MXPA97010266A - Molecular and oligomeric precursors of silanopara materials reticula - Google Patents

Abstract

The present invention relates to novel molecular and oligomeric organosilicon compounds containing fluorine atoms, soluble in fluorinated solvents and useful as precursors of cross-linked or cross-linked materials.

Description

TITLE MOLECULAR AND OLIGOMERIC PRECURSORS OF SILANO FOR RETICULATED MATERIALS BACKGROUND OF THE INVENTION.

This invention relates to organosilicon compounds and in particular relates to molecular and oligomeric organosilicon compounds containing fluorine atoms. Various types of organosilicon compounds containing fluorine are known in the chemistry of the organosilicon including, for example, fluorine-containing alkoxysilanes such as the alkoxysilanes of the formula (RfH20) iSi, in which R £ = CF3 to C.0F21, described in U.S. Patent 2,993,925; (CF3 (CF2) xCX2CH2CH20) 4 Si (x = 0-4 and X = H or F) in U.S. Patent 3,491,134; and HSi.OCH.CFab 'and CH: = CHSi (OCH2CF3) 3 in U.S. Patent 4,652,663. U.S. Patent 5,378,790 describes more complex compounds, called "stars" of the formula X (SiQ3) "in which Q is Ci alkoxy up to about Cβ, Ci acyloxy up to about Cβ, or halogen. However, no fluoroalkoxy Q is described in REF: 26517 processes are not provided for the preparation of precursors with a fluoroalkoxy Q. There has also been great interest in recent years in polymers with a regular, three-dimensional structure, similar to a tree. Such polymers are called dendrimers. These tree-like molecules are the result of a controlled repetitive growth that starts from a polyfunctional nucleus. From the nucleus, two or more identical branches emanate, each branch contains additional branching sites at their ends. With successive generations a fractal, similar to a sphere evolves until its additional growth is limited by surface congestion. Although most such polymers are completely organic, a few organosilicon dendrimers have been prepared. D. Seyferth et al., In "Synthesis of an Organosilicon Dendrimer Containing 324 Si-H Bonds", Organometallics 1994, 13, 2682-690 describe starting from tetravinylsilane as a central molecule, a succession of hydrosilations catalysed by Pt alternatives of all the groups vinyl with HSiCl3 and vinyls of all the SiCl groups introduced with CH2 = CHMgBr in tetrahydrofuran which provide a divergent synthesis of four generations of polycarboxylan dendrimers in which the Si atoms are linked by CH2CH2 groups. The chlorosilane of each generation was not introduced with LiAlH4 to the corresponding silicon hydride. Compounds with fluorinated ends or fluoroalkoxy or alkoxy ends are not mentioned or provided. The Applicant has prepared novel fluorine-containing organosilicon compounds of the "star" and "dendrimer" type and novel fluorine-containing polysilicates, which are particularly useful in conventional sol-gel chemistry conducted in fluorinated solvents.

BRIEF DESCRIPTION OF THE INVENTION The present invention provides a compound of formula I X (Si (OCaH2aRf) 3) n I wherein: X is at least one organic link selected from the group consisting of: (a) R1p? SiY4-m; (b) Annular structures Ib (i> Zb (li) Ib (üi) (c) R \ -Si (OSi (CH3) 2Y) 4-m; (d) CH3SiY2OSiY2CH3; (e) Y3SiOSiY3; (f) Y2 (CH3) Si ( CH2) bSi (CH3) Y2; 5 (g) Y3Si (CH2) bSiY3; (i) substituted benzene, including all isomers, selected from the group consisting of: 10 (i) C6H3 (SiZ3-cYc) 3; ) CeH2 (SiZ3.cYc) 4, (iii) CßH (SiZ3.cYc) 5, and (iv) C6 (SiZ3-cYc) 6, and (j) substituted cyclohexane, including all the stereoisomers, selected from the group consisting of of: (i) 1,2-C 6 H 10 (Y) _; 1,3-C 6 H 10 (Y) 2; 1,4-C 6 H 10 (Y) 2; (ii) 1,2,4-C 6 H 9 (Y) 3; 1, 2,, 3-C6H9 (Y) 3; 1.3.5-C6H9 (Y) 3; (iii) 1,2,3,4-C6H8 (Y) 4; 1, 2, 4, 5-C6H8 (Y) 4; 1, 2,3,5-CßH9 (Y) 4; (iv) 1,2,3,4,5-C6H7 (Y) 5; and (v) c H6 (Y) 6; and 25 (k) Y (CF) VY Rf has up to about 18 carbon atoms and is selected from the group consisting of: (a) perfluoroalkyl of C_ up to about C_8; (b) - [CF2CF (CF3) 0] r-CF2-CF2-CF3, wherein r is an integer of at least 1; (c) -CF2- (CF2-0) q-CF3, wherein q is an integer of at least 2; and (d) -CH2-C (CF3) 2-CF2-CF2-CF3; wherein up to 50% of the fluorine of the Rf group is optionally substituted with hydrogen; a is an integer from 1 to about 10; b is an integer from 1 to approximately ; c is 1, 2 or 3; m is 0, 1 or 2; n is an integer greater than or equal to 2; v is an integer from 2 to approximately 14; R1 is alkyl of d up to about C? aril; Y is - (CR'R3) kCRVCR6R (CR8R9) h- R2 to R9 are each independently hydrogen, C_ alkyl to about C8, or aryl, provided that at least one of R4 to R7 is hydrogen; k and h are each independently an integer from 0 to 10, provided that each of k or h is zero; and Z is alkyl of C. to about C < , 3,3,3-trifluoropropyl, aralkyl or aryl. The present invention also provides a compound of formula IA X (R10Si (OCaH2aRf) _) n IA wherein: X is at least one organic link selected from the group consisting of: (a) R, rSiY4-, "; (b) Annular structures IA < 0) U) lA (b) (ii) IA (b) (iii) (c) R1mSi (OSi (CH3) 2Y) 4 -, -; (d) CH3SiY2OSiY2CH3; (e) Y3SiOSiY3; (f) Y2 (CH3) Si (CH2) bSi (CH3) Y2; (g) Y3Si (CH2) bSiY3; 5 (h) Y3SiC6H4SiY3; (i) substituted benzene, including all isomers, selected from the group consisting of: (i) C6H3 (SiZ3.cYc) 3; 10 (ii) C6H2 (SiZ3-cYc) 4; (iii) C6H (SÍZ3.CYC) 5; and (iv) C6 (SiZ3-cYc) 6; and (j) substituted cyclohexane, including all stereoisomers, selected from the group consisting of: (i) 1,2-C6H10 (Y) 2; 1,3-C6H10 (Y) 2; 1,4- CeHio (Y) 2; (ii) 1,2,4-C6H9 (Y) 3; 1,2,3-C6H9 (Y) 3; 1,3,5- C6H9 (Y) 3; 20 (iii) 1,2,3,4-C6H8 (Y) 4; 1, 2, 4, 5-C6H8 (Y) and, 1,2,3,5-C6H9 (Y) 4; (iv) 1,2,3,4,5-C6H7 (Y) 5; and (v) C6H, (Y) 6; Rf have up to about 18 carbon atoms and is selected from the group consisting of: (a) perfluoroalkyl of Ci up to about C_8; (b) - [CF_CF (CF3) 0] r-CF2-CF2-CF3, wherein r is an integer of at least 1; (c) -CF2- (CF2-0) q-CF3, wherein q is an integer of at least 2; and (d) -CH2-C (CF3) 2-CF2-CF2-CF3; wherein up to 50% of the fluorine of the Rf group is optionally substituted with hydrogen; Z is C_ alkyl to about C4, 3,3,3-trifluoropropyl, aralkyl or aryl; Y is - (CRR3) CR4R5CR6R (CRßR9) h-; R1 is Ci alkyl to about C8 or aryl; R2 to R9 are each independently hydrogen, alkyl of up to about C8, or aryl, provided that at least one of R4 to R7 is hydrogen; R10 is Ci alkyl to about C8 or CaH2aR £; m is 0, 1 or 2; k and h are each independently an integer from 0 to 10, provided that at least one of k or h is zero; a is an integer from 1 to about 10; b is an integer from 1 to about 10; c is 1, 2 or 3; and n is an integer greater than or equal to 2. The present invention also provides a compound of formula II If [(CH_) fSi (CH3) 3-d ((CH2) eSi (OR10) d] 4 II wherein: d is 1, 2 or 3; e is an integer from 2 to about 10; f is an integer from 2 to about 10; R10 is C_alkyl to about C8 or a is an integer from 1 to about Rf has up to about 18 carbon atoms and is selected from the group consisting of: (a) perfluoroalkyl of C_ to about C_8; (b) - [CF2CF (CF3) 0] r-CF2-CF2-CF3, wherein r is an integer of at least 1; (c) -CF2- (CF2-0) q-CF3, wherein q is an integer of at least 2; and (d) -CH_-C (CF3) 2-CF2-CF2-CF3; wherein up to 50% of the fluorine of the Rf group is optionally substituted with hydrogen.

The present invention further provides an oligomeric compound of formula III SiíOCH ^ Rfh-.O- /; III where: z is an integer from 0.5 to 3.0; a is an integer from 1 to about 10; and Rf has up to about 18 carbon atoms and is selected from the group consisting of: (a) perfluoroalkyl of C_ to about C? 8; (b) - [CF2CF (CF3) 0] r-CF2-CF2-CF3, wherein r is an integer of at least 1; (c) -CF2- (CF2-0) q-CF3, wherein q is an integer of at least 2; and (d) -CH2-C (CF3) 2-CF2-CF2-CF3; wherein up to 50% of the fluorine of the Rf group is optionally substituted with hydrogen.

The present invention also provides an oligomeric compound of formula IV Rf- (CH2) y-Si (OR) 14) 3.zOz / 2 IV where z is a number from 0.5 to 2.5; and is an integer from 2 to about 10; each R14 is independently C_ alkyl to about C8; carboxy from C_ to about C10, fluorocarboxy from C_ to about Cio or CaH2aRf; a is an integer from 1 to about Rf has up to about 18 carbon atoms and is selected from the group consisting of: (a) perfluoroalkyl of Ci up to about C? 8; (b) - [CF2CF (CF3) 0] r-CF2-CF2-CF3, wherein r is an integer of at least 1; (c) -CF2- (CF2-0) q-CF3, wherein q is an integer of at least 2; and (d) -CH: -C (CF3) 2-CF2-CF2-CF3; wherein up to 50% of the fluorine of the Rf group is optionally substituted with hydrogen.

DETAILED DESCRIPTION OF THE INVENTION For the compounds of formula I, IA, II, III and IV as defined above, the Rf group may be a fluoroalkyl or perfluoroalkyl group, which may be either normal or branched, and have up to about 18 carbon atoms, preferably from one to eight carbon atoms, particularly preferably from one to three carbon atoms. Normal perfluoroalkyl groups include, for example, trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluorooctyl, perfluorodecyl, perfluorododecyl, and perfluorooctadecyl. Rf is preferably CF3, C2F5 or C3F7. It was considered less practical to synthesize the fluorine-containing compounds of the formulas I, IA, II, III and IV wherein Rf has more than eighteen carbon atoms, although such fluorosilanes could be preferably suitable in all applications contemplated for this class of compounds . A typical synthetic suitable branched fluoroalkyl group is -CH2-C (CF3) 2-CF2-CF2-CF3. The Rf groups may also be certain perfluoro (alkyleneoxy) alkyl radicals. These include the perfluoro (methylene (polymethyleneoxy) methyl) (c) and perfluoro ((polyisopropyleneoxy) propyl) radicals (b). For the compounds of formula I and IA, X is preferably (a) RamSiY4-m; the annular structures of formulas Ib (i) - (iii) and IA (b) (i) - (iii); (c) R ^ Yes (ÓSi (CH3) 2Y) 4_m or (k) Y (CF2) vY. The most preferred organic bond X, is where O is, k is O or 1, h is O or 1, and all of R 2 to R 9 are hydrogen. Rf is preferably CF3, C2F5 or n-C3F7. Z is preferably CH 3; the preferred aralkyl is benzyl and the preferred aryl is phenyl. n is preferably 2-6, more preferably 2, 3 or 4; a is preferably 1; and v is preferably 4, 6, 8 or 10, more preferably 6. Representative examples of the compounds of formula I are: Si (CH2CH2SÍ (0CH2CF3) 3) ti Si (CH2CH2Si (OCH2CF2CF3) 3) 4; Si (CH2CH2Si (OCH2 (CF2) 2CF3) 3) 4; Si (OSi (CH3) 2CH2CH2Si (OCH2CF3) 3) 4; 5 Si (OSi (CH3) 2CH2CH2Si (OCH2 (CF2) 2CF3) 3) 4; Si (OSi (CH3) 2CH2CH2CH2Si (OCH2CF3) 3) 4; Cyclo- ((CH3) (CF3CH20) 3SiCH2CH2) SiO) y, cyclo- ((CH3) (CF3CH20) 3SiCH2CH2CH2) SiO) y, cyclo- (CH3) (CF3CH20) 3SiCH2CH2CH2) SiO) 5; Cyclo- (CH 3 (CF 3 (CF 2) 2 CH 20) 3 SiCH 2 CH 2) SiO) y, (CF 3 CH 20) 3 SiCH 2 CH 2 (CF 2) 6 CH 2 CH 2 Si (OCH 2 CF 3) 3; (CF3 (CF2) 2CH20) 3SiCH2CH2 (CF2) 6CH2CH2Si (OCH2 (CF2) 2CF3) 3; and (CF3CH_0) 3Si (CH2) 6 (CF2) 6 (CH2) 6Si (OCH2CF3) 3. The representative examples of formula IA are: YES (CH_CH2SÍCH3 (OCH2CF3) 2) 4; Si (CH2CH2SiCH3 (0CH2 (CF2) 2CF3) 2) y, Si (OSi (CH3) 2CH2CH SiCH3 (OCH2CF3) 2) 4; Si (OSi (CH3) 2CH CH2SÍCH3 (OCH2 (CF2) 2CF3) 2) if Si (OSi (CH3) 2CH2CH2CH2SiCH3 (OCH2CF3) 2) y, (CF3CH20) 2CH3SiCH2CH2 (CF2) 6CH2CH2SiCH3 (OCH2CF3) 2; (CF3 (CF2) 2CH20) 2CH3SiCH2CH2 (CF2) 6CH2CH2SiCH3 (OCH2-25 (CF2) 2CF3); (CF3CH20) 2CH3Si (CH2) 6 (CF2) 6 (CH2) 6SÍCH3 (OCH2CF3) 2; Si (CH2CH2Si (CH2CH2CF2CF3) (OCH2CF3) 2) 4; Si (CH2CH2Si (CH2CH2CF2CF3) (OCH2 (CF2) 2CF3) 2) 4; Si (OSi (CH3) 2CH2CH2Si (CH2CH2CF2CF3) (OCH2CF3) 2), S i (OSi (CH3) 2CH2CH2Si (CH2CH2CF2CF3) (OCH2 (CF2) 2CF3) 2) 4; Si (OSi (CH3) 2CH2CH2CH2Si (CH2CH2CF2CF3XOCH2CF3) 2), (CF3CH20) 2 (CF3CF2CH2CH2) SiCH2CH2 (CF2) 6CH2CH2Si (CH2- CH2CF2CF3) (OCH2CF3) 2; (CF3 (CF2) 2CH20) 2 (CF3CF2CH2CH2) SiCH2CH2 (CF2) 6CH2CH2- Si (CH2CH2CF2CF3) (OCH2 (CF2) 2CF3) 3, (CF3CH20) 2 (CF3CF2CH2CH2) Si (CH2) 6 (CF2) 6 (CH2) 6YES (CH2, CH2CF2CF3) (OCH2CF3) 2; Cyclo- ((CH3) (CF3CH20) 2CH3SiCH2CH2) SiO), cyclo- ((CH3) (CF3CH20) 2CH3SiCH2CH2CH2) SiO), cyclo- ((CH3) (CF3CH20) 2CH3SÍCH2CH2CH2) SÍO) 5; and Cyclo- ((CH3) (CF3 (CF2) 2CH_0) 2SÍCH2CH2) SiO) 4.

For the compounds of formula II as defined above, preferably f is 2 or 3; e is preferably 2 or 3; and R 1 ° is preferably CH2CF3, CH.C2F6, or CH: C3F7. Representative examples of formula II are Si (CH_CH? CH2Si (CH3) 2CH2CH2CH2Si (OCH2CH3) 3) 4; Si (CH2CH2CH2Si (CH3) 2CH2CH_CH2Si (OcH2CF3) 3) 4; Si (CH2CH2CH2SÍCH3 (CH2CHCHSi (OCH2CH3) 3) 2) 4 / Si (CH2CH2CH2SiCH3 (CH2CH2CH2Si (OCH2CF3) 3) 2) 4; and Si (CH2CH2CH2SÍ (CH2CH2CH2Si (OCH2CF3) 3) 3) 4.

Preferably the fluoroalkoxysilanes of formula I, formula IA and formula II are soluble in one or more fluorinated solvents. Perfluoro aliphatic solvent systems (e.g., perfluoro (butyl THF)), polyfluoro aliphatic (e.g., C3F7OCHFCF3) and perfluoroaromatic (e.g., hexafluorobenzene) can be used. Preferred solvents comprise perfluoro (butyl THF), for example, "FLUOROINERT" FC-75; "FLUOROINERT" FC-40, a mixture of perfluoroalkylamines; perfluoro phenanthrene, for example "FLUTEC" PP-11, C3F7OCHFCF3, for example, "FREON" El; hexafluorobenzene (Cf.Fr,); perfluoromethylcyclohexane, CoFn (CF3); and perfluoro (n-ethylmorpholine). The solubilities of the compounds of formula I were determined in hexafluorobenzene (CbF < -,), perfluoro (butyl THF) (FC-75), hexane, and tetrahydrofuran. { THF) and are shown below in Table I.

Table I Solubility of Fluoroalkoxy Silanes Compound C6F6 FC-75 Hexane THF Si (CH2CH2Si (0CH2CF3) 3) 4 Y N N Y Si (CH2CH2Si (OCH2C3F7) 3) 4 Y Y N N (CH3 (CH2CH2Si (OCH2CF3) 3) SiO) 4 Y N N Y (CH3 (CH2CH2Si (OCH2C3F7) 3) SiO) 4 Y Y N Y Si (OSi (CH3) 2CH2CH2Si (OCH2CF3) 3) 4 YNNY Si (OSi (CH3) 2CH2CH2Si (OCH2C3F7) 3) 4 YYNY [(CF2) 3CH2CH2SY (OCH2CF3) 3] 2 YNNY [(CF2) 3CH2CH2Si (OCH2C3F7) 3] 2 YYNY The synthesis of the compounds of formula I and IA were obtained from hydrosilylation reactions, that is, an addition reaction between a compound having a Si-H group with a compound containing aliphatic unsaturation, such as an alkene, in the presence of a catalyst or initiator of free radicals. The precursor segments contain -CH = CH2 groups that react with other precursor segments which contain terminal Si-H bonds. Any precursor segment may contain vinyl or another unsaturated group capable of the addition of Si-H. For example, Si (CH = CH2) 4 reacts with HSi (OCH2CF3) 3 to form the Si precursors (CH2CH2Si (OCH2CF3) 3] 4; Si (CH = CH2) 4 reacts with HSiCH3 (OCH2CF3) 2 to form the precursor Si (CH2CH2SiCH3 (OCH2CF3) 2) 4; and cyclo- [(CH3) HSiO] 4 reacts with CH2 = CH-Si (OCH2C3F7) 3 to form the cyclo- precursor ((CH3) (CF3 (CF2) 2CH20) 3SÍCH2CH2) SiO) 4. All the following equations provide for the preparation of the compounds of formula I by the addition of a silane through the carbon-carbon double bond for various definitions of X: (Note that the preparation of the compounds of formula IA proceeded in similarly, except that the group Si (R10) (OC3H2aR £) 2 in all cases replaces Si (OC_H2aR) 3). (a) when X is R1p, SiY4-m: Ec. ÍA: R \ -Si [(CR2R3) kCR4 = CRcR7] 4-m + 4 -m H (CR8R9) hSi (OCaH2aRf) 3? R \ "YES t (CR R3) kCR4HCR6R7 (CR8R ') ,, Si (OCaH2aRf) 3] 4-m Ec. IB: R'n.Si [(CR: R3) kH] 4.m + 4-m CR-CR * (CR8R9) hSi (OCaH2aRf) 3? R \ -Si [(CR2R3) kCR R5CRf'H (CR8R9) tlSÍ (OCaH2aRf) 3] 4- »(b) when X is an annular structure of the type Ib (i), Ib (ii) or Ib (iii), as defined above, which can be abbreviated (SiO) uZu (YSi (OCaH2aRf) 3) U where u = 3 for Ib (i), u = 4 for Ib (ii), and u = 5 for Ib (iii); so Ec. 2A: (YES) uZu [(CR2R3) kCR4 = CR6R7] u + u H (CR9R9) hSÍ (OCaH2aR £) 3? (SiO) UZU ((CR2R3) kCR4HCR6R7 (CR8R9) hSi (OCaH2aRf) 3] u Ec. 2B: (SiO) uZu [(CR2R3) kH] u + u CR4R5 = CR6 (CR8R9) hSi (OCaH2aRf) 3? (SiO) UZU [(CR2R3) kCR4R5CR6H (CR8R9) hSi (0CaH2aRf) 3] u (c) when X is R ^ Si (OSi (CH3) 2Y)?. " Ec. 3A: R: mSi (OSi (CH3) 2 (CR2R3) kCR4 = CR6R7] 4-In + 4-m H (CR8R9) hSi (OCaH2aRf) 3 R- Si (OSi (CH3) 2 (CR2R3) kCR4HCR ': R7 (CR8R9 ) hSi (OCaH2aRf) 3] 4_m Ec.3B: RamS i (OS i (CH3) 2 (CR2R3) kH] 4-m + 4-m CRR5 = CR6 (CR8R9) hS i (OCaH2aRf) 3 R ^ Si (OSi (CH3) 2 (CR2R3) kCR4R5 = CR6 (CR8R9 ) hSi (OCaH2aRf) 3] 4- " (d) when X is CH3SiY2OSiY2CH3: Eq. 4A: CH3S i ((CR2R3) kCR4 = CR6R7) 2OS i ((CR2R3) kCR4 = CR6R7) 2CH3 + 4H (CR8R9) hSi (OCaH2aRf) 3? CH3Si ((CR2R3) kCR4HCR6R7 (CReR9) hSi (OCaH2a Rf) 3) 2OSI ((CR2R3) kCR4HCR6R7 (CR8R9) hSi (OCaH2aRf) 3) 2CH3 Ec. 4B: CH? SK (CR'R3) kH) 2OSi ((CR2R3) kH) 2CH3 + 4 CR4R5 = CR6 (CR8R9) hSÍ (OCaH2aR £) 3? CH3Si ((CR2R3) kCR4R5CR6H (CR8R9) h Si (OCaH2aRf) 3) 2OSi ((CR2R3) kCR4R5CR6H (CRßR9) hSi (OCaH2aRf) 3) 2CH3 (e) when X is Y3SiOSiY3 Ec. 5A: If ((CR2R3) kCR4 = CR6R7) 3OSi ((CR2R3) kCR4 = CR6R7) 3 + 6H (CR8R9) hSÍ (OCaH2aRf) 3? If ((CR2R3) kCR4HCR6R7 (CR8R9) hSi (OCaH2a R £) 3) 3OSÍ ((CR2R3) kCR4HCR6R7 (CR8R9) hSÍ (OCaH2aRf) 3) 3 Ec. 5B: If ((CR2R3) kH) 3OSÍ ((CR2R3) kH) 3 + 6 CR4R5 = CR6 (CR8R9) hSi (OCaH2aR £) 3 -Si ((CR2R3) kCR4R5CR6H (CR8R9) hSi (OCaH2aRf) 3) 3OSi ((CR2R3) kCR4R5CR6H (CR8R9) hSi (OCaH2aR £) 3) 3 (f) when X is Y2 (CH3) Si (CH2) bSi (CH3) Y2 Ec. 6A: If ((CR2R3) kCR4 = CR6R7), - (CH3) (CH2) hSÍ ((CR2R3) kCR4 = CR6R7) 2 (CH3) + 4 HÍCRVASMOCaHi-a f) ..? Yes ((CR2R3) kCR4HCR6R7 (CR8R9) hSÍ (OCaH2a Ri) 3) 2 (CH3) (CH2) bSi ((CR2R3) kCR4HCR6R7 (CR8R9) hSÍ (OCaH2aRf) 3) 2 (CH3) Ec. 6B: If ((CR2R3) kH) 2 (CH3) (CH2) bSi ((CR2R3) kH) 2 (CH3) + 4 CRV * - = CR6 (CR8R9h, Si (OC _2aRt) 3? Si ((CR2R3) kCR4R5CR6H (CR8R9 ) hSi (OCaH2aRf) 3) 2 (CH3) (CH,) bSi ((CR2R3) kCR4R5CR6H (CR8R9) hSi (OCaH2aR £) 3) 3 (CH3) (g) when X is Y3Si (CH2) bSiY3: Ec. 7A: If ((CR2R3) kCR4 = CRbR ') 3 (CH < -) bSi ((CR 2ZrR> 3J) kCR> 44 = -C r -Rt.b 6Rt') 3 + 6 H (CR8R9) hSi ( OCaH2aRf) 3? Yes ((CR2R3) kCR4HCR6R7 (CR8R9) hSÍ (OCaH2a Rf) 3) 3 (CH2) bS i ((CR2R3) kCR4HCRbR7 (CR8R9) hS i (OCaH2aR £) 3) 3 It is. 7B: If ((CR2R3) kH) 3 (CH2) bSi ((CR2R3) kH) 3 + 6 CR4R5 = CR6 (CR8R9) hSY (OCaH2aR £) 3 ? If ((CR2R3) kCR4R5CR6H (CR8R9) hSi (OCaH2aRf) 3) 3 (CH2) bSi ((CR2R3) k CR4R5CR6H (CR8R9) hSi (OCaH2aR £) 3) 3 (h) when X is Y3SiCfiH4SiY3: Ec. 8A: If ((CR2R3) kCR4 = CR6R7) 3C6H4Si ((CR2R3) kCR4 = CR6R7) 3 + 6 H (CR8R9) hSi (OCaH2aR £) 3? If ((CR2R3) kCR4HCR6R7 (CR8R9) h Si (OCaH2aRf) 3) 3C6H4Si ((CR2R3) kCR HCR ° R7 (CR8R9) hSÍ (OCaH2aRf) 3) 3 Eq. 8B: If ((CR2R3) kH) 3C6H4Si ((CR2R3) kH) 3 +6 CRR5 = CR6 (CR8R9) hSi (OCaH2aR £) 3? If ((CR2R3) kCR4R5CR6H (CR8R9) hSi (OCaH2aRf) 3) 3C6H4SY ((CR2R3) k CR4R5CR6H (CR8R9) hSi (OCaH2aRf) 3) 3 (i) when X is a substituted benzene structure of the type, as defined above, which may be abbreviated C6H6-w (SiZ3_cYc) w, where w represents the number of substitutions on the benzene ring: Ec. 9A: w x (OCaH2aRf) 3Si (CR8R9) hH + C6H6 - ". SiZ3_c ((CR2R3) kCR ^ CRVj,? C, H6.W [SiZ3.c ((CR2R3) kCR4HCRbR7 (CR8R9) hSi (OCaH2aRf) 3) c) w Ec. 9B: w x CR4R5 = CR6 (CR8R9) hSi (OCaH2aR £) 3 + C6H6.w [SiZ3-c ((CR2R3) kH) c] w? CßHe- [SiZ3-c ((CR2R3) kCR4R5CR6H (CR8R9) hSi (OCaH2aRf) 3) c) w (j) when X is a substituted cyclohexane of the type, as defined above, which may be abbreviated C h H 12 -w Y ", where d w is the number of substituents; so: Ec. 10A: C6H12-w ((CR2R3) kCR4 = CR6R7) w + [(OCaH2aRf) 3 Si (CR8R9) hH]? C6H12.W ((CR2R3) kCR4HCR6R7 (CR8R9) hSi (OCaH2aRf) 3) " For convenience, the reaction of the equations denoted as A or B above is chosen depending on the commercial availability of the starting reagents. In each set of equations where an A and a B are represented, h = 0 in Equation A and k = 0 in Equation B. Specific sources of reagents are listed here later just before the Examples. An effective amount of a transition metal catalyst such as platinum, or a free radical initiator, was employed. Examples of suitable free radical initiators include the azo compounds "VAZO" available from E. I. du Pont de Nemours and Company, Wilmington, DE. These reactions can be conducted at a temperature of about 25 ° C to about 100 ° C. Preferably, the process is conducted at about 80 ° C to about 100 ° C. The pressure used is typically the environment, approximately 1 atm (1.01 x 105 Pa). The reactions were carried out under an inert gas atmosphere, although the use of an air atmosphere is not excluded. The reaction time is typically from about 4 hours to about 24 hours. The use of solvents in these reactions is not required. Suitable solvents that can be used are those capable of dissolving reagents, such as toluene or THF, and which do not interfere with the reaction or generate undesirable byproducts. The desired product can be isolated by any means known to those skilled in the art. Preferably, the desired product is isolated by removing the volatile products under reduced pressure. NMR and mass spectrometry have been used to characterize the product's defects.

Typically, the yields of the material that completely reacted exceeds 95%, with the main impurities being either reversed hydrosilation (Markovnikov) or unreacted -CH = CH2-groups containing incompletely substituted material. The following shows the preparation of the compounds of formula I (k) (and IA (k) when the Si group (OCaH2aRf) 3 is replaced with Si (R10) (OCaH2aR £) 2): Eq HA: CR7R6 = CR4 (CR3R) k (CF2) v (CR2R3) kCR4 = CR6R7 + Hsi (OCaH2aR £) 3 - > (0C_H2aR £) 3SiCR7R6CR4H (CR3R) k (CF2) v (CR2R3) kCR HCR6 R Si (OCaH ^ aRf) 3 The synthesis of the compounds of formula I (k) (and IA (k) when the Si group is replaced) OCaH2aRf) 3 with Si (R10) (OCaH2aRf) 2) can also be performed by inserting unsaturated trifluoroalkoxysilanes or trihalosilanes into the CI bond of I (CF2) VI, followed by reduction of CI to CH using the standard organic reduction reagents , as shown later in Equation 11B. (P. Girard et al., J.A. Chem. Soc. (1980), vol 102, pp 2693-269B describe the use of Sml2 in reduction reactions). Examples of suitable reagents are metallic zinc, tri-n-butyl tin hydride or samarium iodide.

Ec 11B: I (CF:) VI + 2 CR4R5 = CR6 (CR8R9) hSÍ (0CaH2aRf) 3? (OCaH2aRf) 3YES (CR9R8) h CR'ICRV (CF2) VCR R5CR6I (CR8R9) hSi (OCaH2aRf) 3 which can be converted to the following ones, for example, samarium iodide (Sml2), (OCaH2aR_) 3Si (CR9R8) hCRbHCRV (C F2) VCR4R5CR6H (CR8R9) h (OCaH2aR £) 3.

The yields of the fluoroalkoxysilanes of formula I can be > 99% using HSi (OCH2CF3) 3 and CH2 = CHSi (OCH2CF3) 3; slightly lower yields are found than using HSi (OCH_C3F7) 3 and CH2 = CHSi (OCH2F7) 3. It is believed that this is due to the steric demands of large tris (heptafluorobutoxy) silanes. Some branches were observed due to the addition (a) of Markovnikov of silyl hydride. The hydrosilylation of HSi (OR10) 3, wherein R10 is as defined above, on polycarbosilane precursors, for example (Si (CH2CH2CH2Si (CH2CH = CH2) 3) 4, leads to the formation of the "dendrimeric" compounds of formula The synthesis of the dendrimers of formula II can begin with the exhaustive allylation of tetrachlorosilane with an excess of 10% of allylmagnesium bromide in diethyl ether (4 h of reflux) to produce tetralylsilane. room temperature for approximately 1-2 days with either trichlorosilane, dichloromethylsilane or chlorodimethylsilane (25% excess in the presence of palladium catalyst, 10"4 to 10" 5 mol per double bond) and an optional solvent, such as toluene or THF, to give the first generation of dendrimers of formula II containing Si-Cl functional groups. Next, all Si-Cl groups were replaced by groups SiCH2CH = CH2 by the reaction with an excess of br. omil of magnesium in diethyl ether to produce dendrimers with 4 to 12 allyl end groups. The hydrosilylation of these dendrimers by HSi (OCH2CF3) 3, HSi (OCH2 (CF2) 2CF3) 3 or HSi (OCH2CH3) 3 produces the dendrimers of formula II. The route offers a unique flexibility. Not only can the degree of branching be adjusted by replacing the HSiCl3 with HSiCl2CH3 or HSiCl (CH3) 2 in the initial hydrosilylation, but the length of the branches can also be varied. With equally high yields, for example, vinyl-based silane dendrimers can be prepared up to the fourth generation using vinylmagnesium chloride in tetrahydrofuran (THF) in the alkenylation step. (See U.S. Patent 5,276,110 incorporated herein by reference). As an additional benefit, the Si-Cl reactive end groups allow easy functionalization of the surface of the dendrimer to produce the compounds of formula II by direct reaction with alcohols or fluoroalcohols. The compounds of formula III were prepared by dissolving a fluorine-containing silane, such as one having the formula Si (OCH2Rf) 4, wherein Rf is as defined in formula III, or mixed silanes, such as Si (OCH2R £) v (OR) 4-x, wherein R is C_ alkyl to about Cß, and x = l-3, in a solvent in which the water is soluble, such as isopropyl alcohol (IPA). A soluble source of fluorine ion, such as CsF, was added to the solution together with less than a 1.5: 1 molar excess of water.

The solution was maintained, with optional heating, until the water was substantially consumed. The alcoholic byproducts and any unreacted water were then removed from the system by, for example, distillation. The remaining material is an oligomeric silicate with sufficient residual fluorine-containing groups that are soluble in fluorinated solvents. Alternatively, polysilicates of formula III can be made by combining a fluorine-containing silane such as Si (OCH2C3F7) 4 (FBS) with a stoichiometric acid deficiency (ie, <2: 1) of trifluoroacetic acid (TFA) or other acid strong fluorocarboxylic The solution will generally be heated to promote an extensive reaction between the silane and the acid. The reaction by-products (ester, alcohol and any unreacted acid) are then removed, for example, by distillation. The preparation of the oligomeric compounds of formula IV can proceed in a similar manner. In the alternative process using a strong fluorocarboxylic acid, heating is optional. Formula III and formula IV are idealized formulas corresponding to a 100% crosslinking of the SiOH group; however, residual non-crosslinked SiOH groups may exist during the preparation. z is the molar ratio of water or other gelling agent to the silane.

Rf is preferably CF3, C2F5 or C3F7 for formula III and C6F13, nC8F17 and nC? 0F21 for formula IV is preferably 1 or 2. Using trifluoroacetic acid and fluorinated solvents, fluorine-containing compounds of formula I, IA, II , III and IV of the present invention can be condensed in silica networks using the non-aqueous solution-gel techniques. For example, Si condensation (OSi (CH3) 2CH2CH2Si (OCH2C3F) 3 by CF3COOH in perfluoro (butyl THF) (FC-75) produces a clear gel, demonstrating that hybrid inorganic networks can be easily formed in fluorinated solvents. of using these novel fluoroalkoxysilanes is that they are soluble in fluorinated solvents, thus the solution-gel condensation can be handled and inorganic / organic cross-linked materials be formed using fluoropolymers dissolved in perfluorinated solvents such as hexafluorobenzene and perfluoro (butyl-THF) using trifluoroacetic acid. Instead of the more conventional gelling agents, these crosslinked materials can then be used to coat a substrate, such as glass, to form a film The fluorine-containing compounds of formula I, IA, III and IV (and those of formula II which are soluble in fluorinated solvents) of the present invention, may also be used in conjunction with fluoropolymers disu They are used to form semi-interpenetrating networks for a variety of applications including adhesion primers. The compounds of formula II are useful in abrasion resistant materials, impact resistant glasses, and can act as crosslinking agents for some functionalized organic polymers.

EXAMPLES All reactions were carried out in a dry chamber or under nitrogen Vacuum Atmospheres Co. In the examples, all commercial reagents were distilled before use. Trichlorosilane, tetravinylsilane, tetrachlorosilane, vinyltrichlorosilane, allyltrichlorosilane, 1,3,5,7-tetramethylcyclotetra-siloxane, tetracis (dimethylsiloxy) -silane, 1,1,3,3-tetramethyldisiloxane, and 1, 3, 5, 7, 9 -pentamethylcyclopenosiloxane were obtained from Aldrich Chemical Co., Milwaukee, WI, Huis America Inc., Piscataway, NJ or PCR Inc. Gainesville, FL. Trifluoroethanol and n-heptafluoro-butanol were obtained from PCR Inc. Si (OCH2CF3) 4, Si (OCH2 (CF2) CF3) 4, HSi (OCH2CF3) 3, CH2 = HSi (OCH2CF3) 3, Si (CH2CH2CH2Si (CH3) 2CH2CH = CH2) 4, Si (CH2CH2CH2SiCH3 (CH2CH = CH2) 2) 4 / and Si (CH2CH2CH2Si (CH2CH = CH2) 3) 4 were synthesized by slight modifications of published procedures. The platinum-divinyl siloxane complex (Pt concentration of 3-3.5% in xylene, Huís PC072) was obtained from Huís America Inc. and diluted 5: 1 by volume (toluene, Pt complex) before use. Toluene and tetrahydrofuran were reactive grade and were obtained by distillation from calcium hydride before use.

The tetraalkylsilane was synthesized by a modification of a published procedure (J. Organomet, Chem., 84 (1975), pp. 199-229). Vinylpolyfluoroalkanes were prepared from I (CF2) 6I available from PCR Inc. Solvents "FLUORINERT" FC-75 and "FLUORINERT" FC-40 were obtained from PCR Inc. Hexafluorobenzene was obtained from Aldrich Chemical, Inc. The experiments of mass spectroscopy were performed on a four-pole mass spectrometer Finnigan 4615B GC / MS (San José, CA). An electronic impact source configuration operating at 200 ° C and a source pressure of 1.0 x 10"6 Torr was used.The mass spectrometer was scanned at a rate of approximately 1000 Daltons / second. recorded as the sum of the most potassium ion (M + 39) .The NMR of the proton and carbon were determined in a GE instrument model QE-300.The elemental analyzes were carried out by Oneida Research Services Inc., One Halsey Road, Whitesboro, NY. The following abbreviations were used in the description and examples: Et = ethyl FBS = tetra (heptafluorobutoxy) silane, Si (OCH2C3F7) 4 FC-75 = perfluoro (butyl THF) FES = tetra (trifluoroethoxy) silane, Si (OCH2CF3) 4 HFB = hexafluorobenzene, CßF6 HFBS = tri (heptafluorobutoxy) silane, HSi (OCH2C3F7) 3 Me = methyl, CH3 PP-11 = perfluoro phenanthrene TEOS = tetraethoxysilane, Si (OCH2CH3) 4 TFA = trifluoroacetic acid, CF3COOH THF = tetrahydrofuran EXAMPLE 1 Synthesis of Si (CH2CH2Si (OCH2CF3) 3) 4 A mixture of 2.39 g (7.34 mmol) of HSi (OCH2CF3) 3, 2 drops of Pt catalyst and 0.255 g (1.87 mmol) of tetravinylsilane was heated at 90 ° C for 6 hr. After cooling, the residual silane was removed in vacuo leaving a brown oil which was identified as Si (CH2CH2Si (OCH2CF3) 3) 4. MS (m / 3) 1480 (M + 39, 100%). 1153 ((H2C = CH) Si (CH2CH2Si (OCH2CF3) 3) 3 + 39, 20%). 13C NMR (C6D6) 1.31, 1.86, 2.31, 2.53 (SiCH2), 61.8 (c, CH2CF3, 2J (CF) = 36.6 Hz), 124.53 (c, CF3, aJ (CF) = 277.9 Hz). Small amounts of -SiCH (CH3) Si (OCH2CF3) 3 groups were observed due to the addition of Markovnikov (-0.55, 7.79 ppm).

EXAMPLE 2 Synthesis of Si (CH2CH2Si (OCH2 (CF2) 2CF3) 3) 4 The reaction was carried out in a similar manner to Example 1 using 0.250 g (1.83 mmol) of tetravinylsilane and 4.597 g (7.34 mmol) of HSi (OCH2 (CF2) 2CF3) 3. The work gave Si (CH2CH2Si (OCH2 (CF2) 2CF3) 3) 4 as a brown oil. 13C NMR (THF-d8) 1.47, 2.06, 2.32, 2.64 (SiCH2), 61.5 (t, CH2CF2, 2J (CF) = 27.2 Hz), 110-120 (M, (CF2) 2CF3). Small amounts of groups -SiCH (CH3) Si (OCH2 (CF2) 2CF3) 3 were observed due to the addition of Markovnikov (-0.4, 7.87 ppm).

EXAMPLE 3 Synthesis of Si (OSi (CH3) 2CH2CH2Si (OCH2CF3) 3) 4 A solution consisting of 0.497 g (1.51 mmol) of Si (OSi (CH3) 2H) 4, 2.149 g (6.10 mmol) of CH2 = CHSi (OCH2CF3) 3 and two drops of Pt catalyst was heated at 90 ° C during 6 hr. After cooling, the solution was stirred for an additional 16 hr at room temperature. Removal of all volatile products under vacuum gave the product, Si (OSi (CH3) 2CH2CH2Si (OCH2CF3) 3) 4, in quantitative yield. Small amounts of groups -SiCH (CH3) Si (OCH2CF3) 3 due to the addition of Markovnikov were also observed by NMR. 13C NMR (C6D6) -0.636, -0.603 (major isomer, CH3Si), 1.47 (minor isomer, CH3Si), 2.10 (SiCH2), 7.37 (SiCH), 7.40 (CH3CH), 9.03 (SiCH2), 62.14 (c (higher ), CH2CF3, 2J (CF) = 36.5 Hz), 62.21 (c (minor), CH, CF3, 2J (CF) = 36.5 Hz), 125.16 (c, CF3, * -J (CF) = 277.7 Hz). MS (m / e) 1736 (M + 39, 100%) EXAMPLE 4 Synthesis of Si (OSi (CH3) 2CH2CH2Si (OCH2 (CF2) 2CF3) 3) 4 The reaction was carried out in a similar manner to Example 3 using 10,049 g (15.4 mmol) of CH2 = CHSi (OCH2 (CF2) 2CF3) 3, 1241 g (3.78 mmol) of Si (OSi (CH3) 2H) 4, and three drops of Pt catalyst in 10 ml of toluene . The work produced 9.95 g (90%) def Si (OSi (CH3) 2CH2CH2Si (OCH2 (CF2) 2CF3) 3) 4 as the sole product. 13C NMR (THF-d8) -0.797, -0.753 (major isomer, CH3Si), 1.03, 1.40, 1.48 (minor isomer, CH3Si), 2.04 (SiCH2), 6.62 (SiCH), 7.30 (CH3CH), 8.89, 8.93 ( SiCH2), 61.61 (t, CH2CF3, 2J (CF) = 27.6 Hz), 105-120 (m, CF3 (CF2) 2). MS (m / e) 2975 (M + 39).

EXAMPLE 5 Synthesis of Si (OSi (CH3) 2CH2CH2CH2Si (OCH2CF3) 3) 4 A mixture consisting of 3,003 g (8.20 mmol) of CH _- = CHCH2Si (0CH2CF3) 3, 0.672 g (2.04 mmol) Si (OSi (CH3) 2H) 4 and one drop of Pt catalyst was heated at 90 ° C for 4 h, then cooled and stirred room temperature for 16 hr. Volatile products were removed under vacuum leaving 3.44 g (94%) of a yellow liquid identified as Si (OSi (CH3) 2CH2CH2CH2Si (OCH2CF3) 3) 4. aH NMR (C D6) 0.26 (s, 6H), 0.72 (m, 4H), 1.61 (m, 2H), 3.71 (c, 6H). 13C NMR (CD -0.53, -0.12 (s, SiCH3), 14.07, 16.78, 16.81 (SiCH :), 61.53 (c, CH_CF3, J (CF) = 36.5 Hz) A small amount of addition product was also observed of Markovnikov by NMR.

EXAMPLE 6 Synthesis of cyclo- ((CH3) (CF3CH2Q) 3SiCH2CH2CH2) SiQ4) A mixture consisting of 3.595 g (9.82 mmol) of cyclo-CH2 = CHCH2Si (OCH2CF3) 3, 0.525 g (2.18 mmol) of ((CH3XH) SiO) 4 and one drop of Pt catalyst was heated at 90 ° C for 4 hrs, then cooled and stirred at room temperature for 16 hr. The volatiles were removed in vacuo leaving 3.94 g of a brown liquid identified as cyclo- ((CH3) (CF3CH20) 3SiCH2CH2CH2) SiO) 4. XH NMR (C6D6) 0.30 (m, 6H), 0.75 (m, 4H), 1.62 (m, 2H), 3.60 (c, 6H). 13C NMR (C6D6) -1.12 (s, SiCH3), 13.67, 16.58, 21.41 (SICH2), 61.52 (c, CH2CF3, 2J (CF) = 36.3 Hz). Some minor peaks were observed in 13C NMR due to Markovnikov addition products.

EXAMPLE 7 Synthesis of cyclo- ((CH3) (CF3CH2Q) 3SiCH2CH2CH2) SiQ5) A mixture consisting of 3,003 g (8.20 mmol) of CH = CHCR2Si (OCH2CF3) 3, 0.493 g (1.64 mmol) of cyclo- ((CH3) (H) SiO) 5 and one drop of Pt catalyst was heated to 90 ° C for 4 hrs, then cooled and stirred at room temperature for 16 hr. The volatiles were removed in vacuo leaving 3.11 g (89% of a thick yellow liquid identified as cyclo-MC ^) (CF3CH20) 3SiCH2CH2CH2) SiO) 5. H NMR (THF-d8) 0.18 (s, 3H), 0.68 (m, 2H), 0.90 (m, 2H), 1.59 (m, 2H), 4.22 (c, 6H). A small amount of Markovnikov addition product was also observed by NMR.

EXAMPLE 8 Synthesis of cyclo- ((CH3) (CF3CH2Q) 3SiCH2CH2) SiO) 4 The reaction was carried out in a similar manner to Example 3 using 0.525 g (1.53 mmol) of cyclo- ((CH3) (CH2 = CH) SiO), 2.00 g (6.22 mmol) of HSi (OCH2CF3) 3 and two drops of Pt catalyst. The work produced ((CH3) ((CF3CH20) 3SiCH2CH2) SiO) 4 as an oil. Some trisubstituted product was observed in the mass spectrum. 13C NMR (C6D6) -1.38, -1.29 (s, CH3Si), 1.90 (SiCH2), 7.95 (SiCH2), 62.14 (c (major), CH2CF3, 2J (CF) = 36.5 Hz), 61. 83 (c (minor), CH2CF3, 2J (CF) = 36. 6 Hz), 124 .53 (c, CF3, 1J (CF) = 278. 0 Hz). MS (m / e) 1687 (M + 39, 100%), 1361 (trisubstituted product + 39, 12%).

EXAMPLE 9 Synthesis of cyclo- ((CH3) (CF3 (CF2) 2CH20) 3SiCH2CH2) Si? 4) This reaction was carried out in a similar way to Example 3 using 0.500 g (1.45 mmol) of cyclo- ((CH3) (CH2 = CH) SiO) 4, 3.64 g (5.81 mmol) of HSi (0CH2 (CF2) 2CF3) 3 and two drops of Pt catalyst. work produced ((CH3) ((CF3 (CF2) 2CH20) 3SiCH2CH2) SiO) 4 as an oil. Some trisubstituted product (4-5%) was observed by NMR. 13 C NMR (THF-d8) -1.70, -1.65 (s, CH3SÍ), 1.75 (SiCH2), 7.80, 7.88 (SiCH2), 61.55 (t, CH2CF3, 2J (CF) = 27.6 Hz), 105-120 (, CF3 (CF2) 2).

EXAMPLE 10 Synthesis of (CF3CH2Q) 3SiCH2CH2 (CF2) ß (CH2CH2Si (OCH2CF3) 3 This preparation was done in a manner similar to Example 3 using 0.258 g (0.782 mmol) of (CH2 = CH (CF2) 3) 2, 0. 526 g (1.61 mmol) of HSi (OCH2CF3) 3 and two drops of Pt catalyst. The work produced ((CF3CH20) 3SiCH2CH2 (CF2) 3) 2 as a single product by NMR. H NMR (C6D6) 0.68-0.79, 2.0-2.1 (m, pattern AA'BB ', SiCH2CH2Si) 3.51 (c, CH2CF3). 13C NMR (C6D6) 0.685 (s, CH2Si), 25.03 (t, CH CF2), 61.74 (c, CH2CF3, 2J (CF) = 34.8 Hz), 105-120 (m, (CF2) 6), 124.28 (c, CF3 JJ (CF) = 277.9 Hz). MS (m / e) 1045 (M + 39, 100%).

EXAMPLE 11 Synthesis of (CF3 (CF2) 2CH2Q) 3SiCH2CH2 (CF2) 6CH2CH2Si (OCH2 (CF2) 2CF3) 3 This preparation was done in a manner similar to Example 3 using 0.252 g (0.713 mmol) of CH2CH (CF2) 6CH = CH2, 0.998 g (1.59 mmol) of HSi (OCH2 (CF2) 2CF3) 3 and three drops of Pt catalyst. The mixture was heated at 120 ° C for 12 hr. The work produced (CF3 (CF2) 2CH20) 3SiCH2CH2 (CF2) 6CH2CH2Si (OCH2 (CF2) 2CF3) 3 as a single product by NMR. : H NMR (THF-d8) 1.1-1.3, 2.18-2.4 (m, pattern AA'BB ', SiCH2CH2Si), 4.48 (t, CH2CF2). 13C NMR (THF-d8) 0. 678 (s, CH2Si), 61.64 (t, OCH2CF2, 2J (CF) = 27.8 Hz), 105-120 (m, CF2 / CF3), the resonance for CH2CF2 is about 25 ppm and was obscured by the solvent. MS (m / e) 1645 (M + 39, 100%), 1019 (monosubstituted product + 39.2%).

EXAMPLE 12 Synthesis of (CF3CH2Q) 3Si (CH2) 6 (CF2) 6 (CH2) 6Si (OCH2CF3) 3 A mixture consisting of 2,002 g (4.29 mmol) of (CH: = CH (CH 2) 4 (CF 2) 3) 2, 2.82 g (8.64 mmol) of HSi (OCH 2 CF 3) 3 and 10 microliters of Pt catalyst was heated to 90 ° C for 4 h, cooled and stirred for 16 h. The excess silane was removed in vacuo yielding 3.98 g (83%) of a thick liquid identified as (CF3CHO) 3Si (CH2) 6 (CF2) 6 (CH2) 6Si (OCH2CF3) 3. 2H NMR (CfiD6) 0.42 (m, SiCH_), 0.82-1.09 (, CH2CH2), 1.20 (m, CH,), 1.38 (m, CH :), 1.62-1.90 (m, CH2CF2), 3.59 (c, CH2CF3 ). 13 C NMR (C6D6) 9.66 (CH2Si), 20.59, 22.19, 28.89 (CH2), 31.0 (t, CH2CF2), 32. 6 (CH2), 61.54 (c, CH2CF3, 2J (CF) = 36.5 Hz), 124 (c, CF3).

EXAMPLE 13 Synthesis of (CF3 (CF2) 2CH2Q) 3Si (CH2) 6 (CF2) 6 (CH2) ßSi (OCH2 (CF2) 2CF3) 3 A mixture consisting of 1.254 g (2.69 mmol) of (CH2 = CH (CH2) 4 (CF2) 3) 2, 3.37 g (5.38 mmol) of HSi (0CH2 (CF2) 2CF3) 3 and 10 microliters of Pt catalyst it was heated at 90 ° C for 4 h, cooled and stirred for 16 h. Excess silane was removed in vacuo yielding 3.69 g (97%) of a thick, colorless liquid, identified as (CF3 (CF2) 2CH20) 3Y (CH2) 6 (CF2) 6 (CH2) 6Y (OCH2 (CF2) 2CF3) 3. X H NMR (THF-de) 0.90 (m, SiCH 2), 1.40 (m, CH 2), 1.40-1.68 (m, (CH 2) 3), 2.03-2.23 (m, CH 2 CF 2), 4.40 (t, CH 2 CF 2). 13 C NMR (C6D6) 9.73 (CH2Si), 21.04, 22.63, 29.49 (CH2), 31.66 (t, CH2CF2), 33.22 (CH2), 61.35 (t, CH2CF3, 2J (CF) = 24.7 Hz). 107-120 (c, resonances of CF2).

EXAMPLE 14 Synthesis of Si (CH2CH2CH2Si (CH3) 2CH2CH2CH2Si (OCH2CH3) 3) 4 Triethoxysilane (5. 567 g, 0.034 mol) was added to 5. 023 g (8.47 mmol) of Si (CH 2 CH 2 CH 2 Si (CH 3) 2 CH 2 CH = CH 2) 4 and 50 microliters of Pt catalyst and heated to reflux for 5 hr. After cooling, an additional 2796 g (0.0017 mol) of triethoxysilane and one drop of Pt catalyst were added, and the solution was refluxed an additional 8 hr and cooled. Excess triethoxysilane was removed in vacuo leaving 7.78 g (74%) of a tea-colored liquid identified as Si (CH2CH2CH2Si (CH3) 2CH2CH2CH2Si (OCH2CH3) 3) 4. Approximately 20% product was observed due to the addition of Markovnikov . H NMR (C6D6) -0.01 (s, SiCH3), 0.19 (s, SÍCH3 product of Markovnikov), 0.58-0.86 (m, CH2), 1.15 (t, OCH2), 1.4-1.8 (m, CH2), 3.76 ( c, CH3). 13C NMR (C6D6) -2.59 (SiCH3), -2.17 (SiCH3, product of Markovnikov), 16.14, 18.52, 19.62, 20.40, 21.21 (CH2), 19.08 (CH3), 58.7 (OCH2).

EXAMPLE 15 Synthesis of Si (CH2CH2CH2Si (CH3) 2CH2CH2CH2Si (OCH2CF3) 3) t To a mixture containing 1.998 g (3.37 mmol) of Si (CH: CH2CH2Si (CH3): CHCH = CH:) 4 and 30 microliters of Pt catalyst solution were added 6.602 g (0.020 mol) of HSi (OCH2CF3) 3 drip during a period of 0.5 hr. After the addition, the mixture was heated at 90 ° C for 6 hr and was stirred at room temperature for 16 hr. After removing the excess silane in vacuo and filtering through activated carbon, 57.4 g (90%) of Si (CH2CH2CH2Si (CH3) 2CH2CH2CH2Si (0CH2CF3) 3) 4 was obtained as a thick tea liquid. tH NMR (C6D6) 0.08 (s, SiCH3), 0.51-0.84 (m, CH2), 1.40-1.62 (m, CH2), 3.70 (c, CH2CF3). 13C NMR (C6D6) -3.04 (SiCH3), 14.24, 17.11, 18.50, 19.55, 19.93, 20.98 (CH2), 61.52 (CH2CF3, 2J (CF) = 36.6 Hz), 124.5 (CF3, XJ (CF) = 278 Hz ).

EXAMPLE 16 Synthesis of Si (CH2CH2CH2SiCH3 (CH2CH2CH2Si (OCH2CH3) 3) 2) t A mixture containing 5.011 g (7.18 mmol) of Si (CH2CH2CH2SiCH3 (CHCH = CH2) 2) 4, 7.035 g (0.043 mol) of triethoxysilane and 30 microliters of Pt catalyst solution was heated to reflux for 5 hr. After being verified by NMR, an additional 2364 g (0.014 mol) of triethoxysilane and 1 drop of Pt catalyst solution were added, and the resulting mixture was refluxed for 8 hr. After cooling and removing the excess silane in vacuo, 10. 74 g (74%) of Si (CH2CH2CH2SiCH3 (CH2CH2CH2Si (OCH2CH3) 3) 2) 4 was obtained as a tea-colored liquid. Approximately 20% of product was observed due to the addition of Markovnikov. H NMR (C6D6) -0.02 (s, SiCH3), 0.08 (s, SiCH3) product of Markovnikov) 0.58-0.82 (m, CH2), 1.13 (t, CH3), 1.38-1.80 (m, CH2), 3.77 ( c, CH2CH3). 13C NMR (C6D6) -4.40 (SiCH3), -4.14 (SiCH3 Markovnikov), 16.25, 18.57, 18.70, 18.78, 19.62, 20.33 (CH2), 19.07 (CH3), 59.78 (OCH2).

EXAMPLE 17 Synthesis of Si (CH2CH2CH2SiCH3 (CH2CH2CH2Si (OCH2CF3) 3) 2) 4 To a mixture containing 1515 g (2.17 mmol) of Si (CH2CH2CH2SiCH3 (CH2CH = CH2) 2) 4 and six drops of Pt catalyst solution dissolved in 20 ml of toluene were added 7.098 g (0.022 mol) of HSi (OCH2CF3 ) 3 per drip during a period of 0.5 hr. After the addition, the mixture was heated at 100 ° C for 8 hr. After cooling, the NMR showed that the reaction was incomplete and an additional 0.718 g (2.2 mmol) of HSi (0CH2CF3) 3 and i drop of Pt catalyst were added. This mixture was heated at 110 ° C for 6 hr and stirred at room temperature for 64 hr. After removing the excess silane under vacuum, 523 g (73%) of Si (CH2CH2CH2SiCH3 (CH2CH2CH2Si (OCH2CF3) 3) 2) 4 was obtained as a thick orange liquid. 13C NMR (C6D6) -5.07 (SiCH3), 14.35, 17.48, 18.42, 19.50, 19.62, 23.08 (CH2), 61.90 (CH2CF3, J (CF) = 36.7 Hz), 124.6 (CF3, 1J (CF) = 278 Hz ).

EXAMPLE 18 Synthesis of Si (CH2CH2CH2Si (CH2CH2CH2Si (OCH2CF3) 3) 3) 4 A mixture containing 1853 g (2.31 mmol) of Si (CH2CH2CH2Si (CH2CH = CH2) 3) 4, 12.091 g (37.07 mmol) of HSi (OCH2CF3) 3, and 10 drops of Pt catalyst solution in 10 ml of toluene was heated to reflux for 6 hours followed by stirring at room temperature for 90 hr. The mixture was heated an additional 4 hr and cooled. After removing excess silane under vacuum, 7.92 g were obtained (73%) of Si (CH2CH2CH2Si (CH2CH2CH2Si (OCH2CF3) 3) 3) 4 as a thick orange liquid. * H NMR (toluene-d8) 0.59-1.00 (m, CH :), 1.40-1.75 (m, CH2), 3.82 (broad c, CH2CF3). 13C NMR (C6D6) 14.08, 16.53, 17.18, 18.0, 18.5. (CH2, remaining line obscured by toluene), 61.30 (CH2CF3, 2J (CF) = 36.6 Hz), 124.2 (CF3,: J (CF) = 278 Hz).

EXAMPLE 19 Preparation of Polysilicates from FBS FBS / 2-propanol / deionized water / O.5% CsF in 2-propanol was combined with mixing in the given sequence at the following levels by weight, 82.2% / 14.2% / 2.4% / 1.2%. The final solution contained a water / FBS molar ratio of 1.33 and 6.07% by weight solids. This solution was heated slowly for two hours until the volatile products could be removed by distillation. 30 minutes after the distillation, the flask was allowed to cool and the content was analyzed by gas chromatography. The analysis indicated that the water had reacted essentially in its entirety. The cooled material was allowed to evaporate at room temperature until it had a loss of 35% of its original weight.The concentrated material was used to make solutions in hexafluorobenzene (8.6%) and in FC-75 (8.9%). homogeneous and formed clear films when they were coated by flow or immersion on glass plates.The NMR of the silicone 29 was tested in the concentrate and indicated a substantial reaction of the starting material (ca. 90%) to form a wide range of polysilicates with structures from Ql to Q4 (the Si atom had 1 to 4 bonds with other Si atoms through oxygen) (Many of the species may contain residual fluorine-containing groups so that the solubility in fluorinated solvents is observed ).

It is noted that in relation to this date, the best method known by the applicant to carry out the aforementioned invention, is the conventional one for the manufacture of the objects to which it relates. Having described the invention as above, property is claimed as contained in the following:

Claims (13)

1. CLAIMS 1. A compound that has the formula I X (Yes (OCaH2aRf) 3) n I characterized in that: X is at least one organic link selected from the group consisting of: (a) R ^ SiY * -, »; (b) Annular structures : b < > Ib di) Ib (i? I) (C) R-, nSi (OSi (CH3) 2Y) 4.m; (d) CH3SiY2OSiY2CH3; (e) Y3SiOSiY3; (f) Y2 (CH3) Si (CH_) bSi (CH3) Y2; (g) Y_Si (CH_) bSiY3; (h) Y3SiC6H4SiY3; (i) substituted benzene, including all isomers, selected from the group consisting of: (i) C6H3 (SiZ3-cYc) 3; 5 (ii) C6H2 (SiZ3-cYc) 4; (iii) C6H (SÍZ3-CYC) 5; and (j) substituted cyclohexane, including all stereoisomers, selected from the group consisting of: (i) 1,2-C6H10 (Y) 2; 1,3-C6H10 (Y) 2; 1,4- CéHio (Y) 2; (ii) 1,2,4-C6H9 (Y) 3; 1, 2,, 3-C6H9 (Y) 3; 1,3,5-C6H9 (Y) 3; 15 (iii) 1,2,3,4-C6H8 (Y) 4; 1, 2, 4, 5-C6H8 (Y), 1,2,3,5-C6H9 (Y) 4; (iv) 1,2,3,4,5-C6H7 (Y) 5; and (v) C6H (, (Y) 6; and (k) Y (CF2) VY 20 Rf has up to about 18 carbon atoms and is selected from the group consisting of: (a) perfluoroalkyl of C_ to about C_8; b) - [CF: CF (CF3) 0] r-CF2-CF2-CF3, wherein r is an integer of at least 1; (c) -CF2- (CF2-0) q-CF3, wherein q is an integer of at least 2; and (d) -CH2-C (CF3) 2-CF2-CF2-CF3; wherein up to 50% of the fluorine of the Rf group is optionally substituted with hydrogen; a is an integer from 1 to approximately 10; b is an integer from 1 to about 10; c is 1, 2 or 3; m is 0, 1 or 2; n is an integer greater than or equal to 2; v is an integer from 2 to about 14; R1 is C_ alkyl to about C8 or aryl; Y is - (CR2R3) CRR5CRbR (CR8R9) h- R2 to R9 are each independently hydrogen, C_ alkyl to about C8, or aryl, provided that at least one of R4 to R7 is hydrogen; k and h are each independently an integer from 0 to 10, provided that each of k or h is zero; Z is C_ alkyl to about C4, 3,3,3-trifluoropropyl, aralkyl or aryl.
2. 2. The compound according to claim 1, characterized in that X is selected from the group consisting of: R * "mSiY4-m; I (i) Ib (ii) Ib (iii) R ^ SKOSKCHaJ? Y) ^ and Y (CF2) VY; and R £ is CF3, C2F5 or C3F7.
3. 3. The compound according to claim 2, characterized in that it is selected from the group consisting of: Si. (CH2CH2Si (0CH2CF3) 3) 4; Si (CH2CH2Si (0CH2CF2CF3) 3) 4; Si (CH2CH2Si (OCH2 (CF2) 2CF3) 3), Si (OSi (CH3); CH2CH2Si (OCH2CF3) 3) 4; Si (OSi (CH3) 2CH2CH2Si (OCH2 (CF2) 2CF3) 3), Si (OSi (CH3): CH2CH2CH2Si (OCH2CF3) 3) 4; Cyclo- ((CH3) (CF3CH_0) 3SiCH2CH2) SiO) 4; Cyclo- ((CH3) (CF3CH20) 3SiCH2CH2CH2) SiO), cyclo- (CH3) (CF3CH20) 3SiCH2CH2CH2) SiO) b; Cyclo- (CH3 (CF3 (CF2) 2CH20) 3SiCH2CH2) SiO), (CF3CH20) 3SiCH2CH2 (CF2) 6CH2CH2Si (OCH2CF3) 3; (CF3 (CF2) 2CH_0) 3SiCH2CH2 (CF2) 6CH2CH2Si (OCH2 (CF2) 2CF3) 3; and (CF3CH20) 3Si (CH2) 6 (CF2) 6 (CH2) 6Si (0CH2CF3) 34. A compound that has the formula I X (R10Si (OCaH2aR £) 2) n IA characterized in that: X is at least one organic link selected from the group consisting of: (a) R ^ SiY,. ,,,; (b) Annular structures IA (b) (i) IA (fc) (11) IA (b) (iii) (c) R1n? Si (OSi (CH3) 2Y) 4-m; (d) CH3SiY2OSiY2CH3; (e) Y3SiOSiY3; (f) Y2 (CH3) YES (CH2) bSY (CH3) Y2; (g) Y3Si (CH2) bSiY3; 5 (h) Y3SiC6H4SiY3; (i) substituted benzene, including all isomers, selected from the group consisting of: (i) C6H3 (SiZ3.cYc) 3; 10 (ii) C6H2 (SiZ3-cYc) 4; (iii) C6H (SiZ3-cYc) 5; and (iv) C6 (SiZ3.cYc) 6; and (j) substituted cyclohexane, including all stereoisomers, selected from the group consisting of: (i) 1,2-C6H10 (Y) 2; 1, 3-C6H? or (Y) 2; 1,4- Ce.H? O (Y) 2; (ii) 1,2,4-C6H9 (Y) 3; 1, 2, 3-C6H9 (Y) 3; 1,3,5- C6H9 (Y) 3; 20 (iii) 1,2,3,4-C6H8 (Y) 4; 1, 2, 4, 5-C6H8 (Y), 1,2,3, 5-CeH9 (Y) 4; (iv) 1, 2,3,4,5-CßH7 (Y) 5; and (v) CfiH6 (Y) 6; Rf have up to about 18 carbon atoms and is selected from the group consisting of: (a) perfluoroalkyl of C_ to about C? 8; (b) - [CF2CF (CF3) 0] r-CF2-CF2-CF3, wherein r is an integer of at least 1; (c) -CF2- (CF2-0) q-CF3, wherein q is an integer of at least 2; and (d) -CH2-C (CF3) 2-CF2-CF2-CF3; each Rf is optionally substituted with one or more hydrogens; Z is C_ alkyl to about C4, 3,3,3-trifluoropropyl, aralkyl or aryl; Y is - (CR: R3) ». CR4R5CR ° R7 (CR8R9) h-; R1 is C_ alkyl to about C8 or aryl; R2 to R9 are each independently hydrogen, alkyl of C. to about C8, or aryl, provided that at least one of R4 to R7 is hydrogen; R10 is Ci alkyl to about C8 or CdH2aRf; m is 0, 1 or 2; k and h are each independently an integer from 0 to 10, provided that at least one of k or h is zero; a is an integer from 1 to about 10; b is an integer from 1 to about 10; c is 1, 2 or 3; and n is an integer greater than or equal to 2. 5. The compound according to claim 4, characterized in that X is selected from the group consisting of: R1, -SiY4-m; IA (b) (i) IA (b) (ii) i (bXiii) and Y (CF2) VY; and R, is CF3, C2F5 or C3F7. 6. The compound according to claim 5, characterized in that it is selected from the group consisting of: Si (CH.CH:SÍCH3 (0CH2CF3) :) 4; Si (CH2CH2SÍCH3 (OCH2 (CF2) 2CF3) 2) 4; Si (OSi (CH3) 2CH2CH2SiCH3 (OCH2CF3) 2), Si (OSi (CH3) 2CH2CH2SiCH3 (OCH2 (CF2) 2CF3) 2), YES (OSI (CH3) 2CH2CH2CH2SiCH3 (OCH2CF3) 2) 4; 5 (CF3CH20) 2CH3SiCH2CH2 (CF2) 6CH2CH2SÍCH3 (OCH2CF3) 2; (CF3 (CF2) 2CH20) 2CH3SiCH2CH2 (CF2) 6CH2CH2SiCH3 (OCH2- (CF2) 2CF3) 2; (CF 3 CH 0) 2CH 3 Si (CH 2) 6 (CF 2) 6 (CH 2) 6 SiCH 3 (OCH 2 CF 3) 2 Si (CH 2 CH 2 Si (CH 2 CH 2 CF 2 CF 3) (OCH 2 CF 3) 2), Si Si (CH 2 CH 2 Si (CH 2 CH 2 CF 2 CF 3) (OCH 2 (CF 2) 2 CF 3) 2), Si (OSi (CH3) 2CH2CH2Si (CH2CH2CF2CF3) (OCH2CF3) 2), Si (OSi (CH3) 2CH2CH2Si (CH2CH2CF2CF3) (OCH2 (CF2) 2CF3) 2), Si (OSi (CH3) 2CH2CH2CH2Si (CH2CH2CF2CF3XOCH2CF3) 2), ( CF3CH20); (CF3CF2CH2CH2) SiCH2CH2 (CF2) 6CH2CH2Si (CH2-15 CH2CF2CF3) (OCH2CF3) 2; (CF3 (CF2) 2CH20) 2 (CF3CF2CH2CH2) SiCH2CH2 (CF2) 6CH2CH2- Si (CH2CH2CF: CF3) (OCH; (CF2) 2CF3) 3; (CF3CH20) 2 (CF3CF2CH2CH2) Si (CH2) 6 (CF2) 6 (CH2) 6Si (CH2.CH: .CF2CF3) (OCH2CF3) 2; and 20 cycle - ((CH3) (CF3CH20) 2CH3SiCH2CH2) SiO) 4; Cyclo- ((CH3) (CF3CH20) 2CH3SiCH2CH2CH2) SiO) 4; Cyclo- ((CH3) (CF3CH20) 2CH3SiCH2CH2CH2) SiO) y, and cyclo- ((CH3) (CF3 (CF2) CH20) 2SiCH2CH2) SiO) 4. 7. A compound having the formula: If [(CH2) fSi (CH3) 3-d ((CH2) eSi (OR10) d] 4 II characterized in that: d is 1, 2 or 3; e is an integer from 2 to about 10; f is an integer from 2 to about 10; R10 is C_ alkyl to about C8 or CaH2aR £; Rf has up to about 18 carbon atoms and is selected from the group consisting of: (a) perfluoroalkyl of C_ to about C.8; (b) - [CF2CF (CF3) 0] r-CF2-CF2-CF3, wherein r is an integer of at least 1; (c) -CF2- (CF2-0) q-CF3, wherein q is an integer of at least 2; and (d) -CH2-C (CF3) 2-CF: -CF2-CF3; wherein up to 50% of the fluorine of the R £ group is optionally substituted with hydrogen; a is an integer from 1 to about 10; 8. The compound according to claim 7, characterized in that R 10 is CaH 2aRf. 9. The compound according to claim 8, characterized in that it consists of: Si (CH2CH2CH2Si (CH3) 2CH2CH2CH2Si (0CH2CH3) 3), Si (CH2CH2CH2Si (CH3) 2CH2CH2CH2Si (0cH2CF3) 3) 4; Si (CH2CH2CH2SiCH3 (CH2CH2CH2SÍ (0CH2CH3) 3) 2), Si (CH2CH2CH2SÍCH3 (CH2CH2CH2Si (OCH2CF3) 3) 2), and Si (CH2CH2CH2SÍ (CH2CH2CH2SÍ (OCH2CF3) 3) 3) 4. 10. An oligomeric compound that has the formula Yes (OC_.H2aRf) 4-_0_2 III characterized in that: z is an integer from 0.5 to 3.0; a is an integer from 1 to approximately 10; and R £ has up to about 18 carbon atoms and is selected from the group consisting of: (a) Ci perfluoroalkyl up to about C 8; (b) - [CF2CF (CF3) 0] r-CF2-CF2-CF3, wherein r is an integer of at least 1; (c) -CF2- (CF2-0) q-CF3, wherein q is an integer of at least 2; and (d) -CH2-C (CF3) 2-CF2-CF2-CF3; wherein up to 50% of the fluorine of the Rf group is optionally substituted with hydrogen. 11. The compound according to claim 10, characterized in that Rf is CF3, C2F5 or C3F7; and a is 1 or 2. 12. An oligomeric compound that has the formula Rf- (CH2) y-Si (OR) 14) 3.zOz / 2 IV characterized in that: z is a number from 0.5 to 2.5; and is an integer from 2 to about 10; each R14 is independently alkyl of d up to about Ce; carboxy from C_ to approximately C_0, fluorocarboxy from C_ to approximately C_0 or CaH2aRf; a is an integer from 1 to about 10; and Rf has up to about 18 carbon atoms and is selected from the group consisting of: (a) perfluoroalkyl of C_ to about Ci8; (b) - [CF2CF (CF3) 0] r-CF2-CF2-CF3, wherein r is an integer of at least 1; (c) -CF2- (CF-0) q-CF3, wherein q is an integer of at least 2; and (d) -CH2-C (CF3) 2-CF2-CF2-CF3; wherein up to 50% of the fluorine of the Rf group is optionally substituted with hydrogen. 13. The oligomeric compound according to claim 12, characterized in that Rf is C6F? 3, n-C8FX or n-C, F? and a is 1 or 2.