WO2010113188A1 - Fluorurated siliconic polymer, synthesis method and use - Google Patents

Abstract

The present invention relates to a fluorurated siliconic polymer with controlled molecular weight and viscosity having a structure composed by means of the chaining of oligo-dialkylsiloxane building-blocks having a limited and selected molecular weight and alternated mainly with siloxane units containing a fluorurated substituent and - to a marginal degree - inert siloxane units or substituted by unsaturated groups. When the latter are present -they are used for subsequent reactions of clamping or cross-linking. The present invention relates, moreover, to a synthesis method of the mentioned polymer and its use.

Description

DESCRIPTION

"Fluorurated siliconic polymer_/ synthesis method and use" [0001] . The present invention relates to a fluorurated siliconic polymer, its synthesis method and use. [0002] . The most frequent and common process, typical of silicone chemistry is hydrolysis and specifically the hydrolysis of organochlorosilanes (such as dimethyl- dichlorosilane) , which is the basic process for the industrial production of the most common silicones (poly- DMS) as well as for the preparation of other possible intermediates suitable for creating alternative methods of producing silicones and for varying their structure and molecular weight and thereby the intrinsic and application properties (cf. W. Noll, "Chemistry and technology of silicones", Academic Press, NY, 1968, chap. V) .

[0003] . For example, the hydrolysis of the DMS in water produces a mixture of linear poly-DMS with 50-80% of rings, while in sulphuric acid at 60-80% mainly linear poly-DMS can be obtained.

[0004] . Moreover, even the presence and nature of the organic solvents, as well as the structure and the molecular weight of the substituents bound to the silicon have an effect on the linear/ring ratio. [0005] . Two-stage industrial processes have also been created: after the hydrolysis of the first stage, potassium hydroxide is added to the hydrolysed mixture and heated to 80-170⁰C for several hours, so as to obtain an increase in the production of rings with a low-medium molecular weight by means of dehydration.

[0006] . Subsequently, the mixture is heated to 170 - 200⁰C and cracked to obtain a distillate composed of rings, mainly with three of four atoms of silicon. [0007] . The ring polysiloxanes, preferably tri- or tetra-siloxanes are then polymerised to open the ring (ring opening polymerisation or ROP) into linear polymers in the presence of single function catalysts or terminators which adjust the molecular weight to the average value desired (cf. US 3,903,047; US 5,169,970). [0008] . Various, non-hydrolytic processes have been experimented, classifiable as condensation processes of functional silanes, substituted by groups with varying relative reactivity. [0009] . Whatever the polycondensation process and its mechanism induced by the catalyst, the result depends on the reaction conditions, on the structure of the silanes and/or siloxanes and on their degree of functionality, determining the molecular weight of the final silicone. [0010] . In the case of poly-DMS, products of various molecular weights and bifunctional products terminated by oxydrylic groups (dimethylsilanols) are commercially available .

[0011] . These can be used as initiators to induce the opening of the siloxane rings of varying structure and- in the presence of catalysts - to obtain various polymers and co-polymers, which as a result of the equilibration reaction always consist of a mixture of linear products and rings . [0012] . Various types of inert and functional poly DMS, used in innumerable applications are commercially available: inert silicones used as insulators, dielectric, lubricant, heat-transmitting liquids; functional polysiloxanes used as reagents to obtain coupling or compatibilisation agents or to couple charges and other liquids or polymers, such as surfactant agents or as intermediates to obtain inert or crosslinkable protective coatings, or as additives for formulas repelling watery or organic liquids, if necessary charged with powders, such as silicas and micronised PTFEs to form fats, or as intermediates to obtain elastomeric compositions of varying structures - including interpolymeric- and of various consistency, from sealants to structural rubbers for gaskets, tubes and films. [0013] . In addition, fluorurated silicones composed of units of the methyl-3, 3 , 3-trifluoropropyl-siloxane type are also commercially available; these are of significant interest for their considerable chemical and interoxidative resistance as well as for their singular surface activity properties of electric insulation, and resistance to friction; their use is known of -in the sphere of various application sectors- as lubricant oils and bases for special greases, to produce elastomers resistant to lubricants and to liquid mineral combustibles with a vitreous transition temperature (Tg) below the temperature of -50⁰C (while the elastomers derived from poly-DMS have Tgs lower than 100⁰C or below 0⁰C) .

[0014] . Other linear fluorurated silicones made from heavier fluoroalkyl groups are not generally available in industrial quantities, in that they are not easy to produce by means of ROP of the siloxane rings of low molecular weight or by direct hydrolysis of the corresponding bichlorosilanes, given the unfavourable ring/linear balance and therefore the tendency to form highly stable fractions of rings.

[0015] . The interest in applications of functional silicones containing perfluoroalkyls with a high molecular weight, specifically up to eight atoms of carbon and above, is due to their ability to manifest a low molecular cohesion energy and consequent low surface energy such as to lower the surface tension in watery- environments or other organic environments at limit values between approximately 15 and 18 dine/cm, distinctly lower than the values given by standard poly- DMS type silicones having a limit around approximately 21 dine/cm.

[0016] . Specifically, fluorosiloxanes with the atom of silicon substituted by a radical containing a fluorurated segment with a chain length of 8 or more carbon atoms, such as for example heptadecafluoro-1, 1, 2, 2 , -tetrahydro- decyltrichlorosilane, have proved of interest given their ability to manifest and confer enhanced surface properties . [0017] . However, given the strong interest in terms of applications in fluorurated silicones having a more substantial polyfluoroalkyl substituent of silicone, composed of numerous perfluorurated atoms of carbon, especially of 8 or more carbon atoms (compared to the method of obtaining the precursors by means of telomerization of the tetrafluoroethylene, characterised by a wide distribution of the molecular weights of the telomere outside the desired target) and inasmuch as such fluorosilicones are particularly active in conferring considerable surface activity properties transmittable to the formulations to which they may be added, recently considerable alarm has arisen regarding the toxicity of the fluorurated components composed of a chain segment of eight or more perfluorurated carbon atoms, including in relation to their use in the class of polymer acrylics used as repellents in the furnishing fabrics and carpets sectors; silicones with substitutents containing fluorurated alkyl segments with 8 or more carbon atoms have also found interesting applications in the field of anti-soiling repellents. [0018] . Fluorurated residues of a high molecular weight have been traced at a considerable distance from production sites of the intermediates and formulations and from the sites of their applications to consumable materials. [0019] . Probably among the factors encouraging migration, as well as the resistance to natural physical and organic demolition agents, transport via the food chain also plays a significant role.

[0020] . The EPA (Environmental Protection Agency) has decided to support in-depth studies of the toxicity of perfluorurated residues with a high molecular weight, with reference to perfluoroctanoic acid (PFOA) , therein including the relative higher precursors, and has issued a recommendation for the voluntary reduction of emission by 95% by 2010, in the aim of eliminating generalised use totally by 2015 (C. M. Srevenson, Environment Sci . Technol . 40, 5590, 2006).

[0021]. The EPA's position has undoubtedly had an effect on industry in terms of self-control and responsible cessation of use of those perfluorurated intermediates of a high molecular weight subject to investigation.

[0022] . The present invention sets out to overcome the drawbacks associated with the use of fluorurated segments with a high number of carbon atoms in the sphere of silicone chain polymeric structures .

[0023] . Such objective is achieved by means of a fluorurated siliconic polymer according to claim 1, by means of a synthesis method according to claim 9 and by means of use of the polymer according to one of the claims from 13 to 19. The dependent claims refer to preferred embodiment variations .

[0024] . Given the two types of limitation described, the most important in relation to safeguarding of the environment and the other - of a technological nature - relative to the identification of an economically viable synthesis method of linear fluorosilicones, as an alternative to the hydrolysis of chlorosilanes substituted by a fluorurated radical with a high molecular weight and thereby predisposed to form mainly silicon rings, where the term "main" is taken to refer to a formation of rings. Specifically, the invention makes it possible to achieve the formation of mainly linear silicon polymers exceeding 95%-98%. To such purpose the authors of the present invention have undertaken the initiatives described below.

[0025] . As regards the length of chain of the fluorurated radicals placed as substituents on the silicone, they decided to consider the perfluorurated segments (Rf-) containing up to a maximum of six carbon atoms and to connect them to the silicone by means of an alkylenic radical (-Rs-) , having the function of a εspacer and composed of 2 to 10 hydrogenated carbon atoms; of optimising the combination of these two structural components so as to achieve the best chemical-physical properties and, specifically, the surface activity and to verify the result in terms of applications. [0026] . To summarise, for the repetitive fluorosiloxane unit characteristic of the invention inasmuch as afferent to the surface activity, the objective structure described by the formula (Ul) is envisaged:

- [(Rf-Rs-) Si (-R') -O] - (Ul) where : - R' is an alkyl or aromatic group, preferably a methyl or phenyl radical; - Rf is a monovalent perfluoroalkyl radical composed of 1 to 6 carbon atoms, preferably 3 to 6; and

- Rs is an alkylenic radical (spacer) composed of 2 to 10 carbon atoms . [0027] . The entire substituent group (Rf-Rs-) , bound to the silicone by means of the spacer, has structural characteristics predictably suitable for exerting a high level of surface activity, in practice comparable to the level of activity generated by a heptadecafluoro-1, 1,2, 2 tetrahydrodecyl type group present in many of the commercial fluorosilicones, but more sensitive than the latter to being broken down by natural chemical and organic aggressive agents and therefore not persisting for long periods like them, as occurs with the perfluorooctyl group.

[0028] . As regards the other limitation, relative to the difficulty of building mainly or exclusively linear fluorurated polysiloxane chains, the authors have envisaged precluding the parasitic formation of rings of various molecular weight, significant by-products of non- conventional silicone synthesis methods by the hydrolysis of excess chlorosilanes, of water or by ROP of siloxane rings of low molecular weight, using instead a process of controlled polycondensation so as to prevent the sequential nature of the single units derived from the fluorurated chlorosilanes and forcing the latter to alternate by condensation with the oligo-dialkyl- siloxane, and preferably oligo-dimethyl (oligo-DMS) or oligo-diethyl building-blocks of limited molecular weight terminated by silanol groups, having the structure (U^λ2) :

HO- (SiM20-)n-H ⁽U' ²⁾ wherein:

- M is preferably a methyl radical or may also be ethyl; and - is the number of dialkylsiloxane units, and an integer between 2 and 7 and, preferably, between 2 and 3.

[0029] . Specifically, the new fluorosilicones are composed of repetitive monosiloxane units strictly alternated with the dialkyl-siloxane units, preferably oligo-DMS, of the following formula (U2) , derived from the aforesaid precursor (U' 2), the monosiloxane units being represented by the following formulas (Ul) and (U3) :

~[(SiM20)n-]- ^(U2)

- [(Rf-Rs-) Si (-R' )-0-]- <^U1) -[(R-')Si(-R")-O-] ⁽U3⁾ wherein:

- R" is a radical other than R' but may be chosen from the same group as R' , or R" may be an alkyl-oxyalkyl or alkyloxy-polyethyleneoxyalkyl radical such as the ethyloxybutyl or tetraethyleneoxymethyl radical- as illustrative, non-limiting examples - or alternatively an unsaturated radical such as vinyl , or other unsaturated or diversely reactive radicals, such as but not limited to, the 4-ethyl-l-cyclohexene-l, 2-epoxy radical or trimethylene-oxypropylene epoxide; and

- the units of the general formulas (Ul) and (U3) are derived from the precursors (U' 1) and (U' 3) of which more will be said subsequently.

[0030] . As regards the details of the structure, each of the following individual polymeric sequences (P. i.) is composed of a succession of monosiloxane units (Ul, U3) each of which is alternated with an oligo-DMS (U2)unit:

- [ (SiM2O] n' ] [Si (RfRs) (R' ) 0] - [ (SiM2O) n" ] [Si (R' ) (R" ) O] - [(SiM2O)n' ' ']- (P. i.) wherein:

- Ti' , n' ' , n'^#/ are chosen in the same range of values as n and like them are preferred.

[0031] . While the average composition of the fluorosilicone of the invention is represented by the following formula (P. aver.):

WO- [ [ (SiM2O) n] s- [Si (RfRs) (R' ) 0] t- [Si (R' ) (R" ) 0] z] y-W

(P. aver. ) wherein:

- W is a monovalent radical of the following general formulas (U4) , (U5) and/or (U6) , respectively derived from the precursors (U' 4), (U' 5) and (U' 6) which will be illustrated below:

[M(R') (R") Si]- ^(ϋ4)

[M(R') (Rf-Rs)Si] - ^(U5) [(RMh(OR)₃-I₁Si]- (^U6> wherein:

- OR is the alkoxy group, preferably methoxy or ethoxy;

- h = 0, 1 or 2;

- s is the number of units corresponding to the general formula (U2) ;

- t is the number of units corresponding to the general formula (Ul) ;

- z is the number of units corresponding to the general formula (U3) ; and - y may vary from 1 to 10.

[0032] . With reference to the average composition of the invention having the structure described by the formula (P. aver.) the total number of the constituent units (s + t + z) may vary from 3, when t = 1 and 2 = 0, up to 10,000, preferably from 20 to 4000, while the value of y may vary from 1 to 10.

[0033] . Moreover, the ratio of the values t/z may vary from 1 to 20, while the ratio in equivalents (t + z + 2)/s may vary from 0.98 to 1.02, preferably from 0.999 to 1.0001. [0034] . The authors of the present invention have developed a process for producing fluorosilicones by means of the inter-polycondensation of oligo- dialkylsiloxanes (U' 2), of selected and limited molecular weights terminated at the extremities by silanol radicals, alternated with an equivalent dose of single chlorosilanic units composed of an important or main proportion, for example of 30% or 50% or 65%, of fluoroalkyl-dichlorosilanes, and for the remaining lesser portion by other dichlorosilanes and monochlorosilanes with hydrocarbilic substituents .

[0035] . Each of the chlorosilanic units is thereby alternated with an oligo-dialkylsiloxane unit so as to construct a specific structural architecture of the polymer, able to confer special characteristics and physical and chemical properties, especially the monochlorosilanes having the function of determining the molecular weight of the final silicone, having foreseen the exclusion from the reaction environment of the presence of water or other unwanted protogenic agents .

[0036] . In fact, the structure chosen for the fluorurated substituents bound to the atom of silicone is particularly suitable for facilitating intermolecular organisation and the formation of micellar structures in the organic or watery carrier liquids and produce low surface or interfacial tension properties. [0037] . In fact, starting with the synthetic intermediates by means of different treatments and formulations liquids with high chemical inertia were obtained, or functionalised so as to manifest sufficient compatibility in watery or organic environments; the new class of fluorosilicones of the invention comprises types with a high fluoride content enabling them to transmit improvements of surface activity through a synergetic effect when surfactants of a different structure are added, or through other structural modifications. That is to say it has proven possible to obtain crosslinkable liquids, able to form conformable and flexible coatings with a protective effect and water or oil repellent, electrical insulation, anti-adhesive properties including in relation, to silicone Pressure Sensitive Adhesives, or by means of introducing the appropriate functional groups and acting on them with crosslinking reactions and with appropriate formulations to obtain elastomers with varies degrees of consistency, with good physical and mechanical properties as well as resistance to solvents and lubricants, even in conditions of heat oxidation. [0038] . Lastly, the specific structure of the repetitive fluorosiloxane units (Ul) is also able to favour aggression of the fluorurated groups present in the molecule by natural physical and chemical demolition agents and consequently represents a step ahead in the issue tackled by the EPA and related to the accumulation of non-degradable polymers with long fluorurated segments.

[0039] . The structures of the polyfluoroalkyldichlorosilanes (U* 1) used - according to the invention - in a mainly stoichiometric ratio for alternating with the oligo-dialkylsilanoxyanic units (U^λ2) - proved essential to achieve the desired surface activity features:

(Rf-Rs-) Si (-R' )C12 (U' 1) wherein Rf, Rs, R' have been previously defined. [0040]. The other dichlorosilanes (ϋ'3) and/or (U'33) are alternated by condensation with the units (U' 2) in a minority stoichiometric proportion and act as modifiers of other properties, such as the vitreous transition temperature, or chemical compatibility or resistance to radiation when aromatic substituents are present : R' (R")SiCl2 ⁽U' ³⁾

Cl-SiM2-R33-SiM2Cl ⁽U'33⁾ wherein:

- R' , R" and M have been described previously;

- R33 is a telechelic, bivalent radical for example the 1,2-ethylene in the intermediate 1,2- bis (chlorodimethylsilil) ethane, the ' 1, 6-hexamethylene in the intermediate 1, 6-bis (chlorodimethylsilil) hexane, the 1, 3-bis-ethylbenzene in the intermediate 1,3- bis (chlorodimethylsilil) -ethylbenzene, the 1,3-bis- dipropylbenzene in the intermediate 1, 3-bis (chloro dimethyl silil propyl) benzene.

[0041] . According to a possible embodiment the monochlorosilanes have the important function of acting as terminators of the chain during polycondensation and are represented by the formula (U'4), (U^X5) or (U'6):

M (R') (R") SiCl (^u'⁴)

M (R') (Rf-Rs-) SiCl (U'5)

(R')h(OR)₃-hSiCl (U'⁶) wherein: - R' , R' ' , M₇ Rf and Rs are defined as previously;

- OR is an alkoxy group preferably methoxy or ethoxy and h = 0 or 1 or 2.

[0042] . Should one want to achieve a perfect stoichiometry in the condensation between the oligo-DMS (U' 2) and the individual chlorosilane units, the equivalents of silanol terminals i (2s) equal the equivalents of the chlorosilanes .

[0043] . The alternate polycondensation of the oligo- dialkylsiloxanes (U' 2) with the chlorosilanes (U' 1), (U' 3), (U' 33), and in the presence of chain terminals (U'4), (U'5), (U'6) may produce inert silicones without unsaturated groups or silicones containing unsaturated groups and active by reactions to be performed subsequently, such as the crosslinking catalysed by peroxides or clamping by addition to poly-hydrosilanes catalysed by elements such as platinum supported either by Platinum or Rhenium compounds or Rhodium and Ruthenium compounds as known to the experts of the sector, the most widely used catalyst being hexachloroplatinic acid in the presence or absence of inhibitors .

[0044] . Should the unsaturated siloxanes be present only at the terminals of the fluorosilicones which the invention relates to, a chain extension reaction may be performed by means of silanisation of the unsaturated terminal groups by means of the addition - for catalysis with derivatives of the Platinum-of polysiloxane hydrides such as those shown in the formulas of the general formulas (U"22) and (U"23) . During the condensation process described in the invention the ratio in the equivalents of the building blocks (U^λ2) and the chlorosilanes mentioned (U^λl, U^X3, U^Λ33, U^λ4, U^λ5, U*6) is kept equal or close to the unit so as to optimise the conversion and the molecular weight. [0045] . In actual fact, operating with a slight excess in equivalents of siloxanes compared to the stoichiometric equivalent of the silanols needed may be preferred, so that the chlorosilanes alternate with the oligo-DMS units; by way of a non-limiting example such excess may be from 0.01 % to 0.5%, while the low ratio of monochloro and dichlorosilanes is the regulating parameter of the molecular weight of the fluorine silicone in inverse proportion.

[0046] . At the end of polycondensation, the polymer may present both reactive functions bound to the last unit at the ends of the chain, that is the chlorosilane and the silanol; it may therefore be beneficial to convert the chlorosilane type terminals by means of a reaction of controlled hydrolysis in silanol type terminals and subsequently proceed with further intermolecular condensation to form a chain extension in controlled conditions, for example but not limited to such, in the presence of tetra methyl guanidine-trifluoroacetate at approximately 60⁰C under a current of anhydrous nitrogen. [0047] . Lastly, once the best and desired molecular weight for the application has been achieved, it may be beneficial to perform a reaction of end-capping of any silanol groups present by means of inertising terminator agents such as disilazane or other monofunctional silanes or siloxanes according to a method well known to experts in the field to stabilise the final product and prevent variations in properties with ageing or heating. This way the best compromise is reached between a minimal presence and total absence of volatile rings and the achievement of the desired viscosity and stability of the silicone obtained .

[0048] . According to the process described by the invention, the objective is to obtain silicone inter- polymers with various predetermined structures and molecular weights characterised by the fact of presenting a chain structure composed of oligo-dialkylsiloxanes with a molecular weight limited to specific, predetermined values and precisely alternated with fluoroalkylsiloxane units, and in the remaining minority proportion optionally by siloxanes with the silicone atom substituted by a hydrocarburic radical, preferably methyl or phenyl, or by a radical of the alkyl-oxyalkyl type or substituted with an unsaturated vinyl or allylic radical; according to the invention the siliconic chains are terminated by an inert or unsaturated siloxane group; the unsaturated units being activated at a subsequent step of crosslinking or clamping; the fluorosilicones of the invention containing unsaturated groups at the terminals only can be activated by a chain extension reaction by means of addition of siloxane hydrides of the type indicated by the formulas (U' 22) and (U' 23) and/or by end-capping, catalysed by derivatives of Platinum or Rhodium or of other derivatives of the homologous derivatives of the metals of the eighth group. [0049]. In one particular embodiment, where the terminal group (U6) has at least one alcoxylic group bound to the silicone, the cross-linking may be conducted by means of a reaction with a polyfunctional reagent for example of the methyl-ethyl diacethoxy silane or tetramethoxy silane type. [0050] . As regards the availability of the reagents silanol-terminated, oligo-dialkylsiloxaic of structure (U^X2), commercial quantities of such intermediates are available starting from average molecular weights in the range 400-700, specifically, for example, a fraction with a value between 5-8 (for example with an average value of 7.2) is available in commerce, a mixture of the homologues with n = 6 and n = 8, with viscosity of about 25 cst at 25°C. [0051] . The authors of the invention prepared the preferred intermediates (U' 2) with n = 2 or n = 3 by means of oxidative hydrolysis respectively of tetra methyl-disiloxane or of hexa-methyltrisiloxane (U' 22) and

(U' 23), performed at 5⁰C in the presence of palladium catalysts supported on charcoal, preferably or on alumina, in the presence of measured quantities of acqueous solutions and tetrahydrofurane (THF) buffered at pH . 6.5-7.2, in the presence of aprotic solvents containing donor atoms of electrons . [0052] . It has been shown that, in such conditions and in the presence of solvents such as tetrahydrofurane, dioxane, glime and acetone, the yields in silandiols

(U' 2, n = 2 and n = 3) were over 80%, probably on account of the establishing of a hydrogen bond between the oxydryl group of the silanol and the aprotic solvent and consequent prevention of unwanted reactions of mutual condensation of the silanols to conserve them for condensation with the chlorosilanes (U' 1, U' 3), in addition it is also worth intervening by controlling the temperature and, if necessary, through the presence of a slight excess of chlorosilanes.

[0053] . The preferred solvents with donor atoms of electrons, according to the procedure are, for example , but not limited to such, dioxane, tetrahydrofurane, monoglime. H- (SiM2 O-Si-M2)-H (U'22)

H- (SiM2O-SiM2O-SiM2) -H ^{(u# 23)} wherein the intermediate (U'22) is preferred. [0054] . The molecular weight of the fluorosilicone according to the invention is regulated by means of the dosage of the molar ration of the monochlorosilanes and dichlorosilanes in the range between 0.5 and 0.002 and, preferably, between 0.1 and 0.005.

[0055] . During the polycondensation process between the oligo-DMS units and chlorosilane units a siloxane bond is formed between the units and HCl is formed which is subtracted from the reaction environment by means of a nitrogen current or reacted or absorbed by means of salification with an amine such as piridine or a tertiary amine . [0056] . The reaction environment is composed of a pure and anhydrous organic solvent, such as a hydrocarbon or an ether, glime, THF, dioxane or mixture of the same. [0057] . In some embodiment methods of the invention- given by way of example and not limited to such, the repetitive unit type (Ul) may be represented by the formulas :

- [Si(CmH2mC4F9) (R')O] - or

- [Si(CmH2mC6F9) (R') O]- [0058] . The dichlorosilane precursors are obtained according to the following formula, for m = 3 :

Rf-I + CH2=CHCH2-D (i)-> (ii) -> (iii)-> RfC3H6SiMCl2 wherein :

- Rf = C3F7 -, C4F9-, C6F13 -; - D = -OH or -OCOM or -Cl; (i)_.: 90-120⁰C; (U) Bu3SnH;

(iii) HSiMCl2 /Pt catalyst, 70-120⁰C.

[0059] . or for m= 4, 6, according to the following alternative formula: CH2=CH- (CH2)p-E (i)-» i±i) -> (iii)-» (iv)-» Cl2MSiC2H4- (CH2)m-Rf wherein:

- E = -Cl or - Br;

- p = 0.2, 4; (i) Mg / ethers;

(ii) I-CH2CH2-Rf, -10-0⁰C;

(iii) acid, purification;

(iv) HSiMCl 2 .

[0060] . The precursors of the terminal units type (U' 4 ) are available commercially, while others such as those type M2Si (C2H4OC2H5) Cl can be obtained by silylation with chlorodimethylsilane (M2HSiCl) of the vinylethylethers or superior homologues such as the vinylbutylethers or the triethylenglycol methylvinylethers in the case of the terminals M₂Si (C₂H₄OC₄H₉) Cl or M₂Si (C₂H₄O (EO) ₃M) Cl .

[0061] . As regards the properties of the f luorosilicones according to the invention, the most interesting results from the point of view of applications were found using as key intermediates the oligo-DMS silanolic precursors , type (U2 ) with n=2 and units according to the invention type (Ul) , formed of fluoroalkylsiloxanes with radicals type C4F9C3H6-, C4F9C4H8-, C6F13C4H8-, C4F9C6H12-, C6F13C6H12- and other siloxane methylvinylic type units (U3, U4) ; fluorosilicones type (P . aver . ) were obtained with viscosity around 150-250 cPs and fluorine contents around 30%-40%.

[0062] . Such products permitted the creation of coatings applicable without dilution with solvent (solvent-less type) , which after crosslinking by means of polysiloxane poly-hydrides and catalysts derived from chloroplatinic acid (CPA) permitted the production of films consistent with the equivalent release properties of commercial fluorurated silicones composed of polyfluoroalkylsiloxanes type [C (8-10) F (17-21) C2H4-Si (M)O-] containing perfluoroalkydic chains with more than 6 perfluorurated carbon atoms .

[0063] . It was found that the aforesaid commercial samples showed a certain fall in release performance over time, due to the migration to the surface of non- crosslinked liquids, the so-called deterioration due to the presence of fluorurated volatiles, a classic component present in the fluorosilicones prepared using co-hydrolysis of the dichlorosilan.es . The fluorosilicone according to the invention showed a release effect particularly resistant to ageing, according to detachment loads from an adhesive support of the standard type for the sector and without the adhesive tape folded onto itself at 180° showing a reduction of adherence, following the release and migration to the surface of volatile cyclic oils.

[0064] . To demonstrate the technical advancement of the process of the invention compared to the process of hydrolysis of chlorosilanes in water, counter-tests performed, according to the process of the invention of alternate polycondensation, but using oligo-DMS alternated with units (Ul, n= 7) formed of siloxane units substituted by C8F17C2H4- produced silicones with viscosity 300-500 cPs and fluorine content of 25%, which had to be spread with the help of a solvent, although after crosslinking by the addition of poly-hydride- polysiloxanes they manifested release effect stability without deterioration for long periods- demonstrating the absence of volatile liquids released by the crosslinked coating and migrating towards the surfaces.

[0065] . Surprisingly, an extremely interesting result was found with fluorosilicone type (P. aver.) with the units (Ul) containing siloxane C4F9C4H8-Si (M) 0- and other methylvinylsiloxane units, each alternated with the oligo-dialkylsiloxane units (U2, m=2) . [0066] . From samples of the fluorosilicone containing the main units [C4F9C4H8-Si (M) 0] and other vinylsiloxane units, having viscosity of 1000 to 3000 cPs, charged with 25- 30% of Cabosil silica silanised and crosslinked by addition of polyhydridepolysiloxanes , in a ratio of SiH/SiV of 1.2, by addition of 100 ppm of CPA then subjecting the formulation to heating at 130-180⁰C in a press at 100 Kg/cm² to obtain sheets and films of elastomer resistant to breaking loads of 60 and 90 Kg/cm².

[0067] . A sheet 1 mm thick of the crosslinked elastomer, immersed in a mixture composed of 85 parts volume of methanol, 7.5 parts of toluene and 7.5 parts of iso-octane and heated to 65⁰C for 48 hours underwent an increase in volume of approximately 6%, much less than a sample of elastomer type poly-DMS.

[0068] . Alternatively, the same rubber with the strengthening charge added could be crosslinnked by 2% in weight with 2,4-dichlorobenzoil peroxide for heating in a press at 130-160⁰C to obtain a sheet resistant to traction of 65 kg/cm2.

[0069] . In another type of application, a sample of 100 grams of fluorosilicone, obtained according to the invention, composed of fluorurated substituents such as C4F9C4H8- and of oligo-DMS (U2) with n =2 and silanol terminals, with viscosity of 220 cPs, dissolved in hexane and mixed with 2% of poly-hydrogenomethyl-polysiloxane, with viscosity of 20 cPs, and with 100 ppm of chloroplatinic acid in iso-propanol, then spread by means of a corrugated roller onto a polyester support and treated in a ventilated stove at 50⁰C to evaporate the solvent, after placing the polyester strip between two sheets of PTFE the packet was placed between the plates of a Carter press and heated to 80°c and then to 120⁰C for two hours under pressure of 10 atm. After resting for 24 hours under the press a consistent, continuous film was obtained showing a good anti-adhesive effect compared to a scotch tape. [0070] . Example 1 [0071].^' STEP 1: SYNTHESIS OF C4F9CH2CH2CH2SiCl2CH3

[0072] . 160 grams of C4F9CH2CH=CH2 nonafluoro- 1, 1,2, 3,3-pentahydroeptene (0.615 moles), 77.84 grams of dichloromethylsilane (0.677 moles), 0.016 grams of a solution at 42.5% in 2-propanol of hexachloroplatinic acid were placed in a stainless steel autoclave in a nitrogen atmosphere.

[0073] . The reaction was conducted at 75-80⁰C for 5 hours, at the end of which it was vacuum distilled to eliminate all traces of excess dichloromethylsilane. The IR spectrum of the residue confirmed the formation of the product and the disappearance of the Si-H groups. [0074]. STEP 2: SYNTHESIS OF 1,3 DIHYDROXYTETRAMETHYL- DISILOXANE

[0075]. 68 grams of tetrahydrofurane, 24.2 grams of water and 1.02 grams of Pd/Al2O3 5% were placed in a PTFE reactor holding 1 litre in a nitrogen atmosphere. While maintaining the temperature at 5-10⁰C drop by drop 68 grams of 1, 1, 3, 3-tetramethyldisiloxane (0.506 moles) were added over two hours. After completing such addition the reaction was continued for another two hours at the same temperature .

[0076] . By means of IR analysis and gaschromatography the 1, 1, 3, 3-tetramethyldisiloxane was proved as having disappeared. The reaction mixture was then filtered to eliminate the catalyst and distilled in a vacuum to obtain a transparent oily product which solidifies into white crystals at room temperature. IR analysis confirmed the formation of the product and the presence of the groups -OH 3183cm^"1; ≡Si-O-Si≡ 1025cm^"1. [0077]. STEP 3: SYNTHESIS OF THE POLYMER

[0078] . A 500ml four-necked flask fitted with a thermometer, a mechanical stirrer, a coolant dripper and a dripper feed funnel, fitted to a heated oil bath, was fed with 111.22 grams (296.6 moles) of C4F9CH2CH2CH2Si(Cl)2CH3, 2.70 grams (19.2 moles) of dichloromethylvinylsilane, 2.31 grams (19.2 moles) of chlorodimethylvinylsilane previously solubilised in 32.50 grams of hexane .

[0079] . The temperature of the organic mixture was raised to 25-30⁰C and, under a nitrogen flow, 98.3 grams of a 55% solution of tetramethyldisiloxane-1, 3-diol

(325.3 moles) were added drop by drop to the tetrahydrofurane . When dripping was completed, while maintaining a nitrogen flow so as to take away the gaseous hydrochloric acid, the reaction mixture was heated to 55-60⁰C. After 5 hours of reaction the organic phase was repeatedly washed with cold water until neutralised. [0080]. A mixture prepared using 1.03 grams (9.0 moles) of trifluoroacetic acid and 0.349 grams (3.0 moles) of tetramethylguanidine keeping the reaction mass at 50⁰C under a slight nitrogen flow for 3.5 hours to remove the condensation water formed was added to the organic solution in hexane of the polymer, separated from the aqueous phase. At the end of the operation the organic salts in the organic mass were removed by repeated rinsing in water and hexane. Lastly, the polymer in solution in hexane was anhydrified with magnesium sulphate, filtered and then distilled in high vacuum to eliminate any traces of volatile substances present in the reaction products.

[0081] . The polymer obtained was colourless, with a viscosity of 207 cPs and vinyl-siloxane content of about 2% molar in relation to the total siloxane units. [0082] . NMR analysis confirmed the formation of the product showing the signals summarised in the following table:

[0083]. The theoretic fluorine content was 30.97% in weight, effective content 30,0%; theoretic molecular weight was 15282 g/mole, effective weight was 15370 g/mole .

[0084] . Example 2

[0085]. 4.53 grams (252.1 moles) of

C4F9CH2CH2CH2Si(Cl)2CH3, 2.20 grams (11.52 moles) of dichloromethylphenylsilane, 2.40 grams (17.03 moles) of dichloromethylvinylsilane, 2.05 grams (17.03 moles) of chlorodimethylvinylsilane previously solubilised in 28.89 grams Of hexane were placed in the same apparatus as Example 1. [0086] . The temperature of the organic mixture was raised to 25-30⁰C and, under a nitrogen flow 87.4 grams of a 55% solution of tetramethyldisiloxane-1.3-diol

(289,2 moles) was dripped in tetrahydrofurane .

[0087] . The polymer was then processed using the procedure as in Example 1.

[0088] . The polymer obtained was yellow, with a viscosity of 274,8 cPs and a content of vinyl siloxane units of about 3% molar compared to the total siloxane units . [0089] . IR analysis confirmed the presence of the phenolic groups at 1429 cm^"1; CF3- at 1357 cm^"1; 2964 cm^"1 CH3-; 1597 cm^"1 CH₂=CH-; 3702 cm^"1 OH- . [0090] . Example 3 [0091]. STEPl: SYNTHESIS OF CH30 (CH2CH20) ₇CH2CH2CH2- SiCl2CH3 [0092]. 80 grams of CH30 (CH2CH20) _9,7CH2CH=CH2 polyglycol AM500 (supplied by Clariant GmbH) (0.16 moles), 20.24 grams of dichloromethylsilane (0.176 moles), 0.01 grams of a 42.5% solution in 2-propanol of hexachloroplatinic acid were placed in a stainless steel autoclave in a nitrogen atmosphere.

[0093] . The reaction was conducted at 75-80⁰C for 5 hours, at the end of which distillation was performed in a vacuum to eliminate any trace of excess dichloromethylsilane. The IR spectrum of the residue confirmed the formation of the products and the disappearance of the Si-H groups. [0094]. STEP 2: SYNTHESIS OF THE POLYMER [0095]. 90.36 grams (240.9 moles) of C4F9CH2CH2CH2Si(Cl)2CH3, 27.78 grams (45,1 moles) of CH30 (CH2CH20)₉,₇CH2CH2CH2SiCl2CH3, 3.63 grams (30,1 moles) of chlorodimethylvinylsilane previously solubilised in 30.1 grams of hexane were placed in the same apparatus as Example 1. [0096] . The temperature of the organic mixture was raised to 25-30⁰C and, under a nitrogen flow, 91.0 grams of a 55% solution of tetramethyldisiloxane-1, 3-diol (301,2 moles) was dripped into tetrahydrofurane . [0097] . The polymer was then synthesised using the same procedure as Example 1. [0098] . The polymer obtained was yellow, with a viscosity of 450 cPs . [0099] . Example 4

[ooioo]. STEP 1: SYNTHESIS OF C₄F₉ (CH₂) ₄CH=CH₂ [00101] . A 1000ml, four-necked flask fitted with a thermometer, a mechanical stirrer, a coolant dripper and a dripper feed funnel, immersed in a coolant bath at - 10⁰C, was filled with 39.83 grams (0.25 moles) of 3- butenylmagnesium bromide (500 ml of solution 0.5 M in THF) (supplied by Sigma Aldrich Co.) .

[00102] . Maintaining the reaction temperature at below O⁰C, and in a constant nitrogen flow, 78.54 grams of C₄F₉CH₂CH₂I (0.21 moles) dissolved in 200ml of ethylic anhydrous ether were added drop by drop. When dripping was completed the organic mass continued to be agitated for one hour at a temperature of about 0⁰C before being carefully poured into a water/ice and sulphuric acid bath. [00103] . The organic solution of ether was washed further with deionised water before distilling the product to obtain 34.8 grams of olefin. IR analysis confirmed the formation of the product with the corresponding signals of the double bond at 1644.24 and 3083.94cm^"1. [00104]. STEP 2: SYNTHES OF C₄F₉ (CH₂) ₄CH₂CH₂SiCl₂CH₃ [00105], 30 grams of C₄F₉(CHa)₄CH=CH₂ (0.099 moles), 12.53 grams of dichloromethylsilane (0.108 moles), 0.003 grams of a 42.5% solution in 2-propanol of hexachloroplatinic acid were placed in a stainless steel autoclave in a nitrogen atmosphere .

[00106] . The reaction was conducted at 75-8O⁰C for 5 hours, at the end of which distillation was performed in a vacuum to eliminate any trace of excess dichloromethylsilane. The IR spectrum of the residue confirmed the formation of the products and the disappearance of the Si-H groups. 39.4 grams of product were recuperated with a yield of 95,3%. [00107]. STEP 3: SYNTHESIS OF THE POLYMER [00108]. 36.6 grams (87.9 moles) of C4F9(CH2)4CH2CH2Si(Cl)2CH3_/ 0.8 grams (5,67 moles) of dichloromethylvinylsilane, 0.684 grams (5,67 moles) of chlorodimethylvinylsilane previously solubilised in 9.6 grams of hexane were placed in the same apparatus as Example 1. [00109] . The temperature of the organic mixture was raised to 25-30⁰C and, under a nitrogen flow 29.12 grams of a 55% solution of tetramethyldisiloxane-1, 3-diol (96.4 moles) were dripped in. [00110] . The polymer was then synthesised using the same procedure as Example 1. [00111] . The polymer obtained was colourless, with a viscosity of 265 cPs and a content of vinyl siloxane units of about 3.9% molar compared to the total siloxane units. [00112] . Example 5

[00113]. 100 grams of the polymer of Example 1 containing 0.71% in weight of vinyl groups was mixed with 4.3 grams of a silicone polymer containing fluoroalkylsiloxane units and ≡Si-H groups corresponding to a percentage of active H equal to 1.2% in weight. The ratio of the Si-H and vinyl groups was about 2:1. 0.36 grams of a catalyst made from a platinum- divinyltetramethyldisiloxane based complex with 0.3-0.35% of platinum (supplied by ABCR GmbH & COD) were added to the polymer mixture.

[00114] . Part of the mixture obtained was then spread on a standard PP polymeric film and placed in the stove at 130-140⁰C for seconds. At the end of this period the surface tension of the treated surface was measured as 15 dine/cm.

[00115] . An evaluation of the adhesion/release force was made by depositing a film of the fluorosilicone mentioned and crosslinked as above on a PP film. Commercial adhesive tape was spread over this and the detachment force of the adhesive tape was recorded as about 80-90% compared to an analogous test of adhesive tape applied to virgin PP film. [00116] . Example 6

[00117] . A sample of fluorosilicone of Example 2 with viscosity 275 cPs in which silanolic terminal groups were present was diluted to 5% in hexane and mixed with a methyl-hydrogen polysiloxane polymer already described in Example 5. The PT catalyst as described in Example 5 was added to a part of the solution. The solution obtained was spread on the polymeric propylene film and placed in the stove for 1 minute at 150⁰C to obtain a film with a surface tension of about 16 dine/cm. [00118] . Example 7 [00119] . In another type of application, a sample of 300 grams of fluorosilicone, obtained according to the invention, formed of fluorurated constituents such as C4F9C3H6- and of oligo-DMS (U2) with n = 2 and with the other siloxanes type (U' 3) with methyl and phenyl type radicals and dimethylphenylsiloxane type terminals with viscosity of 200 cPs, was charged with 20% of PTFE in fine powder and homogenised by means of a roll mill, a grease was obtained with good resting stability without significant separation of the oil and with good lubricant properties when put onto ball bearings. [00120] . Example 8 [00121]. STEP 1: SYNTHESIS C4F9 (CH2) 2CH=CH2 [00122] . A 1000ml, four-necked flask fitted with a thermometer, a mechanical stirrer, a coolant dripper and a dripper feed funnel, immersed in a coolant bath at - 10⁰C, was filled with 300 ml of solution 1 M in THF of vinylmagnesium bromide (0.3 moles) (supplied by Sigma Aldrich Co.)

[00123] . Maintaining the reaction temperature at below 0⁰C, and in a constant nitrogen flow, 100 grams of C₄F₉CH₂CH₂I (0.267 moles) dissolved in 250ml of ethyl anhydrous ether were added drop by drop . When dripping was completed the organic mass continued to be agitated for one hour at a temperature of about 0⁰C before being carefully poured into a water/ice and sulphuric acid bath.

[00124] . The organic solution of ether was washed further with deionised water before distilling the product, to obtain 42.4 grams of olefin. [00125]. STEP 2: SYNTHESIS OF C4F9 (CH2) 2CH2CH2SiCl2CH3 [00126]. 27.4 grams of C₄F₉ (CH₂) ₂CH=CH₂ (0.1 moles), 12.65 grams of dichloromethylsilane (0.11 moles), 0.003 grams of a 42.5% solution in 2-propanol of hexachloroplatinic acid were placed in a stainless steel autoclave in a nitrogen atmosphere. [00127] . The reaction was conducted at 75-80⁰C for 5 hours, at the end of which distillation was performed in a vacuum to eliminate any trace of excess dichloromethylsilane. The IR spectrum of the residue confirmed the formation of the products and the disappearance of the Si-H groups. 36.6 grams of product were recuperated with a yield of 94.2%.

[00128]. STEP 3: SYNTHESIS OF THE 3,4-EPOXY CICLOHEXYL ETHYL-METHYL DICHLOROSILANE [00129]. 12.42 grams of 4-vinyl-l-ciclohexene-l, 2-epoxy (supplied by Sigma Aldrich) (0.1 moles), 12.65 grams of dichloromethylsilane (0.11 moles), 0.0015 grams of a 42.5% solution in 2-propanol of hexachloroplatinic acid were placed in a stainless steel autoclave in a nitrogen atmosphere . [00130] . The reaction was conducted at 75-80⁰C for 5 hours, at the end of which distillation was performed in a vacuum to eliminate any trace of excess dichloromethylsilane. The IR spectrum of the residue confirmed the formation of the product and the disappearance of the Si-H groups.

[00131]. STEP 4: SYNTHESIS OF THE POLYMER [00132]. 34.19 grams (87.9 moles) of C4F9(CH2)2CH2CH2Si(Cl)2CH3, 1.36 grams (5.67 moles) of 3,4-epoxy ciclohexyl ethyl-methyl dichlorosilane, 0.617 grams (5.67 moles) of chlorotrimethylsilane previously solubilised in 9.6 grams of hexane were placed in the same apparatus as example 1 , STEP 3.

[00133] . The temperature of the organic mixture was raised to 25-3O⁰C and, under a nitrogen flow, 29.12 grams of a 55% solution of tetramethyldisiloxane-1, 3-diol (96.4 moles) were added drop by drop.

[00134] . The polymer was then synthesised using the same procedure as Example 1.

[00135] . The polymer obtained was yellow, with a viscosity of 265 cPs .

[00136] . A mixture of THF and hexane, 50% volume, containing 20 parts of the fluorosilicone, 10 parts of epoxy oligomer type polyphenylglycidylether-copolymer- formaldehyde (Aldrich, Mn =345), 0.5 parts of 4-octo- oxyphenyl-phenyl iodonium hexafluoroantimoniate was prepared. 0.1 parts of Mischler ketone as photosensitizer.

[00137] . A portion of solution was spread on a polypropylene tape, after which the solvent was made to evaporate and the tape was illuminated with a 150 watt

Hanovia bulb for a few minutes until a film consistent with water- and oil- repellent properties was obtained.

[00138] . Example 9

[00139] . Another experiment was conducted with the fluorosilicone in Example 8 STEP 4, with viscosity 265 cPs; it was made to react with metacrylic acid at 10% less than the theoretical value after which the modified silicone (20 parts) was carried in a 50 % vol. mixture of THF and hexane, and 2 parts of trimethylolpropanotriacrylate, 0.2 parts of photoactivator Darocur 1116 were added; the solution was spread on a polyester strip and the solvent evaporated to obtain a dry film, the product was illuminated with a Hanovia bulb for a few minutes until a consistent film with water- and oil- repellent properties was obtained. [00140] . Example 10

[00141] . A 500ml four necked flask fitted with a thermometer, a mechanical stirrer, a coolant dripper and a dripper feed funnel, fitted to a heated oil bath, was filled with 115.34 grams (307.6 moles) of C4F.9CH2CH2CH2Si(Cl) 2CH3, 2.56 grams (19,8 moles) of dichlorodimethylsilane, 2.39 grams (19,8 moles) of chlorodimethylvinylsilane previously solubilised in 33.70 grams of hexane . [00142] . The temperature of the organic mixture was raised to 25-3O⁰C and, in a nitrogen atmosphere, 101.9 grams of a 55% solution of tetramethyldisiloxane-1, 3-diol

(337.3 moles) was added drop by drop to the tetrahydrofurane . When dripping was . completed the reaction mixture was heated to 55-6O⁰C. After 5 hours of reaction the organic phase was repeatedly washed with cold water until neutralised.

[00143]. 1.03 grams (9.0 moles) of trifluoroacetic acid and 0.349 grams (3.0 moles) of tetramethylguanidine were added to the hexane solution of the polymer separated from the aqueous phase, keeping the reaction mass in reflux for 3.5 hours and gradually removing the condensation water forming. At the end of the operation the organic salts in the organic mass were removed by repeated rinsing in water and hexane. Lastly, the polymer in solution in hexane was anhydrified with magnesium sulphate, filtered and then distilled in high vacuum to eliminate any traces of cyclics forming during the reaction. [00144] . The polymer obtained was colourless, with a viscosity of 239 cPs .

[00145] . 40 grams of polymer, with a content of vinyl groups of 0.35% in weight, were made into a solution with 80 grams of anhydrous hexane. 0.84 grams (6.2 moles) of trichlorosilane and 0.005 grams of a 42.5% solution in 2- propanol of hexachloroplatinic acid were added to such solution. Having verified the disappearance of the vinyl groups it was then distilled in a vacuum to eliminate the excess trichlorosilane and hexane. The polymer was then treated with anhydrous ethanol at 50⁰C for 2 hours under a nitrogen flow to eliminate the HCl that had formed. At the end of treatment the ethanol was distilled in a vacuum. [00146] . Upon completion, a portion of the polymer was mixed with 15% of CaCO3 , to which 5% of methyltriacetoxysilane was then added and spread on the bottom of a Petri slide before being exposed to the air at room temperature: within a short time a film formed on the surface . [00147] . The next day, when several drops of water were placed on the surface of the film they did not spread but acquired an almost spherical shape.

[00148] . 40 grams of polymer of Example 1 with viscosity 239 cPs, and a content of vinyl groups of 0.35% in weight were made into a solution with 80 grams of anhydrous hexane. 0.84 grams (6.2 moles) of trichlorosilane and 0.005 grams of a 42.5% solution in 2-propanol of hexachloroplatinic acid were added to such solution. Having verified the disappearance of the vinyl groups it was then distilled in a vacuum to eliminate the excess trichlorosilane and hexane. The polymer was then treated with anhydrous ethanol at 50⁰C for 2 hours under a nitrogen flow to eliminate the HCl that had formed. At the end of treatment the ethanol was distilled in a vacuum. [00149] . Upon completion, a portion of the polymer was mixed with 15% of CaCO3 , to which 5% of methyltriacetoxysilane was then added and spread on the bottom of a Petri slide before being exposed to the air at room temperature: within a short time a film formed on the surface .

[00150] . The next day, when several drops of water were placed on the surface of the film they did not spread but acquired an almost spherical shape. [00151] . A person skilled in the art may make modifications to the embodiments of the fluorurated siliconic polymer and to the method described above so as to satisfy contingent requirements while remaining within the sphere of protection as defined by the following claims.

[00152] . Each of the features described as pertaining to one possible embodiment is protected independently of the other embodiments described.

Claims

1. Fluorurated siliconic polymer with structure of oligo- dialkylsiloxane blocks alternating with siloxane units of the following general formula (P.aver.): WO- [ [ (SiM2O) n] s- [Si (RfRs) (R' ) 0] t- [Si (R' ) (R" ) 0] z] y-W

(P. aver . )

wherein:

- M is a methyl or ethyl radical;

- n is an integer between 2 and 7; - s is the number of oligo-dialkylsiloxane units;

- Rf is a perfluorurated radical containing up to a maximum of six carbon atoms;

- Rs is a linear alkylenic radical composed of 2 to 10 hydrogenated carbon atoms; - R' is an alkyl or aromatic group;

- t is the number of perfluorurated siloxane units;

- R" is a radical different from R' , chosen from the same group as R' , or R" is an alkyloxyalkyl radical or alkyloxy-polyethylenoxyalkyl , such as the ethyloxybutyl or tetraethylenoxymethyl radical or an unsaturated radical such as vinyl, allyl or other unsaturated or diversely reactive radical, such as the radical 4-ethyl- 1-cyclohexene-1,2-epoxide or trimethylenoxypropylen- epoxide; - z is the number of siloxane units; - each siloxane unit type t or z is followed and/or preceded by an s-type unit; wherein each W siloxane unit is bound to an s type unit;

- y is an integer from 1 to 10; - W is a monovalent radical of the following general formula (U4) , (U5) and/or (U6) :

[M(R') (R") Si]- ^(U4)

[M(R') (Rf-Rs)Si]- ^(U5) t(R')_h(OR)₃-hSi]- <^U6) wherein:

- M, R', R'', Rf, Rs are defined as above;

- OR is a methoxy or ethoxy group; and

- h = 0 or 1 or 2; and wherein: - (s + t + z) is an integer from 3 to 10,000 when t = 1 and z = 0.

2. Fluorurated siliconic polymer according to claim 1, wherein n is an integer 2 or 3.

3. Fluorurated siliconic polymer according to claim 1 or 2, wherein (s + t + z) is an integer from 20 to 4000.

4. Fluorurated siliconic polymer according to any of the previous claims, wherein Rf is a perfluorurated radical composed of 3 to 6 carbon atoms.

5. Fluorurated siliconic polymer according to any of the previous claims, wherein R' is a methyl or phenyl radical .

6. Fluorurated siliconic polymer according to any of the previous claims, wherein the ratio t/z is comprised between 1 to 20.

7. Fluorurated siliconic polymer according to any of the previous claims, wherein the ratio in equivalents (t + z + 2)/s is 0.98 to 1.02.

8. Fluorurated siliconic polymer according to claim 7, wherein the ratio in equivalents (t + z + 2)/s is 0.999 to 1.0001.

9. Synthesis method of a fluorurated siliconic polymer according to any of the previous claims comprising the polycondensation reaction between a compound of the following general formula (U' 2): HO- (SiM2O-)n-H ⁽U' ²⁾ and a compound of the general formula (U' 1) :

(Rf-Rs-) Si (-R' )C12 ⁽U' 1⁾ and/or with at least one of the compounds of the general formula (U'3) (U'33): R' (R")SiCl₂ ⁽U'³⁾

Cl-SiM2-R33-SiM2Cl ⁽U'3³⁾ wherein R33 is a telechelic bivalent radical, such as 1,2-ethylene in the intermediate 1»2- bis (chlorodimethylsilil) -ethane, 1, 6-hexamethylene in the intermediate 1, 6-bis (chlorodimethylsilil) hexane, 1,3-bis- ethylbenzene in the intermediate 1,3- bis (chlorodimethylsilil) -ethylbenzene, 1,3-bis-dipropyl- benzene in the intermediate 1, 3-bis (chlorodimethyl- sililpropyl) benzene; and with at least one of the compounds of the general formula (U'4), (U'5) and/or (U'6):

M(R' ) (R") SiCl ^(u'4)

M(R' ) (Rf-Rs-) SiCl (U'5)

(R' )_h (OR)₃-_IiSiCl. (U'⁶)

10. Method according to claim 9, wherein the molecular weight of the polymer is regulated by dosing the molar ratio of monochlorosilanes and dichlorosilanes .

11. Method according to any of the claims 9 or 10, comprising a chain extension phase of the polymer with an increase of the average molecular weight by reaction among the terminal groups of the polymer chains .

12. Method according to any of the claims from 9 to 11, comprising a phase of functionalisation of the main polymer chain by means of clamping of functional groups lateral to said main polymer chain, so as to modify the properties of the polymer in view of a desired application.

13. Use of the silicone as is without the use of relative thinner solvents to reduce the viscosity.

14. Use of the fluorurated siliconic polymer according to any of the previous claims, as an inert liquid to produce lubricants and grease with a low friction coefficient and resistant to abrasion, especially at temperatures between 150 and 25O⁰C.

15. Use of the fluorurated siliconic polymer according to any of the previous claims, containing an unsaturated group crosslinkable by means of treatment with peroxides or radiation.

16. Use of the fluorurated siliconic polymer according to any of the previous claims, containing a vinyl type unsaturated group, to produce a reaction with polyhydrosiloxanes, preferably fluorurated, for the purpose of creating a catalytic polyaddition reaction with derivatives of palladium.

17. Use of the fluorurated siliconic polymer according to any of the previous claims, containing a reagent group of the type 4-ethyl-1-ciclohexene-1,2-epoxide to perform a ■crosslinking reaction catalysed by UV radiation in the presence of catalysts with a cationic crosslinking mechanism.

18. Use of the fluorurated siliconic polymer according to any of the previous claims, having anti-adhesive properties towards supports treated with siliconic adhesives and able to operate and resist at temperatures of 150-250⁰C.

19. Use of the fluorurated siliconic polymer according to any of the previous claims, containing vinyl units destined for use as an injectable sealant, for example as sealant for encapsulants .