another aspect of the invention is a system for storing energy electrical circuit comprising at least one negative electrode and at least one electrode positive, the positive electrode having at least partly a defined material previously.
In a preferred aspect, the electrical energy storage system is characterized in that that the storage system of the electrical energy is a primary generator, secondary or supercapacity.

-26a-The present invention aims at a system for which the negative electrode is chosen from a metallic lithium or one of its alloys optionally in the form of nanometric dispersion in a lithium oxide, double nitrides of lithium and a transition metal, oxides with low potential of general formula Lit + yTi2_, 14O4, where x> 0 and Y: 5 1, M002, W02, carbon, carbon products from the pyrolysis of Contents organic ceramic fibers and lithium-aluminum alloys or lithium-silicon.
One aspect of the invention is a light modulation system comprising two supports, at least one of which is transparent, covered with driver to tin oxide or doped indium oxide base, a layer of an electrolyte and a against electrode, characterized in that the electrolyte is a defined material previously.

The invention also aims at a previously defined system comprising in more of the material, at least one dye that may change color according to his degree of oxidation.

- 26b-The following examples are provided to illustrate embodiments of the invention, and should at no time be considered as in limiting the scope.

Example 1 In a 500 mL reactor, 110 g of a commercial trifunctional polymer prepared by anionic polymerization of ethylene oxide from 1,1,1-tris (hydroxymethyl) propane are dissolved in 250 mL of THF. 33.6 g of tert-butoxide of potassium are added, followed by 86 g of 4-vinyloxy-1-glycidoxy-butane:

O

-27-The mixture is heated for 3 hours at 50 ° C. At the end of the reaction, the termination of chains is obtained by methyl groups from the addition of 37 g of sulphate of methyl. The block polymer has the formula:

CH2 (OCH2CH2) n '[OCH2CH (CH2OC4H5OCH = CH2)] p'OCH3 C2H5H2 (OCH2CH2) n [OCH2CH (CH2OC4H8OCH = CH2)] POCH3 CH2- (OCH2CH2) n "[OCH2CH (CH2OC4H8OCH = CH2)] p" OCH3 in which n + n '+ n "is of the order of 20, and p + p '+ p "is of the order of 5.

The polymer solution is centrifuged and the THF is removed. Purification lo is carried out by dissolving in 200 mL of dichloromethane and extraction with water (400 mL). The polymer is then precipitated in 2 L of ethyl ether maintained at -C.

A polymer electrolyte is obtained by dissolving the polymer thus obtained in a mixture of acetone (55% by weight) in the presence of lithium, of to obtain a ratio of oxygen oxyethylene groups per ion lithium from 16: 1. To this solution are added 1% by weight relative to the polymer contained in the solution (C4H9OC6H4IC6H5) + [FSO2) 2N] -. The polymer is spread from the solution in the form of 35 m thick film on a high polyethylene support density and cross-linked by UV irradiation at 365 nm for 20 seconds, corresponding to a energy of 20 mJoules / cm 2. The polymer obtained is a resilient elastomer whose conductivity is from 10-5 Scm 'to 25 C.

Example 2

-28-The formai of commercial glycerol is separated into its two isomers (4-hydroxymethyl-1,3-dioxolane and 5-hydroxy-1,3-dioxane according to the method of Hibbert and al. [J. Am. Chem. Soc. 50, 3120 (1928)]. To 10.4 g of 4-hydroxymethyl-1,3-dioxolane (isomer 1) are added with vigorous stirring 5.8 g of KOH previously crushed in a mix, 200 mg of tetrabutylammonium chloride acting as a catalyst for phase transfer. 9.2 g of epichlorohydrin are then added gradually to keep the temperature below 30 C
by a external cooling. The formed KCi is separated by filtration and the (4-glycidoxyméthyl) -1,3-dioxolane obtained is purified by two distillations.

O

OO

This monomer is copolymerized with ethylene oxide under the conditions of Example 12 using potassium tert-butoxide as an initiator anionic. The molar ratio of the monomers is selected from 95 (EO) to 5 (monomer bifunctional). The polymer is precipitated with hexane. The molecular mass measured by chromatography Steric exclusion is 45 x 103 g. A polymer electrolyte is prepared by dissolution Li (CF 3 SO 2) 2N salt in a concentration such that O / Li = 24: 1 in a solvent common, acetonitrile, to which 1% of the dimethylphenacylsulfonium salt is added [C6H5 (= O) CH 2 S (CH 3) 2] + (CF3SO2) 2N-. The solution is spread using a template for after evaporation of the solvent, form a film 24 m thick. The crosslinking is performed by irradiation with a Hanovia UV lamp for a dose of 40 mJ / cm2.
The polymer obtained is as before a conductive elastomer (10.5 Scm ' at C and 1.3 x 10-3 Scm 'at 80 ° C).

-29-Example 3 Diethylene glycol monovinyl ether (BASF) is esterified with methacryloyl to form A random polymer is obtained by anionic polymerization of this monomer with some co-methoxy (oligooxyethylene) methacrylate, the mass of which oxyethylene is The ratio of the two monomers is 85:15 (oligo-EO / dioxolane).
The initiator Anionic used is phosphazene base P4-t-bu in anhydrous THF. The The polymerization is carried out at 25 ° C. in 24 hours. The polymer is precipitated by the ether lo diethyl, and purified by two dissolution / precipitation in the couple of solvents THF / ether. The polymer is formed into a thin film by spreading from a solution in acetonitrile containing lithium trifluoromethanesulfonate in concentration such as the ratio of the concentrations of the oxygen atoms of ether type provided by the lithium salt is 20: 1. A cationic thermal initiator, toluene 2-nitrobenzyl sulphonate is added at a rate of 0.8% by weight. We add also from the colloidal silica at 12% by weight of the polymer. The viscosity of mixture is adjusted so as to evaporate a film 45 m thick. The movie as well obtained is cross-linked by heating for 1 hour at 80 ° C. The polymer electrolyte got is a resilient elastomer whose conductivity is 2 x 10.5 Scm 'at 25 C.

Example 4 11.6 g of 1,4-butanediol monovinyl ether (BASF) are treated in 100 mL of THF per 2.6 g of sodium hydride. The solution obtained is reacted to the reflux under

-30-nitrogen with 15.2 g of commercial chloromethyl-4-styrene (Aldrich). The 4-vinyloxybutoxyméthyl-4-styrene I- O- (CH 2) 4 O-CH 2 O

is obtained after filtration and evaporation of THF. The monomer is purified by s distillation. A polymer of styrene and 4-vinyloxybutoxymethyl-4-styrene (91: 9 molar) is prepared by priming with sec-butyllithium (5 x 10-3 molar / total of monomers) in toluene at -30 C. After 8 hours, the polymer is precipitated in the methanol.

The cationic photoinitiator bis (trifluoromethanesulfonylimide of 4-octyloxyoxyphenyl (diphenyl) sulfonium is prepared by exchange in water between the corresponding commercial sulfonium hexafluorophosphate, and the salt of potassium of Imide K (CF3SO2) 2N. A film is prepared by evaporation of a solution of substituted polystyrene copolymer and 0.5% by weight of the initiator toluene to obtain a 10 mm thick film on an aluminum substrate.
The polymer is subjected to UV radiation at 254 nm at 40 mJ / cm 2) for 5 minutes.
seconds.
The crosslinked polymer is insoluble in all the usual solvents and presents a very good dielectric strength.

2o Example 5 5 g of styrene polymer of Example 4 and 400 mg of maleic anhydride are dissolved in 15 mL of THF and spread as a film on a substratum of aluminum of 8 .mu.m thick. The polymer is subjected to UV radiation at at a dose of 60 mJ / cm 2. The crosslinked film obtained is insoluble in all solvents and its adhesion to the aluminum substrate makes it possible to deform it (mandrel test

-31-4 mm, "ASTM standard D 3359 crosshatch adhesion test: 5) without delamination appreciable polymer.

Example 6 10.4 g of 5-hydroxy-2,3-dioxane (isomer 2 of Example 2) are reacted with 9.65 ml of methacryloyl chloride in the presence of 8 g of pyridine at 0 ° C. in 50 mL of THF to obtain 5-methacryloxy-1,3-dioxane which is purified by distillation.

H3C O - ~ / -C 0 / \
H2C O /) O

A copolymer of methyl methacrylate, butyl and 5-methacryloxy-2,3-dioxane is prepared by anionic initiation with thiophenoxide tetrabutylammonium (FLUKA) in THF. The molar ratios are 65:25:10.
The polymer is precipitated in ethanol and purified by two dissolutions /
precipitation in the THF couple: ethanol. A film of this polymer, added with 0.8% by weight of 2,4-dinitro-benzyl toluenesulfonate, obtained by spreading a solution in THF

on a polytetrafluoroethylene support, is crosslinked by heating 4 minutes at 80 C.
This polymer is transparent and insoluble in all the usual solvents. A 300 C, the The polymer reconverts into its monomers and can be recycled.

Example 7 2-hydroxyethyloxazoline is prepared by azeotropic dehydration of salt formed between 3-hydroxypropionic acid and aminoethanol. 4- (2-methacryloxypropyl ethyl) -1,3-oxazoline is prepared by the action of methacryloyl chloride on the derivative hydroxylated in the presence of triethylamine at 0 C. The monomer has the formula

-32-OND
A copolymer of butyl methacrylate and 4- (2-methacryloxy-ethyl) -1,3-oxazoline (90:10 molar) is prepared by anionic polymerization by the "base phosphazene P4 "
(Fluka) in anhydrous THF over 12 hours. The polymer is precipitated in ethanol.

A solution containing 10% by weight of this polymer in dichloromethane to which added 0.5% by weight of busulfan (1,4-butanediol dimethanesulfonate) is spread on a polytetrafluoroethylene surface and the solvent is evaporated. The polymer is heated to 70 C for 10 minutes under dry air atmosphere. Crosslinking by opening cationic oxazoline ring gives, after detachment of the support, a flexible film transparent insoluble in the usual solvents.

Example 8 13.4 g of commercial 1,2,6-hexanetriol are added with 12.4 ml of diethoxymethane and the mixture is refluxed in the presence of 500 mg of toluene acid sulfonic acid acting as a catalyst for transacetalization. Ethanol is eliminated at 80 C

and the 4- (4-hydroxybutyl) -1,2-dioxolane obtained is purified by distillation.
7.3 g of this product and 4.6 g of epichlorohydrin are reacted in the presence of 2.8 g of hydroxide powdered potassium in the presence of tetrabutylammonium chloride, so at forming the monomer 4 - [(4-glycidyloxy) -butyl] -1,3-dioxolane CH2CH2CH2CH2-O-CH2 --- N ~ -7 O

A copolymer of ethylene oxide and this monomer in the molar ratio 93: 7 is prepared by anionic initiation with potassium tert-butoxide in THF.
The polymer is purified by centrifugation and precipitation in ether. A
electrolyte

-33-The polymer is formed by adding lithium salt Li [CF 3 SO 2 C (CN) 2] in the report O / Li = 18: 1. The polymer is crosslinked by addition of 0.8% by weight of the initiator bisfluorosulfonyl cumene-Fire-cyclopentadienylimide [CH3CH (CH3) C6HSFe (CSHS] + [(FSO2) 2N] - and UV irradiation at a dose of 40 mJ / cm 2.
The s polymer is an elastomer insoluble in all solvents and its conductivity is greater than 10 'Scm' at 55 C.

Example 9 13.2 g of commercial 3-allyloxy-1,2-propanediol, 12 mL of trimethyl-orthoformate and 11.1 ml of γ-caprolactone are heated to 90 ° C. in the presence of 500 mg of toluenesulphonic acid. The methanol formed and the excess orthoformate methyl are distilled off and the spiro-ester formed is purified by distillation. The grouping allyl is epoxidized by the magnesium salt of the monoperoxy acid peroxyphthalic in acetonitrile. The monomer O

obtained is purified by distillation and copolymerized with ethylene oxide in the conditions of Example 12 in a 93: 7 molar ratio. The polymer obtained is transformed into an ionic conductor by adding Li [(CH 3) 2 N SO 2 N SO 2 CF 3] salt in the ratio O / Li = 14: 1. The addition of bis- (trifluoromethanesulfonate 4-fluoropyridinium to 2o reason of 1% by weight allows the crosslinking of the polymer at 80 C with increase of volume.

Example 10

-34-15 g of co-methoxy (polyethylene glycol) of commercial mass 900 are treated in 100 ml of anhydrous THF with 600 mg of sodium hydride. After cessation of release of hydrogen, the excess of sodium hydride is removed by centrifugation and at the solution is added 2.5 g of 4-chloromethyl-styrene. The by-product of the reaction (NaCl) is removed by centrifugation and the macromonomer is separated by precipitation in an ether-hexane (50:50) mixture maintained at -20 ° C. A copolymer of this monomer and vinyl styrene ether of Example 4 is prepared by polymerization anionic in an 85:15 molar ratio by priming by sec-butyllithium added of tetramethylethylenediamine so as to obtain a polymer of mass 2.5 x 103. This the polymer is converted into a polymer electrolyte by dissolution of Li (CF3SO2) 2N in the Oe ratio, 1e / Li of 25: 1. The polymer is crosslinked by the addition of dimethylphenacylsulphonium fluorosulfonylimide [C6H5C (= O) CH2S (CH3) 2] + (CF3SO2) 2N- (1% by weight) and irradiation at 265 nm at the dose of 40 mJ / cm 2.

Example 11 An electrochromic device on a flexible support is produced by deposit cathode sputtering of a 700 nm layer of tungsten oxide W03 on a 60 m thick polyethylene terephthalate (PET) backing beforehand of doped tin oxide (SnO2: F) (100 nm). The counter-electrode is a film of mixed of Lio.5TiO2CeO2 oxides (800 nm) on the same support. Both electrodes are laminated on either side of a film of the polymer electrolyte of Example 1 (30 m). The system thus assembled, the edges of which are sealed after adding the feeds of currents (0.5 cm and 20 m thick copper strips) can be used vary the light transmission of the solar spectrum from 85 to 8% by application of a potential of

-35-2V for 300 seconds at 25 C. Reverse polarity brings transmission back at his initial value. The system can be cycled over 104 cycles without loss of properties optics.

Example 12 This example illustrates the preparation of a crosslinkable polyepoxide according to the invention. The anionic polymerization was carried out in a reactor commercial in Parr stainless steel with a capacity of 2 liters and equipped with an agitator and of a valve foot to empty it from below. All transfer operations have been made under an inert atmosphere using argon or very dry nitrogen and without oxygen. We can also use reactors of other capacities or whose interior is covered with glass.

The reactor used was dried in the following manner. We introduced empty 250 ml of dry toluene, and the reactor is then heated to 150 ° C. for 15 minutes.
minutes. The Toluene is then emptied hot through the foot valve. We then pump under vacuum for about 10 minutes.

The monomer with dual functionality O
was prepared by reaction of butanediol monovinyl ether (BASF) on epichlorohydrin presence of powdered KOH and a phase transfer agent, either hydrogen sulphate tetrabutyl ammonium. Ethylene oxide was distilled, solvents and other monomers were dried on molecular sieves before being introduced into the reactor,

-36-in order to lower their water content to less than 100 ppm, a value verified by the method from Karl-Fischer.

In the empty reactor, free of traces of water and impurities, at the ambient temperature of 20 C a mixture of 30.03 g of (4-vinyloxybutyl) -glycidyl ether, 50.05 g of butylene oxide and 120.2 g of ethylene oxide. We have then introduced 20 × 10.3 moles of potassium tert-butoxide in 20 ml of THF. The temperature was maintained at 25 C for 23 hours to give 190 g of a mixed liquid at room temperature to which 0.2 g of Santonox R is added as antioxidant and stabilizer. According to the proportions initiator / monomer, the mass molecular weight is less than 10,000.

Example 13 For this example, the polymerization was carried out in the reactor according to the procedure of Example 12, and the monomers were dried in a manner similar to this example.

In the reactor containing 151 g of toluene, a mixture of 11.39 is introduced.
4- (vinyloxybutyl) glycidyl ether and 88.6 g of ethylene oxide. The temperature of 2o reactor was brought to 100 C and then introduced 2 x 10-3 mole of tert-butoxide potassium in 2 mL of THF. The reactor temperature is maintained at 100 C
for 4.5 hours. A pressure drop of 6.8 x 105 Pa is observed at 1.2 x 105 Pa. On then lower the temperature to 50 C and add 0.1 g of Santonox R
dissolved in 8 ml of toluene. The solution of the reactor is recovered through the foot valve.
After Evaporation of the solvent gives 89 g of copolymer whose mass molecular

-37-average Mõ is 39,000. The average molecular mass M, was evaluated by comparing the viscosity of a solution of the polymer with the viscosity of solutions of poly (ethylene oxide) of known mass.

s Example 14 For this example, the polymerization was carried out in a reactor according to the procedure of Example 12, and the monomers were dried in a manner similar to this example.

In the reactor containing 151 g of toluene, a mixture of 11.42 is introduced.
g of (4-vinyloxybutyl) glycidyl ether, 3.2 g of butylene oxide and 79.8 g oxide ethylene. The temperature of the reactor is brought to 100 ° C. and 112 is introduced.
mg (10-3 mole) of potassium tert-butoxide in 1 ml of THF. After 1.5 hours, we add 5 x 10 moles of potassium tert-butoxide in 0.5 ml of THF. The temperature is kept at 100 C for an additional 17 hours. There is a drop in pressure of 5.9 x 105 Pa at 1.5 x 105 Pa. Then the temperature is lowered to 70 C and we add 0.1 g of Santonox R dissolved in 8 mL of toluene. We recover the solution of reactor through the foot valve. After evaporation of the solvent, we obtain 70 g of copolymer whose average molecular weight M is 46,000, such that measured by the comparative method of Example 13.

Example 15 For this example, all the manipulations are done in a box gloves under inert and anhydrous atmosphere (<1 vpm H2O, 02). A solution is obtained by dissolving the polymer of Example 13 in 100 ml of the solvent mixture

-38-acetonitrile: toluene (4: 1) at a concentration of 0.5 g / cc. After dissolution full of polymer, a solution B is obtained by the dissolution in solution A of bis (trifluoroacetic rométhanesulfonimidure) of lithium, LiN (SO2CF3) 2, so as to obtain a report Oxygen polymer oxygen, O / Li, 30: 1. A solution C is obtained by the dissolution in solution B of 1% by weight relative to the polymer of bis (penta-diphenyliodonium fluoroethanesulfonylimide, [N (SO2C2F5) 2] - [C6H5) 2I] +, which is a cationic polymerization initiator activated during radiation exposure ultra-purples. The polymer matrix is shaped as a thin film about 30 gm on a peelable polypropylene carrier of 28 gm, by a conventional method Solvent coating of solution C, followed by drying. The matrix obtained polymer is subsequently cross-linked by UV irradiation centered on the length wave 365 nm for 10 seconds at a power of 3300 W / cm2. The polymer electrolyte obtained has good mechanical properties and is insoluble in the mix of acetonitrile solvent: toluene (4: 1). The polymer matrix is thereafter dried under vacuum at 1.5 85 C for two hours. A measurement by DSC performed on the matrix supercooled gives a glass transition temperature at half height of -65 C. This measured, as well as that performed for the following examples indicates that the temperature of Glass transition is not affected by crosslinking. As comparison, the PEO homopolymer has a glass transition temperature of -66 C.

Example 16 Under the handling conditions of Example 15, a solution A is obtained by dissolving the polymer of Example 13 in 100 ml of the mixture of solvent acetonitrile: toluene (4: 1) at a concentration of 0.5 g / cc. After dissolution full of polymer, a solution B is obtained by the dissolution in solution A of 1% by weight

-39-relative to the polymer of [N (SO2C2F5) 2] - [C6H5) 2I] +. The polymer matrix is implementation form in the form of a thin film of about 30 m on a peelable support of 28 m polypropylene, by a conventional solvent coating method of the solution B. The polymer matrix obtained is crosslinked by UV irradiation centered on the wavelength 365 nm for 10 seconds at a power of 3300 W / cm2.
The matrix that is obtained has good mechanical properties and is insoluble in the solvents of the initial polymer. The polymer matrix is subsequently dried vacuum to 85 C for two hours. A measurement by DSC performed on the matrix supercooled gives a glass transition temperature at half height of -68 C.

Example 17 Under the handling conditions of Example 15, a solution A is obtained by dissolving the polymer of Example 14 in 100 ml of the mixture of solvent acetonitrile: toluene (4: 1) at a concentration of 0.5 g / cc. After dissolution full of polymer, a solution B is obtained by the dissolution in solution A of lithium bis (trifluoromethanesulfonimide), LiN (SO2CF3) 2, so that obtain a O / Li ratio of 30: 1. A solution C is obtained by the dissolution in the solution B of 1% by weight relative to the polymer of [N (SOZC2F5) 2] - [C6H5) 21] +. The matrix polymer is spread in the form of a 30 gm film on the polypropylene support. The matrix obtained polymer is crosslinked under the conditions mentioned above.
The matrix obtained has good mechanical properties and is insoluble in the solvent mixture acetonitrile: toluene (4: 1). The polymer matrix is by the dried under vacuum at 85 C for two hours. A measurement by DSC indicates a temperature of glass transition of -64 C.

-40-Example 18 Under the handling conditions of Example 15, a solution A is obtained by dissolving the polymer of Example 14 in 100 ml of the mixture acetonitrile: toluene (4: 1) at a concentration of 0.5 g / mL. After dissolution full of polymer, a solution B is obtained by the dissolution in solution A of 1% by weight relative to the polymer of [N (SO2C2F5) 2] - [C6H5) 2I] +. The polymer matrix is spread in the form of a thin film 30 m on a peelable polypropylene support such as described previously. After crosslinking and drying under the conditions of the example 14, the polymer matrix obtained at a glass transition temperature measured by DSC, from -io 66 C.

Example 19 Under the handling conditions of Example 15, a solution is obtained by dissolution in the polymer of Example 12 of bis (trifluoromethanesulfonimidide) of lithium, LiN (SO2CF3) 2, so as to obtain an O / Li ratio of 30: 1. At this solution is added 1% by weight relative to the polymer of [N (SO2C2F5) 2] - [C6H5) 2I] +. The matrix polymer spread in the form of a thin film according to the procedure of the example 15. The polymer is crosslinked by 10 seconds of UV irradiation at 365 nm at a power of 3300 GW / cm2. The matrix obtained has good mechanical properties and is insoluble in the solvents of the polymer before crosslinking. A measurement by DSC
indicated a glass transition temperature of -65 C.

Example 20 This example is intended to illustrate the utility of the polymers of the invention for to prepare plasticized electrolytes. All manipulations are performed in a glove box

-41-under an inert and anhydrous atmosphere (<1 vpm H2O, 02). The polymer of the example 1 is dissolved in a mixture of γ-butyrolactone with ethylene carbonate (50:50 v: v) containing lithium hexafluorophosphate at a concentration of 1 mol per liter. AT
this mixture is added 1% by weight relative to the polymer of [N (SO2C2F5) 2] "[C6H5) 2I] +

The mixture is spread in the form of a thin film of about 30 gm on a support Polypropylene peelable 28 gm and is not dried. The polymer matrix laminated obtained is crosslinked by 10 seconds of irradiation under the conditions of example 15, to give an elastomer having good mechanical properties despite its content high in liquid plasticizers that are not exuded. Conductivity is better than 10-3 Scm 'at 25 C.

Example 21 Under the handling conditions of Example 15, a solution A is obtained by dissolving the polymer of Example 13 in 100 ml of the mixture is acetonitrile: toluene (4: 1) at a concentration of 0.5 g / cc. After complete dissolution of polymer, a solution B is obtained by the dissolution in the solution A of salt LiN (SO2CF3) 2 so as to obtain an O / Li ratio of 30: 1. A solution C is obtained by dissolution of polyoxyethylene 200,000 molar mass in 100 ml of the mixture acetonitrile: toluene (4: 1) at a concentration of 0.5 g / cc. After dissolution full of polyoxyethylene, a solution D is obtained by the dissolution in the solution C of LiN (SO2CF3) 2 so as to obtain an O / Li ratio of 30: 1. An E solution is obtained by mixing a portion of each of the solutions B and D. The proportion of solution B and D is adjusted so as to obtain in solution E a volume proportion of polymer 80% solution B and 20% solution D polymer. A solution F
is obtained by the dissolution in solution E of 1% by weight with respect to polymers of

-42-[N (SO2C2F5) 2] - [C6H5) 2I] +. Solution F is spread according to the described technique previously. The polymer obtained is crosslinked according to the procedure of the example 15. The matrix obtained has good mechanical properties, and its temperature of transition glassy is -62 C.

Example 22 This example illustrates the addition of a co-polymerizable reactive plasticizer. In the handling conditions of Example 15, a solution A is obtained by dissolution of polymer of Example 13 in 100 ml of the mixture acetonitrile: toluene (4: 1) to a concentration of 0.5 g / cc. After complete dissolution of the polymer, a solution B is dissolved in solution A of LiN (SO2CF3) 2 so as to obtain a report O / Li of 30: 1. A solution C is obtained by dissolution in triethylene divinyl ether (DVE-3, ISP) of LiN (SO2CF3) 2 so as to obtain an O / Li ratio from 30: 1.
A solution D is obtained by mixing a portion of each of the solutions B and C.

The proportion of solution B and C is adjusted to obtain in solution D
a volume proportion of the 80% solution B polymer and the polymer of the solution C of 20%. A solution E is obtained by the dissolution in solution D of 1.2% in weight relative to polymers of [N (SO2C2F5) 2] - [C6H5) 2I] +. Solution E is spread in the form of a thin film according to the procedure mentioned above. The matrix obtained polymer is crosslinked following 10 seconds of UV irradiation at 365 nm at a power of 3300 W / cm2. The film has good mechanical properties and is insoluble in the solvents of the polymer. A similar polymer is obtained by replacement of DVE-3 of solution C with trimethylolpropane trivinyléther. The Blending solutions B and C is done in proportions 70: 30%.

-43-Example 23 Under the handling conditions of Example 15, a electrochemical generator using a negative electrode of lithium metal of 30 gm laminated thickness on an 8 m nickel current collector. The separator is consisting of the polymer matrix of Example 19. The positive electrode contains a mixture of vanadium oxide powder, carbon black (Shawinigan black) and a polyether-based terpolymer containing bis (trifluoromethanesulfonimide) in a molar ratio O / Li of 30: 1, said positive electrode having a capacity of 6 Coulomb / cm2. The composite material is spread from the solution onto a lo 8 m thick aluminum current collector to give a film 45 m thick. The electrochemical generator is assembled by hot pressing to under vacuum. After 12 cycles at 80 C, the generator has a very good behavior in cycling in terms of coulombic efficiency and a capacity that remains constant.

is Example 24 Under the handling conditions of Example 15, a solution A is obtained by dissolution in the polymer of Example 1, hexafluorophosphate of lithium to obtain an O / Li ratio of 30: 1. A solution B is obtained by adding of 1% by weight relative to the polymer of [N (SO2C2F5) 2] - [C6H5) 2I] + in the solution A.

The polymer matrix is shaped in the form of a thin film of about 30 m on a peelable 28 m polypropylene support, by coating solution B.
The matrix obtained polymer is then crosslinked by 10 seconds of UV irradiation at 365 nm to a power of 3300 gW / cm2.

-44-An electrochemical generator is made using a negative electrode which contains graphite in a mass fraction of 90% and a polymer of fluoride of vinylidene-co-hexafluoro propene, in a mass fraction of 10%. The called Negative electrode has a capacity of 3.56 C / cm2. The electrode is obtained by solvent-phase coating (acetone) on a copper current collector 16 m thick to give a film 56 m thick. The separator includes a polymer membrane as described in the preceding paragraph (membrane polymer of a thickness of 15 m containing lithium hexafluorophosphate in a report molar O / Li 30: 1). The positive electrode contains a mixture of cobaltite lithium, LiCoO2, in a mass fraction of 91.6%, carbon black in a fraction mass of 2.7% and a vinylidene fluoride polymer co-hexafluoro propene, in a mass fraction of 5.7%. Said positive electrode has a capacity 4.08 C / cm2. The electrode is obtained by coating in solvent phase (acetone) on a manifold aluminum current 8 m thick to give a 49 m film i5 thick. At the time of assembly of the electrochemical generator, the separator is immersed for 30 minutes in the ethyl-methyl carbonate / carbonate solvent mixture of ethylene (equivolumic 1: 1) containing lithium hexafluorophosphate a concentration of 1 molar, then the cathode and the anode are immersed 10 minutes in the LiPF6 solution in the solvent mixture ethyl-methyl carbonate / carbonate ethylene (Equivolumic 1: 1) containing lithium hexafluorophosphate at a concentration of 1 molar, then the cathode and the anode are immersed 10 minutes in the same solution.
After immersion, the solvent occupies 41% of the volume of the separator, 51% of the volume of the cathode and 45% of the volume of the anode. The electrochemical generator is over there following quickly assembled by light pressing at 25 C of the negative electrode, of the separator 25 and the positive electrode, and put in a waterproof bag. After 12 cycles at 25 C, the

-45-generator has a very good behavior in cycling on the plane of effectiveness coulombic and a capacity that remains constant.

Example 25 Under the handling conditions of Example 15, a solution A is obtained by dissolving the polymer of Example 12 in a mixture of butyrolactone with ethylene carbonate (50:50 v / v) containing hexafluorophosphate lithium to a concentration of 1 molar so as to obtain a volume ratio of 50%
polymer and 50% solvent mixture. A solution B is obtained by adding to A of 1% in weight per ratio to the polymer of [N (SO2C2F5) 2] - [C6H5) 2I] +

An electrochemical generator is made using a negative electrode which contains graphite in a mass fraction of 58%, a polymer of fluoride vinylidene co-hexafluoro propene in a mass fraction of 5.8%, the polymer of Example 12 in a mass fraction of 3.2% and a mixture of butyrolactone, ethylene carbonate (50:50 v / v) and containing the LiPF6 salt (1 molar), at a fraction mass of 33%. 1% by weight is also added relative to the polymer of example 12 pyridinium bis-fluorosulfonimide [N (SO 2 F) 2] - [C 5 H 5) NH] +, an initiator of cationic polymerization which is activated thermally. The electrode is obtained by 2o solvent-phase coating (2-butanone) on a copper collector of 16 m thick followed by a three-hour anneal at 80 ° C. in order to cross-link in the electrode the polymer of example 12. Said negative electrode has a capacity of 3.6 C / cm 2.
The positive electrode contains a mixture of iron phosphate double and lithium (LiFePO4) in a mass fraction of 58%, a fluoride polymer of vinylidene co-hexafluoro propene in a mass fraction of 5.8%, the polymer of example 12

-46-in a mass fraction of 3.2% and a mixture of y-butyrolactone / carbonate ethylene (50:50) containing 1 molar lithium hexafluorophosphate, in a mass fraction of 33%. 1% by weight relative to the polymer is also added of Example 12 of [N (SO 2 F) 2] - [C 5 H 5) NH] +. The electrode is obtained by coating phase solvent (butanone) on an 8 m aluminum current collector thick followed annealing for three hours at 80 ° C. in order to crosslink the electrode polymer of Example 12. The said positive electrode has a capacity of 3.99 C / cm 2.
The solution B is spread by coating directly onto the negative electrode in the form of of a film thin 15 gm and cross-linked by 10 seconds of UV irradiation at 365 Mn at a power lo of 3300 W / cm2. The electrochemical generator is then rapidly assembled by light pressing at 25 C of the half-battery consisting of the negative electrode and the separator and of the positive electrode and put in a waterproof bag. After 8 cycles at 25 C, the generator has a very good behavior in cycling in terms of effectiveness coulombic and a capacity that remains constant.

Example 26 For this example, the polymerization was carried out in a reactor according to the procedure of Example 12, and the monomers were dried in a manner similar to this example.

1-Propenyl glycidyl ether was prepared by isomerization of the allyl glycidyl commercial ether using the catalyst RuC12 [P (C6H5) 2] 3 at a rate of 0.5%
molar to 120 C. In the empty reactor, free from water and impurities, and containing 500 g of toluene, a mixture of 5.67 g of propenyl glycidyl ether, 16.1 g of butylene oxide and 177.6 g of ethylene oxide. The temperature

-47-of the reactor is brought to 99 ° C. and 2 × 10 -3 mol of tert-amylate of potassium in 2 ml of toluene. The temperature is maintained at 99 ° C. for 24 hours.

A pressure drop of 12.3 x 105 Pa is observed at 3.4 x 105 Pa.
then the temperature at 45 C and 0.2 g of Santonox R dissolved in 8 ml of toluene. The solution of the reactor is then recovered through the foot valve.
After Evaporation of the solvent gives 180 g of copolymer whose mass molecular average M, is 44,000 measured by the comparative method of Example 13.

Example 27 For this example, the polymerization was carried out in a reactor according to the procedure of Example 12, and the monomers were dried in a manner similar to this example.

In the reactor without traces of water and impurities and at the temperature 20 C, a mixture of 20.05 g of 1-propenyl glycidyl Ether, 60.10 g of butylene oxide and 119.9 g of ethylene oxide. We introduce 20 x 10-3 mole of tert-potassium butanolate in 20 mL of THF and bring the temperature of the reactor to C. The reactor temperature is maintained at about 25 C for 26 hours.
We 20 observed a pressure drop of 6.3 x 105 Pa at 3.6 x 105 Pa.
then 0.2 g of Santonox R dissolved in 8 ml of toluene. 180 g of liquid mixture are obtained viscous reactor through the foot valve. From the proportions of monomer and of potassium tert-butanolate, the estimated molecular mass is of the order 10,000.

2s Example 28

-48-Under the conditions of manipulation of Example 15, a solution A is obtained by dissolving the polymer of Example 26 in 100 ml of the mixture acetonitrile: toluene (4: 1) at a concentration of 0.5 g / cc. After dissolution full of polymer, a solution B is obtained by the dissolution in solution A of LiN (SO2CF3) 2, so as to obtain an O / Li ratio of 30: 1. A solution C is obtained by the dissolution in solution B of 1% by weight relative to the polymer of [N (SO2C2F5) 2] - [C6H5) 2I] +. The polymer matrix is shaped into form of a film thin according to the procedure mentioned above. The polymer matrix obtained is cross-linked after 12 seconds of UV irradiation at 365 nm at a power of GW / cm2. The matrix obtained has good mechanical properties and is insoluble in the solvents of the polymer before irradiation. The polymer matrix is the following dried under vacuum at 85 ° C. for two hours. The transition temperature vitreous is found by DSC at -62 C.

Example 29 Under the handling conditions of Example 15, a solution A is obtained by dissolution in the polymer of Example 20 of the lithium salt LiN (SO2CF3) 2 so as to obtain an O / Li ratio of 30: 1. A solution B is obtained by the dissolution 1% by weight relative to the polymer of [N (SO2C2F5) 2] - [C6H5) 2I] +. The solution B is spread to form a thin film according to the procedure mentioned previously, and cross-linked by 12 seconds of UV irradiation at 365 nm at a power of 3200 W / cm2.
The matrix obtained has good mechanical properties and is insoluble in the solvents of the polymer before irradiation. The glass transition temperature is observed by DSC at -64 C.

-49-Example 30 Under the handling conditions of Example 15, a solution A is obtained by dissolving the polymer of Example 27 in a mixture of tetraethylsulfamide with ethylene carbonate (60:40) containing lithium hexafluorophosphate at a concentration of 1 molar so as to obtain a volume ratio of 50% polymer and 50% solvent mixture. A solution B
is obtained by the dissolution of 1% by weight relative to the polymer of [N (S02C2F5) 2] -[C6H5) 2I] +. Solution B is spread to form a thin film of about 30 m on a polypropylene support, without evaporating the solvents. The polymer matrix obtained is cross-linked by 12 seconds of UV irradiation at 365 nm at a power of 3200 GW / cm2.
The matrix obtained has good mechanical properties and does not exude any solvent.
Although the present invention has been described using implementations specific, it is understood that several variations and modifications may add to implemented, and the present application is intended to cover such changes, uses or adaptations of the present invention according to, in general, the principles of invention and including any variation of the present description which will become known or Convention in the field of activity in which this invention, and which can be applied to the essential elements mentioned above, in agreement with the scope 2o of the following claims.

Claims (38)

1. Ionically conductive material consisting of at least one polymer and one less ionic compound, characterized in that:

the polymer is a crosslinked polymer prepared by anionic polymerization followed by crosslinking by cationic polymerization of a monomer corresponding to the formula (A) n Q (Y) p optionally with one or more other monomers, in which :

Q represents a bond, CO, SO2, or an organic radical of valence n + p non-reactive with initiators of the anionic polymerization or a cationic polymerization, the organic radical is chosen from a radical alkyl, alkylaryl and arylalkyl optionally having oxa substituents or aza, and having 1 to 30 carbon atoms;

* A is a reactive radical in anionic polymerization;

Y is a reactive radical in cationic polymerization and non-reactive vis-à-vis screw an agent initiating the anionic polymerization and represents the function crosslinkable crosslinked polymer, * n varies between 1 and 3;

* p varies between 1 and 6; and the ionic compound is constituted by at least one salt M n + X n-, in which M
n +
represents an inorganic, organic or any organometallic cation of charge n, and X- is a monovalent anion, two or more X- anions are linked together by covalent chains, belonging to the chain of a polymer or a different polymer chain. 2. Material according to claim 1 wherein:

A is selected from Y is selected from wherein :

Z represents O or CH 2;

R represents H, an alkyl or oxa-alkyl radical of 1 to 12 carbon atoms, CN or CH 2 COOR 1 in which R 1 is H or an alkyl or oxa-alkyl radical of 1 to 12 carbon of carbon;

- R1 represents H or an alkyl radical of 1 to 12 carbon atoms; and - r varies between 1 and 6. 3. Material according to claim 1, characterized in that the polymer is a random copolymer, a block copolymer or a star copolymer having units derived from a monomer (A) n Q (Y) p and units derived from one or more other monomers. 4. Material according to claim 1, characterized in that the polymer reticulated is shaped before crosslinking. 5. Material according to any one of claims 1 to 4, characterized in that than the polymer is crosslinked by the cationic polymerization of the Y groups. 6. Material according to claim 5, characterized in that the polymerization cationic group Y is also made in the presence of other monomers, oligomers or polymers carrying functions that are activated by agents initiating cationic polymerizations, radicals or both. Material according to claim 6, characterized in that the others monomers are oxygenated derivatives of dioxolanes chosen from spiroorthoformates and spiroorthocarbonates. 8. Material according to claim 6, characterized in that the polymerization cationic Y groups in the presence of monomer, oligomer or polymer, is made by thermal means, by actinic radiation action, or both, in presence or not an initiator. 9. Material according to any one of claims 1 to 8, characterized in that it further contains at least one plasticizer. 10. Material according to claim 5, characterized in that an additive is added in the form of powders, fibers or both, optionally treated, so that its surface has increased compatibility and adhesion to the polymer or of the polymer blends. 11. Material according to claim 10, characterized in that the additive is organic or inorganic, and optionally has properties of conduction ionic or electronic intrinsic, optical properties, a constant dielectric high, piezoelectric properties, or a combination thereof. 12. Material according to claim 1, characterized in that the polymer is a homopolymer of a monomer (A) n Q (Y) p wherein A is a group or a copolymer of the monomer (A) n Q (Y) p and an epoxide. 13. Material according to claim 12, characterized in that the epoxide is oxide ethylene. 14. Material according to claim 12, characterized in that the monomer (A) n Q (Y) p is selected from the compounds:

wherein :

R5 represents a divalent alkyl or oxa-alkyl radical of 0 to 12 atoms of carbon; and - R1 represents H or an alkyl radical of 1 to 12 carbon atoms. 15. Material according to claim 13, characterized in that at least one monomer is copolymerized in addition to ethylene oxide. 16. Material according to claim 15, characterized in that the comonomer is selected from a propylene oxide, a butylene oxide, a monoepoxide of diene from 4 to 10 carbon atoms and ethers of glycidol with groups methyl, ethyl or allyl. 17. Material according to claim 1, characterized in that the polymer reticle is a homopolymer of a monomer (A) n Q (Y) p in which A is a group or a copolymer of the monomer (A) n Q (Y) p and a styrenic monomer. 18. Material according to claim 17, characterized in that the monomer styrene is .alpha.-alkyl (oligoethoxy) - omega.-vinylbenzyl of formula General in which :

p varies between 2 and 60;

R 6 is a monovalent alkyl radical of 1 to 18 carbon atoms, or aryl radical monovalent from 5 to 18 carbon atoms;

Q is (CH 2) q, -CO- or -SO 2 -; and - q varies between 0 and 4. 19. Material according to claim 17, characterized in that the monomer (A) n Q (Y) p is selected from in which R 'represents H or an alkyl radical of 1 to 12 atoms of carbon, Q is (CH 2) q, - CO- or -SO 2 -, and R 7 is a divalent alkyl or an oxa-alkyl of 1 to 12 atoms of carbon. 20. Material according to claim 18, characterized in that at least one other monomer is copolymerized in addition to the .alpha.-alkyl (oligoethoxy) -egome.
vinylbenzyl. 21. Material according to claim 1, characterized in that the polymer reticle is a homopolymer of a monomer (A) n Q (Y) p in which A is in which R represents H, an alkyl or oxa-alkyl radical of 1 to 12 atoms of carbon, CN or CH2COOR1 in which R1 is H, an alkyl or oxa-alkyl radical of 1 to 12 carbon carbon, or a copolymer of the monomer (A) n Q (Y) p and a monomer having a double bond activated by a carbonyl group. 22. Material according to claim 21, characterized in that the monomer having a double bond activated by a carbonyl group is an acrylate, a methacrylate or an italate of .alpha.-alkyl (oligoethoxy) ethyl of the general formula:

in which p varies between 2 and 60;

R represents H, an alkyl or oxa-alkyl radical of 1 to 12 carbon atoms, CN or CH 2 COOR 1 in which R 1 is H or an alkyl or oxa-alkyl radical of 1 to 12 carbon of carbon; and R 6 is a monovalent alkyl radical of 1 to 18 carbon atoms, or aryl radical monovalent from 5 to 18 carbon atoms. 23. Material according to claim 21, characterized in that the monomer (A) n Q (Y) p is chosen from:

in which R 'represents H or an alkyl radical of 1 to 12 atoms of carbon, and R8 represents a divalent alkyl or oxa-alkyl radical of 0 to 12 atoms of carbon. 24. Material according to claim 22, characterized in that at least one other monomer selected from an organic acrylate and a metal acrylate is copolymerized in addition to acrylate, methacrylate or itaconate of .alpha.-alkyl (oligoéthoxy) ethyl. 25. Material according to claim 1, characterized in that it contains a salt of lithium or a mixture of lithium salt and a salt of another cation. 26. Material according to claim 1, characterized in that the salt is chosen among salts of anions ClO4-, BF4-, PF6-, AsF6-, SbF4-, CF3SO3-, [(CF3SO2) 2CH] -, [(CF 3 SO 2) 2 CH] -, [(CF 3 SO 2) C (CN) 2] -, (R x SO 2 N SO 2 R 'x) -, (R x SO 2 C (SO 2 R' x) R x ") -, of the anions derived from cyclopentadiene and its analogues aza carrying groups electroattractors, anions derived from pyrimidine-trione or 1,3-dioxane-4,5-dione carrying electron-withdrawing groups, derivatives of malononitrile, [(CF 3 SO 2) NSO 2 N (R 9) 2] - where R 9 represents alkyl of 1 to 30 carbon atoms, anion derived from 4,5-dicyano-1,2,3-triazole, 3,5-bistrifluoromethyl-1,2,4-triazole and tricyanomethane, R x and R x- being identical or different groups chosen from a halogen and C n F2n + 1 where n varies between 0 and 8 and in which R x "
represents R x, RSO2- or R x SO2-. 27. Material according to claim 26, characterized in that it contains at less a salt of ClO4-, BF4, PF6-, CF3SO3-, (FSO2) 2N-, (CF3SO2) 2N-, (C2F5SO2) 2N-, [(CF3SO2) 2CH] -, [(CF3SO2) C (CN) 2] -, [(CF3SO2) 3C] -, [(CF3SO2) NSO2N (R9) 2] - where R9 represents alkyl of 1 to 30 carbon atoms, anions derived from 4,5-dicyano-1,2,3 triazole, 3,5-bistrifluoromethyl-1,2,4-triazole or tricyanomethane. 28. Material according to claim 1, characterized in that two or more fractions of X- anions are either carried by the polymer chain, or part of a different polymer chain. 29. Material according to claim 1, characterized in that the polymerization cationic form of acetal bonds between groups Y and ends of chains from anionic polymerization. 30. Material according to claim 1, characterized in that the mass of Polymers before crosslinking is between 2 x 103 and 60 x 103 g / mol. 31. An electrochemical cell comprising an electrolyte, the electrolyte is consisting at least in part by a material as defined in claim 1. 32. An electrical energy storage system comprising at least one negative electrode and at least one positive electrode, the positive electrode having at least in part a material according to any one of claims 1 to 30. 33. The electrical energy storage system according to claim 32, characterized in that the electrical energy storage system is a generator primary, secondary or supercapacity. 34. System according to claim 32 or 33, characterized in that the electrode negative is selected from a lithium metal or one of its alloys optionally in the form of nanometric dispersion in a lithium oxide, nitrides double of lithium and a transition metal, oxides with low potential of formula General Li1 + y Ti2-x / 404, where x> = 0 and y <= 1, MoO2, WO2, carbon, carbon products from the pyrolysis of organic materials of ceramic fibers and alloys lithium-aluminum or lithium-silicon. 35. System according to claim 32 or 33, characterized in that the electrode positive electrode further comprises another electrode material selected from oxides of vanadium Li y VO x wherein 2x-5 <= y <= 2x-3; 2.15 <=
x <= 2.5, manganese spinels Li y Mn2-x M x O4 where M is Li, Cr, Al, V or Ni, 0 <= x <= 0.5 and 0 <= y <= 2, polydisulfides organic compounds, polyquinones, FeS, FeS2, iron sulphate, phosphates and phospho iron and lithium silicates of olivine or Nasicon structure or products of substitution iron with manganese, used alone or as a mixture. 36. System according to claim 32 or 33, characterized in that the material comprises a plasticizer having polar liquids selected from cyclic carbonates and acyclic, a .gamma.-butyrolactone, carboxylic acid esters, of the tetraalkylsulfamides, dialkyl ethers of mono, di, tri and tetraethylene glycols, oligomers with masses less than 2000 g / mol, and mixtures thereof. 37. A light modulation system comprising two supports, including minus one transparency, covered with a conductor based on tin oxide or oxide doped indium, a layer of an electrolyte and a counter-electrode, characterized in that that the electrolyte is a material as defined in claim 1. 38. The system of claim 37 further comprising the material, at least a dye that may change color depending on its degree of oxidation.