NEW FLUORINATED COMPOUNDS, THEIR SYNTHESIS AND USE

Technical field

The present invention relates to new fluorinated compounds, to

their synthesis and to their use particularly but not exclusively as

surfactants and as slip agents.

Background art

Fluorinated surfactants are currently widespread, since they

reduce surface tension more than any other known surfactant. Currently,

thanks to their particular properties, fluorinated surfactants are used

for example in the field of extinguishing agents, such as extinguishing

foams, because they increase the wettability of the extinguishing agent

such as water. In particular, fluorinated surfactants have a film-forming

action on the surface, blocking the combustible vapors and making it

difficult for them to reignite. In formulations for extinguishing foams,

fluorinated surfactants make the foam more fluid and therefore faster in

spreading on the front of the fire and also more resistant to hydrocarbon

pollution.

Categories of fluorinated surfactants, disclosed in scientific and

patent publications, are already commercially available.

US4278552 and US4511733 disclose fluorinated amino acids obtained

from the reaction between fluorinated epoxides and primary or secondary

amines having the general formula HN (R2) -Rl-COOQ. No reference is made to

the possibility to replace the amines with other groups or to the

possibility to react a fluorinated epoxide with an amine group in the

absence of other acid groups or related salts on the organic molecule.

US6706923 discloses fluorinated iodo and/or alkenyl surfactants

which use allyl glycidyl ether as epoxide group among the initial

reagents for the synthesis. Besides relating to products that are

different from the ones described here, US6706923 mentions neither the

possibility to open the epoxide with hydroxyl groups nor the properties

of the products that can be thus obtained.

US3172910 discloses fluorinated compounds having the formula Rf-

(CH ₂ ) _m -S- (CH ₂ ) _n COOH. To produce these compounds (see, in this regard,

FR2083422, US3686283, FR2113219, EP0526976A1, US4845300 and US6391948) it

is first necessary to synthesize fluorinated thiols having the general

formula Rf (CH ₂ ) _m SH, a phase which requires many onerous steps, including

the addition of ethylene to the perfluoroalkyliodides C _n F _2n+ iI, the

subsequent reaction with thiourea, and finally the corresponding basic

hydrolysis of the addition product. These operations are generally

accompanied by odorous emissions that cannot be neglected from the plant

and environmental standpoint .

Disclosure of the invention

The aim of the present invention is therefore to provide

fluorinated compounds that overcome the drawbacks of known products .

An object is to provide fluorinated products having improved

surfactant properties, a balance between oil- and water-repellence that

makes them suitable for various uses, and a significant lubricating

power.

Another object is to provide a method that is fast, inexpensive,

safe, non-toxic and characterized by high yields, for the synthesis of

the fluorinated products cited above.

Another object is to provide particularly advantageous uses of the

fluorinated products cited above.

This aim and these and- other objects are achieved by a fluorinated

compound as claimed in claim 1.

This aim and these and other objects are also achieved by a method

for synthesizing the fluorinated compounds according to the invention as

claimed in claim 9.

This aim and these and other objects are also achieved by the use

of the compounds according to the invention as claimed in claims 14 and

15.

Ways of carrying out the invention

In a first aspect, the invention relates to new fluorinated

compounds having the general formula (I)

(I) where

Rf is a saturated perfluorocarbon chain or a mixture of saturated

perfluorocarbon chains which are preferably linear, optionally comprising

ramified or cyclic portions, having the formula C _n F _2n+I - in which n is an

integer comprised between 4 and 20, preferably between 6 and 14, and more

preferably is 6 or 8;

R is selected between hydrogen and a linear or ramified alkyl C ₁ -C ₅

group, preferably R is CH ₃ - and more preferably R is H;

B is selected among :

i) an ether group -0-,

ii ) a thioether group -S-,

iii) an amine having the general formula N

R ₂ where R ₂ is selected among :

iii-a) hydrogen,

iii-b) C ₁ -C5 alkyl

1 I AU 1 • 1 • 1 • -c \ ) a group 1 havi • ng ^' J t-Ih-e f _Jγ ormul T a where R and Rf

are a R ₁ is selected among:

i) a linear or ramified group having the formula — (C _p H _2P ) -, where

p is an integer comprised between 1 and 50, preferably between 2 and 10;

15 ii) a group having the formula - (C _p H _2P ) _q -Cgϊ- ₄ - (C _p iH _2P i) r~ where q

and r are each independently 0 or 1, pi is an integer comprised between 1

and 50 and p is as defined above;

iii) a group having the formula - (C _p H _2P ) _q -CeH,}- (CH ₂ CH ₂ O) _D ~ where

p and q are as defined above and D is an integer comprised between 1 and

0 40; iv) a group having the formula (C _p H _2p ) CeH ₄ (CHaCHO)^.

CH ₃ where p is defined above and F is an integer comprised between 1 and 40;

■v) a group selected among:

^v~a) -(CH ₂ CH ₂ O)-C ₆ H ₄ -(CH ₂ CH ₂ O ₇ - D D ₁ 5

v-b) -(CH ₂ CH O) -C ₆ H ₄ -(CH ₂ CH O) — I F I F ₁

CH ₃ CH ₃

v-c) -(CH ₂ CH ₂ O) -C ₆ H ₄ -(CH ₂ CH O) — D I F

CH ₃

where D is as defined above, Di and Fi are integers and each is

independently comprised between 1 and 40 ;

vi ) a group having the formula — ( CH2CH2O ) D~ where D is defined

above ;

^CH 3 vii) a group having the formula /QLJ Q _U _ Q _λ where F is as defined

F above; viii) an ethylene oxide and propylene oxide block copolymer having

the formula CH- ₃

I ³ -(CH ₂ CH-O)-(CH ₂ CH ₂ -O)-

F D where F and D are as defined above;

ix) an ethylene oxide-propylene oxide-ethylene oxide block

copolymer having the formula CH- _s CH-*

I . I

-(CH ₂ CH- O)-(CH ₂ CH ₂ -O)-(CH ₂ CH- O)-

F D G where F and D are as defined above, G is an integer comprised between 1

and 40;

t, A and b are each independently 0 or 1;

T is an atom of carbon or an atom of nitrogen;

R ₃ is selected among:

i) R, where R is as defined above,

ii) a-PQ group where P is an anionic group or its corresponding

neutral conjugate acid, and preferably is selected among:

ii-a) -COOQ,

ii-b) -SO ₃ Q,

ii-c) -OSO ₃ Q,

and Q is selected among:

ii-d) hydrogen,

ii-e) a cation of alkaline metals,

ii-f) an ammonium ion, optionally mono-, di- or

trisubs'tituted with one or more of:

ii-f-1) Ci-Cio alkyl, as CH ₃ -, (CH ₃ ) ₃ C-, C ₄ H ₉ -, C ₈ H ₁₇ -,

preferably C1-C5 alkyl,

ii-f-2) a group having the formula where R and Rf are as defined above, or

ii-f-3) C ₁ -C ₅ hydroxyalkyl;

iii) a group -R ₉ -PQ where P and Q are as defined above and where Rg

is selected among:

iii-a) a linear or ramified group having the formula -

(C _p gH ₂ ( _p9 ))- where p9 is an integer comprised between 1 and

50, preferably between 2 and 10.;

iii-b) a . group having the formula - (C _p gH ₂ ( _P9 ) ) (C _p i ₉ H ₂ (pi ₉ ) ) r ₉ ~ where q9 and r9 are each independently 0 or

1, pl9 is an integer comprised between 1 and 50, and p9 is as

defined above;

iii-c) a group having the formula — (C _p gH ₂ ( _p9 ) ) _q9 ~CgH ₄ -

(CH ₂ CF^O) _D g- where p9 and q9 are as defined above and Dg is

an integer comprised between 1 and 40;

. . . ^ . . . . - . -(Cp ₉ H ₂ Pg)-C ₆ H ₄ -(CH ₂ CH O)- lii-d) a group having the formula r-

CH ₃ ^Fs where p9 has been defined above and Fg is an integer

comprised between 1 and 40;

iii-e) a group selected among: iii-e-l) (CH ₂ CH ₂ O)-C ₆ H ₄ -(CH ₂ CH ₂ O)—

D ₉ D ₁₉

iii-e-2) -(CH ₂ CH O) -C ₆ H ₄ -(CH ₂ CH O) —

I F ₉ I F ₁₉ CH ₃ ⁹ CH ₃

iii-e-3) -(CH ₂ CH ₂ O) -C ₆ H ₄ -(CH ₂ CH O)— 10 ° ⁹ C ^C HH ₃ ^F9

where Dg and Fg are as defined above, Dig and Fig are integers

and each is independently comprised between 1 and 40;

iii-f) a group having the formula — (CH ₂ CH ₂ O) _D9 ~ where Dg is

as defined above;

CH ₃

I D iii-g) a group having the formula ._ , , I . . _ . where Fg is as

—(L-H ₂ Un- O)- defined above; F ₉

iii-h)- an ethylene oxide and propylene oxide block copolymer

having the formula

CH ₃

-(CH ₂ CH- O)-(CH ₂ CH ₂ - O)- 0 ^F 9 ° ⁹ where Fg and D ₉ are as defined above;

iii-i) an ethylene oxide-propylene oxide-ethylene oxide block

copolymer having the formula ^•

CH ₃ CH ₃

-(CH ₂ CH- O)-(CH ₂ CH ₂ -O)-(CH ₂ CH- O)- 5 F ₉ D ₉ G ₉

where Fg and Dg are as defined above and Gg is an integer

comprised between 1 and 40 ;

R ₄ is hydrogen or a linear or ramified C ₁ -C ₅ alkyl group; preferably

methyl, more preferably H;

Y is hydrogen or a group having the formula ( II )

(H ) where

u, v and z are integers and each is independently equal to 0 or 1;

E is defined as B;

R ₅ is hydrogen or a linear or ramified C ₁ -C ₅ alkyl group; preferably

methyl and more preferably H;

Rβ is selected among:

i) R, where R is as defined above

ii) a group -PQ, where P and Q are as defined above;

iii) a group -R ₁₀ -PQ, where P and Q are as defined above and Rio is

selected among:

iii-a) a linear or ramified group having the formula -

(C _p ioH ₂ ( _p io) ) ~ where plO is an integer comprised between 1 and

50, preferably between 2 and 10;

iii-b) a - (CpI ₀ H _{2 (p} io) ) _q io-C ₆ H ₄ - (CpI ₁₀ H ₂ (piio) ) no" group, where

qlO and rlO are integers and each is independently equal to 0

or 1, pllO is an integer comprised between 1 and 50, plO is

as defined above ;

iii-c) a~ ( CpIoH ₂ (pio) ) qio~CgH4- ( CH ₂ CH ₂ O ) Dio~ group, where plO

and qlO are as defined above and D ₁₀ is an integer comprised

between 1 and 40;

-(Cp _1o H ₂ Pio)-C ₆ H ₄ -(CH ₂ CH O)- iii-d) a group having the formula ' MO ^•

CH ₃ where plO is as defined above and FlO is an integer comprised

between 1 and 40;

iii-e) a group selected among

iii-e-1) -(CH ₂ CH ₂ O) -C ₆ H ₄ -(CH ₂ CH ₂ O)

^D 10 D ₁₁₀

iii e ₂₎ " ^(CH 2 ^{CH 0)} - ^C 6 ^H 4-(CH ₂ CH O) — L ^F 10 I ^F 110 L-π3 CH ₃

iii-e-3) -(CH ₂ CH ₂

where D ₁₀ and Fχo are as defined above, Duo and Fno are

integers and each is independently comprised between 1 and

40;

iii-f) a group having the formula - (CH ₂ CH ₂ O) DIO~ where D ₁₀ is

as defined above;

CH ₃ iii-g) a group having the formula -(CH ₂ CH-O)- where F10 is

F ₁₀ as defined above;

iii-h) an ethylene oxide and propylene oxide block copolymer

having the formula

CH ₃

-(CH ₂ CH- O)-(CH ₂ CH ₂ - O)- F ₁₀ D ₁₀

where Fi o and Dio are as defined above ;

iii-i ) an ethylene oxide-propylene oxide-ethylene oxide block

copolymer having the formula

CH ₃ CH ₃

-(CH ₂ CH- O)-(CH ₂ CH ₂ - O)-(CH ₂ CH- O)- F ₁₀ D ₁₀ G ₁₀

where Fχo and Di o are as ^■ defined above and Gio is an integer

comprised between 1 and 40 ;

R ₇ is selected between :

i ) hydrogen,

ii ) a group having the formula RTCH2CHCH2— _w here Rf and R are

OR as defined above;

R ₈ is selected among:

i) a linear or ramified group having the formula — (C _P8 H ₂ ( _P8 ) ) ~

where p8 is an integer comprised between 1 and 50, preferably

between 2 and 10;

ii) a group having the formula - (C _p gH ₂ ( _P8 ) ) q ₈ ~C ₆ H4- (CpIeH ₂ ( _P i ₈ ) ) r8~

where g8 and rδ are each independently equal to 0 or 1, pl8 is an

integer comprised between 1 and 50, and p8 is as defined above;

iii) a group having the formula - (C _p sH ₂ ( _P8 ) ) _qS ^{^} C _θ H,}- (CH ₂ CH ₂ O) _D8 ~

where p8 and q8 are as defined above and Ds is an integer comprised

between 1 and 40;

-(Cp ₈ H ₂ Pa)-C ₆ H ₄ -(CH ₂ CH O)- iv) a group having the formula | p where pδ is

CH ₃ ⁸ as defined above and FQ is an integer comprised between 1 and 40;

v) a group selected among: _v - _a ) (CH ₃ CH ₂ O)-C ₆ H ₄ -(CH ₃ CH ₂ O)--

D ₈ D ₁₈

-(CH ₂ CH O) -C ₆ H ₄ -(CH ₂ CH O) — v-b) I F ₈ I F ₁₈

CH3 CH3

v- c ) -(CH ₂ CH ₂ O) -C ₆ H ₄ -(CH ₂ CH O) —

where Ds and Fβ are as defined above, Die and Fig are integers each

independently comprised between 1 and 40;

vi) a group having the formula -(CH ₂ CH ₂ O) _D g- where Ds is as

defined above;

CH ₃ vii) a group having the formula _fCH CH-OV- where Fs is as

F ₈ defined above;

viii) an ethylene oxide and propylene oxide block copolymer having

the formula I 3

-(CH ₂ CH- O)-(CH ₂ CH ₂ - O)- F ₈ D ₈

where Fg and Dg are as defined above;

ix) an ethylene oxide-propylene oxide-ethylene oxide block

copolymer having the formula

where Fg and Dg are as defined above and Gg is an integer comprised

between 1 and 40;

wherein:

if T is carbon, then b is 1,

if T is nitrogen, then b is 0, and

if B is -N(R ₂ )-, then A and v are both equal to 0.

In a highly preferred embodiment, in which in the compounds having

the formula (I) B is oxygen or sulfur, it has been found surprisingly

that these compounds reduce to a greater extent than known products the

surface tension of the formulations that contain them. Without intending

to be bound to particular theories, it is believed that this may be due

to the decrease of the polarity of the molecule and to its better

orientation in the system.

In compounds having the formula (I) in which instead B is -NR ₂ -,

and both A and v are equal to zero, they have proved to be surprisingly

suitable as cationic surfactants for applications in water-based systems

or as fluorinatect solid lubricants.

Among the compounds having the formula (I), attention is called to

the subgroup in which A is zero, and more preferably the subgroup in

which t=0, v=0, z=0, u=l, R ₈ =-C _P8 H _2p8 , R ₇ =CH ₃ -, a group having the

general formula (III) :

RfCH ₂ CHCH ₂ -B-(Cp ₈ H ₂ P ₈ )CH ₃

^0R (III)

As also detailed hereinafter, the compounds having the formula

(III) in which B is an ether or thioether bridge have physical properties

which are similar to the traditional RF-RH waxes disclosed for example in

US5202041, but their production process is faster and less expensive, so

that their use is preferable with respect to said waxes. As also

described hereinafter, the compounds having the general formula (I) , and

preferably the ones in which A and v are 0, have been found to be

particularly suitable for use as slip agents to be used for example in

sports activities on snow.

Compounds having the formula (I), especially but not exclusively in

the cases in which there are two perfluorinated chains and with A=I, can

be used advantageously in the papermaking sector to obtain oil- and

water-repellent paper to be used in various fields but in particular in

the food sector, the packaging sector, as labels, et cetera.

In the examples that follow, n, when present, can assume the values

4, 6, 8, 10, 12, 14, 16, 18. In one embodiment, the products from Ia) to

4b) in which n is present are constituted by a mixture of homologous

products with a variable n, wherein n is selected among the discrete

values cited above.

Preferred examples of compounds having the formula (I) are:

la) KOOC CH- H COOK

C ₈ F ₁₇ CH ₂ CHCH ₂ CH ₂ CHCH ₂ F ₁₇ C ₈

OH OH

Ib) 8 17 2 2 -CH

OH

Preferred examples of compounds (I) with B and optionally E, equal

g) C ₈ F ₁₇ CH ₂ CHCH ₂ SCH ₂ CH ₂ SO ₃ Na

OH

C ₈ F ₁₇ CH ₂ CHCH ₂ SCH ₂ CH ₂ CH ₂ SO ₃ Na h) OH

C _n F _2n+1 CH ₂ CHCH ₂ SCH ₂ C ₆ H ₄ SO ₃ Li i ) OH

m) C _n F2n+iCH2CHCH2SC8H-i ₇

OH

Specific examples of compounds (I) with B, and optionally E, equal

are :

^{a )}

^{3b )} C _n F _2n+ ICH ₂ CHCH ₂ OCH ₂ CH ₂ SO ₃ Li

OH

^{3 c )}

3d) C _n F _2n+ ICH ₂ CHCH ₂ O(CH ₂ CH ₂ O) H

13

OH

^3e > C _n F _2n+1 CH ₂ CHCH ₂ O(CH ₂ CH ₂ ) ₁₇ CH ₃

OH

Specific examples of compounds (I) with B, and optionally E, equal

to -N(R ₂ )- are:

^{4 a} >

^4b >

In another aspect, the invention relates to compositions comprising

the compounds having the formula (I) as described above. The compounds

having the general formula (I) can be used as such or in the form of

compositions such as aqueous solutions or solutions of other solvents,

such as alcohols such as methanol, ethanol, n-propanol, isopropanol, amyl

alcohol, n-hexanol and the like, ketones such as acetone, methyl ethyl

ketone, methyl isobutyl ketone, methyl-n-propyl ketone, diethyl ketone

and the like, glycols such as diethylene glycol, propylene glycol and the

like, esters such as ethyl acetate, butyl acetate, ethyl propionate,

butyl propionate, dioxane, n-methyl pyrrolidinone, tetrahydrofuran,

dimethylforrαamide, toluene, chloroform, methyl chloride, dichloromethane .

These solvents can be used pure or in a mixture, in the presence of water

or not .

Compounds having the general formula (I) can be used as such or

with other fluorinated compounds which are similar or different, such as

for example fluorinated and non-fluorinated amphoteric surfactants such

as betaines, fluorinated and non-fluorinated anionic surfactants such as

carboxylic or sulfonic acids, sulfuric esters, phosphates and phosphoric

acids, thiosulfates et cetera, fluorinated and non-fluorinated cationic

surfactants such as amine salts, quaternary amine compounds.

In the compositions that comprise the compounds of formula (I) in

the field of paints and in preparations for extinguishing foams, the

quantity of fluorinated compound (I) is comprised between 0.001% and 10%

by weight, preferably between 0.001% and 5% and more preferably between

0.1% and 2% by- weight on the weight of the final composition.

If the compounds (I) are used as solid lubricants for snow sports

equipment, they can be used alone or in a mixture for example with

paraffins, mixtures of paraffins, mixtures of paraffins and mineral oils,

fluorinated compounds such as Rf-Rh and fluorinated compounds such as Rf-

Rf, PTFE, boron nitride, molybdenum sulfide, fluorographite . In these

mixtures the compound having the formula (I) is present in a quantity

comprised between 0.3% and 30%, preferably between 3% and 15%.

Some particularly preferred compositions will be discussed

hereinafter in the context of their specific applications.

Some of the characteristics of the invention might be defined in

detail only with regard to a single product category comprised in the

general formula (I) . However, if not. specified, the person skilled in the

art will understand immediately, by relying on ordinary knowledge in the

field, that the definition of these characteristics and advantages can be

extended to all the compounds having the formula (I) .

In another aspect, the invention relates to the use of the

compounds having the formula (I) as defined above and of the compositions

that comprise them. The compounds according to the invention, as such or

in the form of compositions, have been found to be particularly suitable

as agents designed to be applied to fluid and solid materials in order to

give these materials a low surface tension.

The compounds having the formula (I) are therefore particularly

suitable to be used:

- as non-specific fluorinated surfactants,

- as solid lubricants, particularly to increase the slipperiness

and oil-hydro-repellence characteristics of surfaces that constitute

hulls of watercraft and the like and/or their cladding materials,

sleighs, chutes, ski bases, and the like;

- as additives in polymerization processes in emulsion,

- as corrosion inhibitors,

- as additives in coatings for wood, glass, metal ^' , brick, cement,

natural and synthetic stone,

- as additives in processes for treating paper, fabrics,

- as additives in enamels and in waxes for floors, for furniture

and for shoes,

- as additives in cleaning products,

- as wetting agents,

- as additives in glass anti-mist formula,

- as additives for extinguishing agents and fire-resistant

compositions .

In particular in the coating sector, it has been found that the

fluorinated compounds having the formula (I), preferably the ones in

which A is 1, more preferably the ones in which A is 1 and Y is hydrogen,

surprisingly have a much higher performance than currently commercially

available surfactants, since for an equal concentration with respect to

known products they have numerous technical advantages . Among these

advantages, mention can be made of:

- improvement of leveling and flow,

- improvement of gloss,

- reduction of the orange-peel phenomenon,

- increase in scratch-resistance,

- improvement of substrate wetting (better preventing the formation

of craters and pinholes),

- better control of pigment separation

- improvement of corrosion resistance.

The compounds having the formula (I) where A is 1 can also be used

with great advantages in the field of extinguishing agents and in

particular in extinguishing foams.

A particularly interesting application of the compounds having the

formula (I) is the preparation of fluoroprotein fire-retardant

compositions. Emulsions based on hydrolyzed animal or plant protein are

widely used in the fire-retardant foam sector, because they form very

dense and stable foams. These products, however, have some disadvantages,

since they form very compact foams, which are difficult to spread over

the front of the fire and the resistance of the foam to the presence of

hydrocarbons is limited. Accordingly, in order to improve the

effectiveness of these protein emulsions, small quantities of fluorinated

surfactants are incorporated, allowing to obtain a foam which is more

fluid, less compact and more resistant to hydrocarbon contamination. The

quantity of fluorinated surfactant to be introduced in the mixture is

such as to have a final concentration generally comprised between 0.005%

and 2%. Higher quantities are possible if required.

Moreover, fluorinated surfactants offer higher resistance to

chemical attacks with respect to normal surfactants.

During specific tests conducted on the compounds according to the

present invention, it has been found that in particular surfactants

having the formula (I) and provided with a hydrophilic part, therefore in

all cases in which A and/or v are different from zero, -B- and/or -E- are

a -N(Ra)- group, and/or in all cases in which there is one or more -

(CH ₂ CH ₂ O) ₀ -, (CH ₂ CH (CH ₃ ) 0) _F - groups, allow to improve the characteristics

of the formulations for extinguishing foams with respect to known

surfactants. These characteristics are determined by means of some

experimental tests, such as for example the measurement of the expansion

ratio, i.e., the ratio between the generated foam volume and the volume

of the initial aqueous solution, the settling time, i.e., the time

required to recover one quarter of aqueous solution from the foam left to

rest in a separation funnel, and the measurement of the fluidity of the

foam, i.e., the rate at which the foam covers a preset portion of an

inclined plane.

Compounds having the formula (I), preferably where A is 0, more

preferably compounds having the formula (III), can be incorporated

advantageously in the bases of skis in order to improve their inherent

characteristics. Bases are constituted generally by high-density

polyethylene and are manufactured by extrusion or sintering of the

powdered polymer. Accordingly, bases can be formed by using a composition

which comprises polyethylene powder and compounds having the formula (I),

where these last are present in a percentage comprised between 2% and 10%

by weight on the final composition. The resulting sheets have a lower

surface tension value than polyethylene without additions.

Moreover, compounds having the formula (I) can be used as

compositions in a mixture with paraffin waxes so as to improve their

functional sliding characteristics. The mixture can be prepared by simple

incorporation by melting, optionally with the addition of compatibility

enhancing agents.

In another aspect, the invention relates to a method for the

synthesis of fluorinated compounds having the formula (I) as defined

above .

The compounds having the formula (I) to which the present invention

relates can be synthesized easily starting from fluorinated epoxides

having the general formula (AA) :

(AA)

obtained in turn according to a per se known process, to which reference

is made here (see for example Cirkva, Ameduri, Paleta in the Journal of

Fluorine Chemistry 84 (1997) 53-57, Matuszczak, Feast in the Journal of

Fluorine Chemistry 102 (2000) 269-277), which is simple and not very

onerous .

The fluorinated epoxide obtained is then made to react with

where Z is hydrogen or a group having the formula (CC) :

H

where the various variables are as defined above. Z differs from Y

because for Y there is the variable R ₇ , which does not exist for Z.

Therefore, the reaction between fluorinated epoxide and amine group

described here is limited to the case in which no other acid polar groups

and their salts are present in the organic molecule.

The addition of the two reagents occurs under different reaction

conditions depending on the B and E groups that are involved.

In a first embodiment, B, and optionally E if present, are equal

and are -S-. In this embodiment the reaction temperature must be

comprised between 2O ⁰ C and 120 ⁰ C.

In this embodiment, the reaction can be performed in the mass or in

the presence of an inert solvent such as ' water, ethanol, isopropanol,

methyl ethyl ketone, tetrahydrofuran, dioxane, methyl isobutyl ketone,

toluene, N methyl pyrrolidinone, alkanes, or mixtures thereof.

In a specific embodiment of the method in the case in which B and E

are -S-, the reagents are placed in a reaction flask provided with

mechanical agitation, thermometer, coolant in countercurrent, a flow of

nitrogen and a thermostat-controlled oil bath. The reaction temperature

is comprised between 20°C and 120°C, preferably between ^' 40 ⁰ C and 80 ⁰ C,

and the disappearance of the epoxide is monitored for example by gas

chromatographic analysis. Usually, the reaction time varies between 4 and

20 hours, preferably between 6 and 12 hours.

If the compound having the formula (BB) contains acid groups of the

-COOH, -SO ₃ H, or -OSO ₃ H type, ' it is possible to salify them preferably

but non necessarily before the addition to the epoxide in order to

improve their solubility by making them react with inorganic bases such

as NaOH, KOH, LiOH, NH ₄ OH and mixtures thereof or with organic bases such

as primary, secondary or tertiary amines and mixtures thereof. The use of

inorganic bases or of tertiary amines can also precede the reaction of

the reagent having the. formula (BB) with the fluorinated epoxide (AA) .

The finished product can be placed in solution or can be kept as such.

In a different embodiment, B and optionally E if present are both

-O- . In this embodiment, it is necessary that Q, if present, be selected

between a cation of alkaline metals and an ammonium ion trisubstituted by

alkyl groups such as R ₂ .

It is also necessary for the reaction to occur in the presence of

an inert solvent such as methyl ethyl ketone, tetrahydrofuran, dioxane,

methyl isobutyl ketone, toluene, t-butyl methyl ether and mixtures

thereof.

It is also necessary to provide, in the reaction environment, a

Lewis acid, preferably in a quantity comprised between 0.001% and 1% by

weight with respect to the mass of epoxide.

The reaction temperature must also be comprised between 20 °C and

120 ⁰ C.

In a specific embodiment of the method, in the case in which B and

E are -O-, the compound having the formula (BB) is placed in a reaction

flask provided with mechanical agitation, thermometer, coolant in

countercurrent, stream of nitrogen and thermostat-controlled oil bath. In

the reaction environment there must be a quantity of a Lewis acid,

usually boron trifluoride etherate, in a quantity comprised between

0,001% and 1% by weight with respect to the mass of epoxide. The

fluorinated epoxide or mixture of epoxides with n of different value is

placed in a dripping funnel. The reaction temperature is comprised

between 20 ⁰ C and 120°C, preferably between 40 ⁰ C and 8O ⁰ C. At this

temperature, the epoxide is added drop by drop to the reaction

environment . The disappearance of the epoxide is monitored for example by

gas chromatographic analysis. Usually, the reaction time varies between 4

and 20 hours, preferably between 6 and 12 hours. The product can be

placed in solution or kept as such.

If B, and optionally E if present, are -N(R ₂ )- (the case in which A

and v are equal to 0) , the addition with the epoxide can occur in the

mass or in the presence of inert solvents such as for example alcohols

such as methanol, ethanol, isopropanol, glycols such as ethylene glycol,

propylene glycol,- ketones such as acetone, methyl ethyl ketone, methyl

isobutyl ketone, esters such as butyl or ethyl acetate, and dioxane,

tetrahydrofuran, N methyl pyrrolidinone and mixtures thereof.

The reaction temperature must be comprised between 20°C and 12O ⁰ C;

Q must also be selected among cations of alkaline metals and, if. (BB)

contains acid groups, they must first be salified with an equimolar

quantity of a strong base.

In a specific embodiment of the method in the case in which B and E

are -N(R ₂ )-, the reagents are placed in a reaction flask equipped with

mechanical agitation, thermometer, coolant in countercurrent, flow of

nitrogen and thermostat-controlled oil bath. The reaction temperature is

comprised between 20°C and 120 ⁰ C, preferably between 40°C and 80 ⁰ C, and

the disappearance of the epoxide is monitored for example by gas

chromatographic analysis. Usually, the reaction time varies between 4 and

20 hours, preferably between 6 and 12 hours. The product can be placed in

solution or kept as such.

If E is present, when B is different from E and one of the two is

-0- while the other is a -S- group or a -N(R ₂ )- group, the different

reactivity of the involved nucleophiles leads to a first addition of the

fluorinated epoxide to the thioether or amine group and then, if

required, also to the addition of the epoxide to the hydroxyl group. The

conditions of addition to the individual functionalities are identical to

the ones described above.

In the cases in which B and E are different from each other ^' and

neither is a -0- group, it is not possible to add selectively the epoxide

first to one group with respect to the other. In this case it is

necessary to add simultaneously the epoxide to both functionalities by

following the- methods already described.

In every embodiment, the method according to the invention leads to

molecules having the formula (I) in which R is hydrogen. However, once

the product of addition has been obtained, it is possible to

functionalize the hydroxyl group with methods which are well-known in the

field, so as to obtain all the other compounds having the formula (I) .

The compounds having the formula (I) described above can also be

used as monomers for synthesis of polymers of different kinds.

If one intends to obtain these polymers,- R is not functionalized

but remains hydrogen. In this way it is possible to use the -OH alcohol

function as a reactive group for the subsequent synthesis of polymers

such .as for example polyurethanes and polyesters,

. The polymers can be used to obtain an oil-hydro-repellence effect

by treating various substrates such as paper, leather, fabrics and

marble.

Other characteristics and advantages of the present invention will

become better apparent from the description of the following preferred

embodiments, intended merely as non-limiting examples. In all the

examples that follow, the percentages are expressed as percentages by

weight unless otherwise specified.

Example 1

The product

is prepared with the procedure described below.

The following are loaded into a four-neck 500 ml flask equipped

with mechanical agitator, thermometer, countercurrent condenser, mounted

on a temperature-controlled oil bath:

a) 15.00 g (0.14 mol) of 3-mercaptopropionic acid

b) 45 g of toluene

c) 18 g of water

d) 5.93 g (0.14 mol) of lithium hydroxide monohydrate.

After ten minutes of agitation at the temperature of 40°C, the

reaction mixture is distilled to remove the solvent and the water present

in the system. The following are added to the solid dehydrated product:

e) 66.64 g (0.14 mol) of fluorinated epoxide.

C ₈ F ₁₇ CH ₂ CHCH ₂ O

( IV)

The temperature of the reaction mass is brought to 9O ⁰ C. After one

hour of reaction, a whitish paste has formed which receives the addition,

after cooling to 7O ⁰ C, of 82 g of 2-propanol. Reaction is performed in

reflux for 3 more hours until the epoxide disappears completely. The

reaction is monitored constantly with GC analysis, extracting the epoxide

with a non-polar solvent. Finally, 164 g of water are added, obtaining a

product with 25% active material with 25% 2-propanol and 50% water.

Example 2

The following are loaded initially into a 1000 ml flask provided

with the same services as in Example 1:

a) 50.00 g of 3-mercaptopropionic acid (0.47 mol)

b) 19.76 g of lithium hydroxide monohydrate (0.47 mol)

c) 69.7 g of water

d) 244.2 g of 2-propanol

Under agitation, and after complete solubilization, the solution is

brought to 60°C and the following are introduced by means of a dripping

funnel and in a nitrogen atmosphere:

e) 224.23 g of fluorinated epoxide (IV) (0.47 mol).

The reaction is monitored by gas chromatographic analysis,

extracting the epoxide with a non-polar solvent such as chloroform. The

reaction ends after 5 hours. The product is solubilized with 190.4 g of

water and 309.8 g of 2-propanol. The solution thus obtained has 25% dry

fraction, 25% water and 50% 2-propanol. It has a clear amber- yellow

color.

Example 3

In the same manner as Example 2, but replacing the fluorinated

epoxide (IV) with 245.34 g of a mixture of fluorinated epoxides having

the general formula

with the following composition : 58 . 0% with n=8

33 . 7 % with n=10

8.3% with n=12 <

with an average molecular weight of 522 g/gmol.

At the end of the reaction, solubilization with water is performed

so as to obtain a solution that comprises 25% dry fraction, 25% water and

50% 2-propanol. The solution is clear amber yellow.

Example ^' 4

The following product is synthesized:

The following are loaded into the same apparatus as Example 1:

a) 21.84 g (0.1 mol) of 11-mercaptoundecanoic acid

b) 5.61 g (0.1 mol) of potassium hydroxide

c) 109.8 g of 2-propanol

d) 10 g of water

Under agitation and after complete solubilization, the pH of the

solution is adjusted so as to obtain a value equal to 7-7.5.

The solution is brought to 6O ⁰ C and the following is introduced by

means of a dripping funnel and in a nitrogen atmosphere :

e) 47.6 g of epoxide (IV) (0.1 mol).

The reaction is monitored by gas chromatographic analysis,

extracting the epoxide with a non-polar solvent such as chloroform. The

reaction ends after 7.5 hours. The product is solubilized with 63.21 g of

water and another 36.62 g of 2-propanol. The solution thus obtained has

25% dry fraction, 25% water and 50% 2-propanol. It has a clear yellow

color.

Example 5

The following product is synthesized:

C ₈ F ₁₇ CH ₂ CHCH ₂ -S-(CH ₂ ) ₃ SO ₃ Na OH

The following are introduced in the same apparatus used in Example

1 but in a 100 ml flask:

a) 13.3 g of epoxide (IV) (0.028 mol)

b) 5.0 g of the sodium salt of 3-mercaptopropansulfonic acid

HS (CH ₂ ) ₃ SO ₃ Na (0.028 mol)

c) 5 g of water

d) 18.3 g of 2-propanol.

Under intense mechanical agitation and at the temperature of 75°C,

complete disappearance of the epoxide occurs after 4.5 hours of reaction.

The product is solubilized with 31.6 g of water so as to obtain a

solution containing 25% dry fraction, 25% 2-propanol and 50% water.

Example 6

The following product is synthesized: CnF ₂ (I .(CH ₂ CHCH ₂ -S-(CH ₂ ) _I yCH ₃

OH

with the procedure described below.

The following components are loaded into the same apparatus of

Example 1 :

a) 47.60 g (0.1 mol) of epoxide having the formula (IV)

b) 28.66 g (0.1 mol) of 1-octadecanthiol;

These are made to react for 8.5 hours in an atmosphere of nitrogen

at 145 ⁰ C. The two compounds are immiscible when cold, but mix perfectly

when hot, forming a single phase. After 8.5 hours, GC analyses show that

the epoxide has disappeared completely.

■ One obtains a yellow product which is soluble in ketones such as

acetone, methyl ethyl ketone, methyl isobutyl ketone and, when hot, in 2-

propanol and in acetates such as butyl acetate and ethyl acetate.

Example 7

The following product is synthesized:

C ₈ F ₁₇ CH ₂ CHCH ₂ SCH ₂ CHCH ₂ SO ₃ Na

OH S

OH

The same apparatus of Example 2 is loaded with:

a) 22.83 g (0.1 mol) of the sodium salt of 2, 3-dimercapto-l-

propansulfonic acid (Aldrich®) ;

b) 95.2 g (0.2moli) of fluorinated epoxide (IV)

c) 118 g of 2-propanol

d) 59 g of water

Under intense mechanical agitation and at the temperature of 75°C,

the complete disappearance of the epoxide is observed after 5.5 hours ^" of

reaction. The product is solubilized with a further 59 g of water and 118

g of 2-propanol so as to obtain a solution containing 25% dry fraction,

50% 2-propanol and 25% water.

Example 8

The following product is synthesized:

where Rf= C ₈ Fi ₇ -

19<n<20

The same apparatus of Example 2 provided with dripping funnel is

loaded with:

a) 35 g (0.039 mol) of polyethylene glycol with an average molecular

weight of 900 g/gmol (Aldrich®) ;

b) ^' 45 g of dioxane.

The system is heated to 8O ⁰ C, a temperature at which the reagent is

perfectly soluble, and 200 μl of BF3 etherate are injected.

The following are added drop by drop

a) 37.0 g (0.078 mol) of epoxide (IV).

Dripping lasts for 1 hour. At the end of the addition, another

200μl of BF3 etherate are added. The reaction continues for another 2

hours at 80°C. The end product is homogeneous, pale yellow and soluble in

water.

Example 9

One proceeds as in Example 8, but the fluorinated epoxide (IV) is

replaced with 40.71 g (0.078 mol) of a mixture of fluorinated epoxides

having the general formula

with the following composition: 58.0% with n=8

33.7% with n=10

8.3% with n=12

with an average molecular weight of 522 g/gmol.

The reaction in this case lasts 4 hours after the end of dripping.

Example 10

The following product is synthesized:

An apparatus as in Example 1 is loaded with:

a) 61.68 g (0.1 mol) of Tergitol® (Aldrich®) ;

b) 50 ^' g of dioxane

Under agitation, the mixture is brought to 80 ⁰ C and 200 μl of BF3

etherate are introduced. The following is loaded drop by drop in 30

minutes

c) 47.6 g (0.1 mol) of fluorinated epoxide (IV) .

After dripping ends, one continues at the temperature of 80°C for 3

more hours, after which the epoxide has disappeared completely.

The dioxane is removed by distillation and with a slight flow of

nitrogen and the product is solubilized with a 50:50 mixture of water and

2-propanol, obtaining a clear pale yellow solution with a 25% dry

fraction.

Example 11

The following product is synthesized:

C ₈ F ₁₇ CH ₂ CHCH ₂ O(CH ₂ CH ₂ O)nCH ₃ OH

with 15<n<17

An apparatus as described in Example 1 is loaded with:

a) 75.0 g (0.1 mol) of polyethylene glycol methyl ether with an

average molecular weight of 750 g/gmol (Aldrich®) ;

b) 50 g of dioxane.

Following the same procedure of Example 10, one obtains a clear

white 25% solution of the product whose formula is cited above.

Example 12

The following product is synthesized:

RfCH ₂ CHCH ₂ O(CH ₂ CH ₂ )ITiCH ₃ ° ^H where Rf is C _n F _2n+ i~ with the following composition: 58.0% with n=8

33.7% with n=10

8.3% with n=12

14<m<16

An apparatus as described in Example 1 is loaded with:

a) 90 g (0.196 mol) of polyethylene monoalcohol with mp=108°C,

dr=0.985 and Mn=460 (Aldrich®)

The reaction mass is brought to 110-115 ⁰ C so as to melt the product

and 200 μl (102 g, 0.196 mol) of the mixture of fluorinated epoxides

described in Example 3 are added.

The mixture of epoxides is loaded in one hour. The reaction mass is

kept at this temperature and under agitation for 3 hours, during which

two doses of BF3 etherate of 200 μl each are added.

The result is a straw yellow product, which melts in a temperature

range between 85°C and 95°C, with a surface tension of 13.8 dynes/cm.

Example 13

One proceeds as described in Example 12, using 93.3 g of

fluorinated epoxide (IV) . The result is a white product with a melting

point comprised between 85 ⁰ C and 90 ⁰ C.

Example 14

The following product is synthesized:

C ₈ F ₁₇ CH ₂ CHCH ₂ O(CH ₂ CH ₂ )^COOLi

OH

The same apparatus of Example 1 is loaded with:

a) • 21.63 g (0.1 mol) of 12-hydroxydodecanoic acid;

b) 4.19 g of lithium hydroxide monohydrate

c) 50 g of methyl isobutyl ketone.

Under agitation, distillation is performed with a Marcusson-type

apparatus at the azeotropic temperature of 92 ⁰ C to remove the water that

is present in the system. Drop by drop, at the temperature of 85°C, 200

μl of BF3 etherate are introduced together with

b) 47.6 g (0.1 mol) of fluorinated epoxide (IV).

Dripping lasts one hour, continuing subseguently with the reaction

for another 4.5 hours at 85 ⁰ C ₇ adding two 200 μl doses of BF3 etherate.

200 g of water are added and then the solvent is _ distilled with

part of the water added at 92 ⁰ C with a flow of nitrogen. Finally, 231 g

of 2-propanol are loaded and the quantity of water removed during

distillation is restored. The result is a pale yellow homogeneous product

with 15%-16% dry material.

Example 15

The following product is synthesized:

C ₈ F ₁₇ CH ₂ CHCH ₂ OCH ₂ CH ₂ SO ₃ Na

OH

The same apparatus of Example 1 is loaded with:

a) 14.81 g (0.1 mol) of sodium salt of isoethionic acid (Aldrich®)

having the formula HOCH ₂ CH ₂ SO ₃ Na;

b) 12 g of dioxane.

Under intense agitation, this mixture is brought to 90 ⁰ C. At this

temperature, by means of a dripping funnel, the following is dripped:

c) 47.6 g (0.1 mol) of fluorinated epoxide (IV).

Before dripping, 200 μl of BF3 etherate are added to the reaction

mass. When dripping ends, another 400 μl of BF3 etherate is added in two

separate doses. The reaction temperature is 90 ⁰ C. The disappearance of

the fluorinated epoxide is monitored by GC analysis . The reaction is

finished after 6.5 hours.

Example 16

The following product is synthesized:

An apparatus similar to the one of Example 1 is loaded with:

a) 2.8 g (0..024 mol)' of hexamethylenediamine

b) 45.70 g (0.096 mol) of epoxide having the formula (IV).

The reaction is performed in the mass at. the temperature of 12O ⁰ C

for 7 hours. The product, when cold, is an orange solid with a melting

point comprised between 60 °C and 65 ⁰ C and a surface tension of 13.4 mN/m.

The product is dissolved in 2-propanol until a 50% solution is obtained.

Example 17

The following product is synthesized:

C ₈ F ₁₇ CH ₂ CHCH ₂ — NN((CCHH ₂₂ )) ₆₆ NN- CH ₂ CHCH ₂ C ₈ F ₁₇ H H

OH ° ^H Using the same procedure as in the preceding example, the following

are made to react:

a) 2.8 g (0.024 mol) of hexamethylenediamine

b) 22.85 g (0.048 mol) of epoxide having the formula (IV)

The reaction is performed at 100 ⁰ C for 3 hours. GC analysis shows

that the intended product has 81% concentration; 9.5% is the product

[C ₈ F ₁₇ CH ₂ CH (OH) CH ₂ ] ₂ N(CH ₂ ) ₆ NHCH ₂ CH(OH)CH ₂ C ₈ F ₁₇ and the remaining percentage

is the monosubstituted product C ₈ F ₁₇ CH ₂ CH (OH) CH ₂ NH (CH ₂ ) ₆ NH ₂ . The mixture of

these products is solid, with a melting point comprised between 45 ⁰ C and

55 ⁰ C. The product can be purified by dissolving it when hot in

tetrahydrofuran. When cold, the intended product precipitates and is

filtered. The yield is 66% . The surface tension of the product is 7 . 6

dyne s /cm.

Example 18

The following product is synthesized: C ₈ F ₁₇ CH ₂ CHCH ₂ - N(CH ₂ ) ₁₇ CH ₃

OH

The same apparatus of Example 1 is loaded with:

a) 26.95 g (0.1 mol) of octadecylamine

b) 47.60 g (0.1 mol) of epoxide having the formula (IV).

The reaction is performed at 12O ⁰ C for 3.5 hours. GC analysis shows

that the intended product has a concentration of approximately 90%, while

the remaining percentage is a mixture of unreacted amine and

disubstituted amine. The end product has a melting point of 68°C-70 ^c C. It

can be placed in an aqueous solution by adding 6.0 g of acetic acid,

161.0 g of 2-propanol and 80.5 g of water. It is a good cationic

surfactant, which at a concentration of 0.01% by weight in water provides

a surface tension of 19.5 mN/m.

Example 19

The surface tensions of various molecules are measured. Table 1

lists the surface tension measurements for some of the products having

the formula (I) that have become evident in the field of paints and in

the field of solid lubricants for snow gear.

Table 1

Table 1 relates to products having the formula ( I ) that have

structural analogies with respect to commercially available ones

(comparison Examples 1 to 5) so as to best highlight the superior

properties of the former.

Further tests carried out in testing laboratories have subsequently

confirmed that even in cases in which the difference in surface tension

between the surfactants according to the invention and known ones was

slight, in practice the surfactants having the formula (I) entailed

distinctly better results. For example, a conspicuous reduction of the

orange peel effect and of pinholes, together with a higher scratch

resistance, have been observed. One of these "visual" tests related to

the semiempirical assessment of the influence of the fluorinated

surfactant on the flow of paints. The results are given in Table 2:

Table 2

where the assessment ranges from 0 = very bad to 5 = excellent. The

various surfactants were tested at equal concentrations.

The fact that the assessments given above regarding the

effectiveness of the surfactants were performed with samples of coating

which were very different from each other shows even .more clearly that

the fluorinated products according to the invention allow to achieve

valid results over a wide range of quantity used and even in very

different systems and fields of application.

Example 20

Assessment of the influence of the presence of the fluorinated

surfactants on fire suppression foams.

A protein concentrate was prepared which was intended for use in

extinguishing foams and had the following formulation:

Protein concentrate at 53% by weight 100 g

water 27 g

2-propanol 7 g

sodium dodecylbenzene sulfonate at 30% by weight 9.5 g

sorbitan monolaurate (HLB 8.6) 4 g

fluorinated surfactant at 25% by weight ^■ 5 g

6 g of this concentrate is taken and diluted with 94 g of deionized

water. The characteristics of the foam were determined according to a

number of simple experiments (cited hereafter), which allow to check the

influence of the addition of the fluorinated surfactant on the foam,

a) Expansion ratio (TE)

100 ml of diluted solution are converted into foam by means of a

mechanical agitator with two whips. The expansion ratio TE is the ratio

TE=V/v, where V is the final foam volume and v is the volume of the

initial solution converted completely into foam;

b) Settling time (TD)

This is defined as the time required to collect in a ^' graduated

cylinder a volume of liquid that corresponds to one quarter of the volume

of solution converted into foam, i.e., in the case, 25 ml;

c) Foaming power (PS)

This is defined as the volume of the foam formed by pouring 500 ml

of foaming solution from a dripping funnel with an output diameter of 13

mm arranged at a height of 450 mm on 100 ml of said solution contained in

a 2-liter container. The volume of the foam is measured 30 seconds after

the introduction of the 500 ml of solution;

d) Foam fluidity (FS)

The fluidity of the foam is determined by measuring the speed with

which the foam flows on a plane that is inclined by 10°.. This inclined

plane is the bottom of a foam containment tray, which is 35 cm long, 21

cm wide and 10 cm high. This portion of the tray is separated from a

second container by a movable panel. This last container contains 2 liter

of foam. The time taken by the foam to travel along the entire inclined

plane of the tray is measured from the moment when the movable panel is

lifted.

The fluorinated surfactant marketed under the name FORAFAC®1157 was

considered as a reference for the tests:

Example 22

The assessment of the effectiveness of the compounds of Examples 6

and 12 was made on a Nordic skiing trail traced with a constant slope and

whose path was at an altitude of 1400 m. Weather and snow conditions were

as follows :

- air, temperature: -1

- relative humidity % : 60

- snow temperature: -4

- snow type: transformed

- snow appearance : grainy

- weather conditions : overcast

A photocell was placed at the beginning and at the end of the

trail to measure travel times. The tests were conducted by a ski

instructor, expert in performing this kind of test. Four pairs of skis

suitable for Nordic skiing races were used; all were treated with MAPLUS

Pl MED® paraffin-based ski wax, and four products, specified below as A,

B, C, D, were applied to them by following the standard application

procedure of these products, which is known in the field. The four applied

products are composed as follows:

- product A: semiperfluorinated alkanes having the general formula

RF-RH, with C ₂₈ -C ₃₂ linear chains, prepared according to Example 2 of

US5202041;

- product B: asymmetric aromatic diester of terephthalic acid, in

particular (asymmetric) octadecyl heptadecafluoroundecyl terephthalate

- product C: product of Example 12

- product D: product of Example 6

The- skier performed five series of tests (five laps of the trail)

for each product, after resetting the skis according to the standard

procedure used by skimen.

The results have allowed to point out that the average of the lap

times when using skis treated with C is 0,24% lower than with product A,

0,29% lower than with product B, and 0.15% lower than with product D.

Although the text has described only some preferred embodiments

according to the invention, the person skilled in the art will realize

that numerous variations of the embodiments described in the text and in

the examples that follow are possible without thereby altering the

inventive concept of the present invention.

The disclosures in Italian Patent Application No. MI2005A001155,

from which this application claims priority, are incorporated herein by

reference.