EP1904428A2 - New fluorinated compounds, their synthesis and use - Google Patents

New fluorinated compounds, their synthesis and use

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Publication number
EP1904428A2
EP1904428A2 EP06755959A EP06755959A EP1904428A2 EP 1904428 A2 EP1904428 A2 EP 1904428A2 EP 06755959 A EP06755959 A EP 06755959A EP 06755959 A EP06755959 A EP 06755959A EP 1904428 A2 EP1904428 A2 EP 1904428A2
Authority
EP
European Patent Office
Prior art keywords
formula
group
defined above
iii
comprised
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP06755959A
Other languages
German (de)
French (fr)
Inventor
Francesco Maniero
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
GUARNIFLON S.P.A.
Original Assignee
MAFLON Srl
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by MAFLON Srl filed Critical MAFLON Srl
Priority to EP11163163A priority Critical patent/EP2343270A3/en
Publication of EP1904428A2 publication Critical patent/EP1904428A2/en
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/12—Oxygen-containing compounds
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    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C215/04—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated
    • C07C215/06—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic
    • C07C215/08—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic with only one hydroxy group and one amino group bound to the carbon skeleton
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    • C07C215/06—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic
    • C07C215/14—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic the nitrogen atom of the amino group being further bound to hydrocarbon groups substituted by amino groups
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    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
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    • C07C229/10—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • C07C229/12—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of acyclic carbon skeletons
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    • C07C309/07—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton
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    • C07C309/10—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing etherified hydroxy groups bound to the carbon skeleton with the oxygen atom of at least one of the etherified hydroxy groups further bound to an acyclic carbon atom
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    • C07C323/11—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
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    • C07C323/66—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton containing sulfur atoms of sulfo, esterified sulfo or halosulfonyl groups, bound to the carbon skeleton
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Definitions

  • the present invention relates to new fluorinated compounds, to
  • fluorinated surfactants are used
  • extinguishing agents such as extinguishing
  • fluorinated surfactants have a film-forming
  • fluorinated surfactants make the foam more fluid and therefore faster in
  • the aim of the present invention is therefore to provide
  • An object is to provide fluorinated products having improved
  • Another object is to provide a method that is fast, inexpensive,
  • the invention relates to new fluorinated
  • Rf is a saturated perfluorocarbon chain or a mixture of saturated
  • perfluorocarbon chains which are preferably linear, optionally comprising
  • R is selected between hydrogen and a linear or ramified alkyl C 1 -C 5
  • R is CH 3 - and more preferably R is H;
  • B is selected among :
  • R 2 where R 2 is selected among :
  • R 1 is selected among:
  • p is an integer comprised between 1 and 50, preferably between 2 and 10;
  • pi is an integer comprised between 1
  • D is an integer comprised between 1 and
  • G is an integer comprised between 1
  • 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:
  • neutral conjugate acid preferably is selected among: ii-a) -COOQ,
  • ammonium ion an ammonium ion, optionally mono-, di- or
  • Ci-Cio alkyl as CH 3 -, (CH 3 ) 3 C-, C 4 H 9 -, C 8 H 17 -,
  • pl9 is an integer comprised between 1 and 50, and p9 is as
  • iii-e a group selected among: iii-e-l) (CH 2 CH 2 O)-C 6 H 4 -(CH 2 CH 2 O)—
  • I D iii-g a group having the formula ._ , , I . . _ . where Fg is as
  • R 4 is hydrogen or a linear or ramified C 1 -C 5 alkyl group; preferably
  • Y is hydrogen or a group having the formula ( II )
  • 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
  • R ⁇ is selected among:
  • plO is an integer comprised between 1 and
  • qlO and rlO are integers and each is independently equal to 0
  • pllO is an integer comprised between 1 and 50, plO is as defined above ;
  • R 7 is selected between :
  • R 8 is selected among:
  • p8 is an integer comprised between 1 and 50, preferably
  • 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)--
  • n when present, can assume the values
  • compositions comprising
  • compositions such as aqueous solutions or solutions of other solvents
  • alcohols such as methanol, ethanol, n-propanol, isopropanol, amyl
  • ketones such as acetone, methyl ethyl
  • 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,
  • fluorinated and non-fluorinated amphoteric surfactants for example fluorinated and non-fluorinated amphoteric surfactants such as fluorinated and non-fluorinated amphoteric surfactants
  • surfactants such as amine salts, quaternary amine compounds.
  • quantity of fluorinated compound (I) is comprised between 0.001% and 10%
  • paraffins mixtures of paraffins, mixtures of paraffins and mineral oils
  • fluorinated compounds such as Rf-Rh and fluorinated compounds such as Rf-
  • the invention relates to the use of the
  • compositions are provided.
  • A is 1, more preferably the ones in which A is 1 and Y is hydrogen,
  • Emulsions based on hydrolyzed animal or plant protein are
  • surfactants are incorporated, allowing to obtain a foam which is more
  • fluorinated surfactants offer higher resistance to
  • the 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
  • foam i.e., the rate at which the foam covers a preset portion of an
  • Bases are constituted generally by high-density
  • polyethylene and are manufactured by extrusion or sintering of the
  • bases can be formed by using a composition
  • compositions in a mixture with paraffin waxes so as to improve their
  • the mixture can be prepared by simple
  • the invention relates to a method for the
  • Z differs from Y
  • B, and optionally E if present, are equal
  • reaction temperature must be
  • reaction can be performed in the mass or in
  • toluene N methyl pyrrolidinone, alkanes, or mixtures thereof.
  • reaction time varies between 4 and
  • inorganic bases or of tertiary amines can also precede the reaction of
  • the finished product can be placed in solution or can be kept as such.
  • B and optionally E if present are both -O- .
  • Q if present, be selected
  • alkyl groups such as R 2 .
  • an inert solvent such as methyl ethyl ketone, tetrahydrofuran, dioxane,
  • Lewis acid preferably in a quantity comprised between 0.001% and 1% by
  • the reaction temperature must also be comprised between 20 °C and
  • fluorinated epoxide or mixture of epoxides with n of different value is
  • reaction temperature is comprised
  • reaction time varies between 4 and 20 hours, preferably between 6 and 12 hours.
  • the product can be
  • glycols such as ethylene glycol
  • propylene glycol - ketones such as acetone, methyl ethyl ketone, methyl
  • esters such as butyl or ethyl acetate, and dioxane
  • the reaction temperature must be comprised between 20°C and 12O 0 C;
  • reaction time varies between 4 and
  • the product can be placed in
  • the polymers can be used to obtain an oil-hydro-repellence effect
  • reaction mixture is distilled to remove the solvent and the water present
  • the temperature of the reaction mass is brought to 9O 0 C. After one
  • reaction is monitored by gas chromatographic analysis
  • reaction is monitored by gas chromatographic analysis, extracting the epoxide with a non-polar solvent such as chloroform.
  • the product is solubilized with 31.6 g of water so as to obtain a
  • propanol and in acetates such as butyl acetate and ethyl acetate.
  • the system is heated to 8O 0 C, a temperature at which the reagent is
  • the reaction in this case lasts 4 hours after the end of dripping.
  • An apparatus as in Example 1 is loaded with:
  • the dioxane is removed by distillation and with a slight flow of
  • reaction mass is brought to 110-115 0 C so as to melt the product
  • the reaction temperature is 90 0 C.
  • the reaction is performed in the mass at. the temperature of 12O 0 C
  • the product is dissolved in 2-propanol until a 50% solution is obtained.
  • the product can be purified by dissolving it when hot in
  • the end product has a melting point of 68°C-70 c C. It
  • surfactant which at a concentration of 0.01% by weight in water provides
  • Table 1 relates to products having the formula ( I ) that have
  • a protein concentrate was prepared which was intended for use in
  • Protein concentrate at 53% by weight 100 g
  • the characteristics of the foam were determined according to a
  • the volume of the foam is measured 30 seconds after
  • the fluidity of the foam is determined by measuring the speed with the fluidity of the foam.
  • This last container contains 2 liter
  • a photocell was placed at the beginning and at the end of the
  • products are composed as follows: - product A: semiperfluorinated alkanes having the general formula
  • The- skier performed five series of tests (five laps of the trail)

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
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Abstract

New fluorinated compounds of formula (I), where the variables are as defined in the claims, and method for their preparation. These compounds are used particularly but not exclusively as fluorinated surfactants or as solid lubricants to increase the characteristics of slipperiness and oil-hydro-repellence of surfaces that constitute hulls of watercraft and the like and/or their cladding materials, sleighs, chutes, bases of skis and the like. These compounds having the general formula (I) can be used as such or in solution, pure or in a mixture with other similar or different fluorinated compounds.

Description

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-
(CH2) m-S- (CH2) nCOOH. 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 (CH2)mSH, a phase which requires many onerous steps, including
the addition of ethylene to the perfluoroalkyliodides CnF2n+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 CnF2n+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 C1-C5
group, preferably R is CH3- 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
R2 where R2 is selected among :
iii-a) hydrogen,
iii-b) C1-C5 alkyl
1 I AU 1 • 1 • 1 • -c \ ) a group 1 havi • ng ' J t-Ih-e f JΓormul T a where R and Rf
are a R1 is selected among:
i) a linear or ramified group having the formula — (CpH2P) -, where
p is an integer comprised between 1 and 50, preferably between 2 and 10;
15 ii) a group having the formula - (CpH2P) q-Cgϊ-4- (CpiH2Pi) 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 - (CpH2P) q-CeH,}- (CH2CH2O) 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 (CpH2p) CeH4 (CHaCHO)^.
CH3 where p is defined above and F is an integer comprised between 1 and 40;
■v) a group selected among:
v~a) -(CH2CH2O)-C6H4-(CH2CH2O7- D D1 5 v-b) -(CH2 CH O) -C6H4-(CH2 CH O) — I F I F1
CH3 CH3
v-c) -(CH2 CH2 O) -C6H4-(CH2 CH O) — D I F
CH3
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 ;
CH3 vii) a group having the formula /QLJ QU_ QΛ where F is as defined
F above; viii) an ethylene oxide and propylene oxide block copolymer having
the formula CH-3
I 3 -(CH2CH-O)-(CH2CH2-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
-(CH2CH- O)-(CH2CH2-O)-(CH2CH- 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;
R3 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) -SO3Q,
ii-c) -OSO3Q,
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 CH3-, (CH3) 3C-, C4H9-, C8H17-,
preferably C1-C5 alkyl,
ii-f-2) a group having the formula where R and Rf are as defined above, or
ii-f-3) C1-C5 hydroxyalkyl;
iii) a group -R9-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 -
(CpgH2(p9))- where p9 is an integer comprised between 1 and
50, preferably between 2 and 10.;
iii-b) a . group having the formula - (CpgH2 (P9) ) (Cpi9H2(pi9) ) r9~ 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 — (CpgH2(p9) ) q9~CgH4-
(CH2CF^O)Dg- where p9 and q9 are as defined above and Dg is
an integer comprised between 1 and 40; . . . ^ . . . . - . -(Cp9H2Pg)-C6H4-(CH2 CH O)- lii-d) a group having the formula r-
CH3 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) (CH2CH2O)-C6H4-(CH2CH2O)—
D9 D19
iii-e-2) -(CH2 CH O) -C6H4-(CH2 CH O) —
I F9 I F19 CH3 9 CH3
iii-e-3) -(CH2 CH2 O) -C6H4-(CH2 CH O)— 10 °9 CCHH3 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 — (CH2CH2O) D9~ where Dg is
as defined above;
CH3
I D iii-g) a group having the formula ._ , , I . . _ . where Fg is as
—(L-H2Un- O)- defined above; F9
iii-h)- an ethylene oxide and propylene oxide block copolymer
having the formula
CH3
-(CH2CH- O)-(CH2CH2- O)- 0 F9 °9 where Fg and D9 are as defined above;
iii-i) an ethylene oxide-propylene oxide-ethylene oxide block
copolymer having the formula •
CH3 CH3
-(CH2CH- O)-(CH2CH2-O)-(CH2CH- O)- 5 F9 D9 G9 where Fg and Dg are as defined above and Gg is an integer
comprised between 1 and 40 ;
R4 is hydrogen or a linear or ramified C1-C5 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;
R5 is hydrogen or a linear or ramified C1-C5 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 -R10-PQ, where P and Q are as defined above and Rio is
selected among:
iii-a) a linear or ramified group having the formula -
(CpioH2(pio) ) ~ where plO is an integer comprised between 1 and
50, preferably between 2 and 10;
iii-b) a - (CpI0H2 (pio) ) qio-C6H4- (CpI10H2 (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~ ( CpIoH2 (pio) ) qio~CgH4- ( CH2CH2O ) Dio~ group, where plO
and qlO are as defined above and D10 is an integer comprised
between 1 and 40;
-(Cp1oH2Pio)-C6H4-(CH2 CH O)- iii-d) a group having the formula ' MO •
CH3 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) -(CH2 CH2 O) -C6H4-(CH2 CH2 O)
D10 D110
iii e 2) "(CH2 CH 0) -C6H4-(CH2 CH O) — L F10 I F110 L-π3 CH3
iii-e-3) -(CH2 CH2
where D10 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 - (CH2CH2O) DIO~ where D10 is
as defined above;
CH3 iii-g) a group having the formula -(CH2CH-O)- where F10 is
F10 as defined above;
iii-h) an ethylene oxide and propylene oxide block copolymer
having the formula
CH3
-(CH2CH- O)-(CH2CH2- O)- F10 D10 where Fi o and Dio are as defined above ;
iii-i ) an ethylene oxide-propylene oxide-ethylene oxide block
copolymer having the formula
CH3 CH3
-(CH2CH- O)-(CH2CH2- O)-(CH2CH- O)- F10 D10 G10
where Fχo and Di o are as ■ defined above and Gio is an integer
comprised between 1 and 40 ;
R7 is selected between :
i ) hydrogen,
ii ) a group having the formula RTCH2CHCH2— where Rf and R are
OR as defined above;
R8 is selected among:
i) a linear or ramified group having the formula — (CP8H2(P8) ) ~
where p8 is an integer comprised between 1 and 50, preferably
between 2 and 10;
ii) a group having the formula - (CpgH2 (P8) ) q8~C6H4- (CpIeH2 (Pi8) ) 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 - (CpsH2 (P8) ) qS ^CθH,}- (CH2CH2O) D8~
where p8 and q8 are as defined above and Ds is an integer comprised
between 1 and 40;
-(Cp8H2Pa)-C6H4-(CH2 CH O)- iv) a group having the formula | p where pδ is
CH3 8 as defined above and FQ is an integer comprised between 1 and 40;
v) a group selected among: v-a) (CH3CH2O)-C6H4-(CH3CH2O)--
D8 D18 -(CH2 CH O) -C6H4-(CH2 CH O) — v-b) I F8 I F18
CH3 CH3
v- c ) -(CH2 CH2 O) -C6H4-(CH2 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 -(CH2CH2O)Dg- where Ds is as
defined above;
CH3 vii) a group having the formula _fCH CH-OV- where Fs is as
F8 defined above;
viii) an ethylene oxide and propylene oxide block copolymer having
the formula I 3
-(CH2CH- O)-(CH2CH2- O)- F8 D8
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(R2)-, 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 -NR2-,
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, R8=-CP8H2p8, R7=CH3-, a group having the
general formula (III) :
RfCH2CHCH2-B-(Cp8H2P8)CH3
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
C8F17CH2CHCH2 CH2CHCH2F17C8
OH OH
Ib) 8 17 2 2 -CH
OH
Preferred examples of compounds (I) with B and optionally E, equal
g) C8F17CH2CHCH2SCH2CH2SO3Na
OH
C8F17CH2CHCH2SCH2CH2CH2SO3Na h) OH
CnF2n+1 CH2CHCH2SCH2C6H4SO3Li i ) OH
m) CnF2n+iCH2CHCH2SC8H-i7
OH
Specific examples of compounds (I) with B, and optionally E, equal
are :
a )
3b ) CnF2n+ICH2CHCH2OCH2CH2SO3Li
OH
3 c )
3d) CnF2n+ICH2CHCH2O(CH2CH2O) H
13
OH
3e > CnF2n+1 CH2CHCH2O(CH2CH2)17CH3
OH
Specific examples of compounds (I) with B, and optionally E, equal
to -N(R2)- 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 -
(CH2CH2O)0-, (CH2CH (CH3) 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 R7, 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 2O0C and 1200C.
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 '400C and 800C,
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, -SO3H, or -OSO3H 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, NH4OH 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 R2.
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
1200C.
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 200C and 120°C, preferably between 400C and 8O0C. 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(R2)- (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 12O0C;
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(R2)-, 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 1200C, preferably between 40°C and 800C, 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(R2)- 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.
C8F17CH2CHCH2 O
( IV)
The temperature of the reaction mass is brought to 9O0C. After one
hour of reaction, a whitish paste has formed which receives the addition,
after cooling to 7O0C, 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 6O0C 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:
C8F17CH2CHCH2-S-(CH2)3SO3Na 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 (CH2) 3SO3Na (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: CnF2(I .(CH2CHCH2-S-(CH2)IyCH3
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 1450C. 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:
C8F17CH2CHCH2SCH2CHCH2SO3Na
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= C8Fi7-
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 8O0C, 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 800C 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:
C8F17CH2CHCH2O(CH2CH2O)nCH3 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:
RfCH2CHCH2O(CH2CH2)ITiCH3 °H where Rf is CnF2n+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 110-1150C 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 850C and 900C.
Example 14
The following product is synthesized:
C8F17CH2CHCH2O(CH2CH2)^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 920C 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 850C7 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 920C 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:
C8F17CH2CHCH2OCH2CH2SO3Na
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 HOCH2CH2SO3Na;
b) 12 g of dioxane.
Under intense agitation, this mixture is brought to 900C. 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 900C. 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 12O0C
for 7 hours. The product, when cold, is an orange solid with a melting
point comprised between 60 °C and 650C 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:
C8F17CH2CHCH2 — NN((CCHH22))66NN- CH2CHCH2C8F17 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 1000C for 3 hours. GC analysis shows
that the intended product has 81% concentration; 9.5% is the product
[C8F17CH2CH (OH) CH2]2N(CH2)6NHCH2CH(OH)CH2C8F17 and the remaining percentage
is the monosubstituted product C8F17CH2CH (OH) CH2NH (CH2) 6NH2. The mixture of
these products is solid, with a melting point comprised between 450C and
550C. 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: C8F17CH2CHCH2- N(CH2)17CH3
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 12O0C 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-70cC. 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 C28-C32 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.

Claims

1. A fluorinated compound having the general formula (I)
( D 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 CnF2n+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 C3.-C5
group, preferably R is CH3- and more preferably R is H;
B is selected among:
i) an ether group -O-,
ii) a thioether group -S-,
iii) an amine having the general formula N- R2 where R2 is selected among:
iii-a) hydrogen,
iii-b) C1-C5 alkyl
iii-c) a group having the formula RfCH2CHCH2- where R and Rf
are as defined above, OR
R1 is selected among: i) a linear or ramified group having the formula — (CpH2p) ~, where
p is an integer comprised between 1 and 50, preferably between 2 and 10;
ii) a group having the formula - (CpH2P) q-CeHU- (CpiH2Pi) 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 - (CpH2P) q-CeH4- (CH2CH2O) D- where
p and q are as defined above and D is an integer comprised between 1 and
40;
iv) a group having the formula (CpH2p) C6H4 (CH3CHO)
CH3 where p is defined above and F is an integer comprised between 1 and 40;
v) a group selected among: v_aj -(CH2 CH2 O) -C6H4-(CH2 CH2 C7- D D1
-(CH2 CH O) -C6H4-(CH2 CH O) —
1 F I F1 v~b> CH3 CH3
-(CH2 CH2 O) -C6H4-(CH2 CH O)—
V-C) D I F
CH, where D is as defined above, D^ 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;
CH3 vii) a group having the formula -(CH2CH- O)- where F is as defined
F above;
viii) an ethylene oxide and propylene oxide block copolymer having
CH3 thΘ fθrmula -(CH2CH- O)-(CH2CH2-O)- F D where F and D are as defined above ;
ix) an ethylene oxide-propylene oxide-ethylene oxide block
copolymer having the formula CH3 CH3
-(CH2CH- O)-(CH2CH2- O)-(CH2CH- 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;
R3 is selected among:
i) R, where R is as defined above,
ii) a group -PQ where P is an anionic group or its corresponding
neutral conjugate acid, and preferably is selected among:
ii-a) -COOQ,
ii-b) -SO3Q,
ii-c) -OSO3Q,
and Q is selected among:
ii-d) hydrogen,
ii-e) a cation of alkaline metals,
ii-f) an ammonium ion, optionally mono-, di- or
trisubstituted with one or more of:
ii-f-1) Ci-Cio alkyl, as CH3-, (CH3) 3C-, C4H9-, C8Hi7-,
preferably C1-C5 alkyl,
ii-f-2) a group having the formula RfCH2CHCH2- where R
and Rf are as defined above , or OR
ii-f-3 ) C1-C5 hydroxyalkyl; iii) a group -R9-PQ where P and Q are as defined above and where Rg
ected among:
iii-a) a linear or ramified group having the formula -
(Cp9fi2(p9))- where p9 is an integer comprised between 1 and
50, preferably between 2 and 10;
iii-b) a group having the formula — (CpgH2(p9) ) qg—CgHU—
(Cpi9H2 (pi9) ) r9~ where g9 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 — (CpgH2(p9) ) qg—CgHή—
(CH2CH2O) D9~ where p9 and q9 are as defined above and Dg is
an integer comprised between 1 and 40; iii-d) a group having the formula "(Cp9H2Pg)-C6H4-(CH2 CH O)-
CH3 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-i) (CH2CH2O)-C6H4-(CH2CH2O)
D9 D19
iii-e-2) -(CH2 CH O) -C6H4-(CH2 CH O) —
I F9 I F19 CH* CH*
where D9 and F9 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 - (CH2CH2O) Dg- where Dg is
as defined above; CH3 iii-g) a group having the formula I where Fg is. as ^ -(CH2CH-O)-
F9 defined above;
iii-h) an ethylene oxide-propylene oxide block copolymer
having the formula . CHs
-(CH2CH-O)-(CH2CH2-O)-
where F9 and Dg are as defined above;
iii-i) an ethylene oxide-propylene oxide-ethylene oxide block
copolymer having the formula CH3 CH3
-(CH2CH- O)-(CH2CH2-OMCH2CH-O)-
F9 D9 G9
where Fg and Dg are as defined above and Gg is an integer
comprised between 1 and 40;
R4 is hydrogen or a linear or ramified C1-C5 alkyl group; preferably
methyl, more preferably H;
Y is hydrogen or a group having the formula (II)
(ID where
u, v and z are integers and each is independently equal to 0 or 1;
E is defined as B;
R5 is hydrogen or a linear or ramified C1-C5 alkyl group; preferably
methyl and more preferably H; Rg 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 -Ri0-PQ, where P and Q are as defined above and Rio is
selected among:
iii-a) a linear or ramified group having the formula -
(CpIoH2(PiO) ) - where plO is an integer comprised between 1 and
50, preferably between 2 and 10;
iii-b) a - (CpioH2(Pio) ) qio-C3H4- (CpnOH2(piio) ) rio~ 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 - (CpIoH2 (pio) ) (CH2CH2O) Di0- group, where
plO and qlO are as defined above and D10 is an integer
comprised between 1 and 40;
-(Cp10H2P1O)-C6H4-(CH2 CH O)- iii-d) a group having the formula I F10
CH3 where plO is as • defined above and FlO is an integer comprised
between 1 and 40;
iii-e) a group selected among
iii-e-l) -(CH2 CH2 O) -C6H4-(CH2 CH2 O) —
D1O D11Q
-(CH2 CH O) -C6H4-(CH2 CH O) —
111 ' I F-io I F110
CH3 10 CH3
iii-e-3 ) -(CH2 CH2
. where D3.0 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 -(CH2CHaO)DiO" where D10 is
as defined above;
CH3 iii-g) a group having the formula | where F10.is
-(CH2CH- O)- as defined above; '
iii-h) an ethylene oxide and propylene oxide block copolymer
having the formula CH3
-(CH2CH- O)-(CH2CH2-O)-
F10 D10
where F3.0 and Dχo are as defined above;
iii-i) an ethylene oxide-propylene oxide-ethylene oxide block
copolymer having the formula CH3 CH3
-(CH2CH- O)-(CH2CH2- OMCH2CH- O)-
F10 D10 G10 where F10 and Dχo .are as defined above and G10 is an integer
comprised between 1 and 40;
R7 is selected between:
i) hydrogen,
ii) a group having the formula where Rf and R are as defined above;
Ra is selected among:
i) a linear or ramified group having the formula - (CpgH2 (P8) ) ~
where p8 is an integer comprised between 1 and 50, preferably between 2 and 10 ;
ii) a group having the formula - (Cp8H2(P8) ) q8~C6H4~ (CpIaH2 (Pi8) ) r8~
where qδ and r8 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 - (Cp8H2(PS) ) q8~CβR<ι~ (CH2CH2O) D8~
where p8 and q8 are as defined above and Ds is an integer comprised
between 1 and 40;
-(Cp8H2Ps)-C6H4-(CH2 CH O7- iv) a group having the formula ' Fg where p8
CH3 is as defined above and Fs is an integer comprised between 1 and 40; v) a group selected among: v_a) (CH3CH2O)—C6H4-(CH3CH2O)
D8 D18
v-c)
where Ds and Fs are as defined above, Die and Fis are integers each
independently comprised between 1 and 40;
vi) a group having the formula -(CH2CH2O)DS- where Ds is as
defined above;
CH3 vii) a group having the formula I where Fs is as
—(CH2CH—O)— defined above;
viii) an ethylene oxide and propylene oxide block copolymer having
the formula CH3 -(CH2CH- O)- (CH2CH2- O)-
where Fs and Ds are as defined above;
ix) an ethylene oxide-propylene oxide-ethylene oxide block
_ CH3 CH3 j copolymer having the formula I I
-(CH2CH-O)-(CH2CH2-OMCH2CH-O)- ^8 D8 G8
where Fs and Dg are as defined above and Gs is an integer comprised
between 1 and 40;
wherein:
0 - if T is carbon, then b is 1,
if T is nitrogen, then b is 0, and
if B is -N(R2)-, then A and v are both equal to 0.
2. The compound according to claim 1, wherein one or more of the
following conditions is met:
5 - n is an integer comprised between 6 and 14, and preferably is
equal to 6 or 8;
R is methyl;
p is an integer comprised between 2 and 10;
P is a group selected among:
0 ii-a) -COOQ
ii-b) -SO3Q
ii-c) -OSO3Q
if Q is ii-f) , then the ammonium ion is optionally mono-, di- or
trisubstituted with one or more of
5 ii-f-1) Ci-C5 alkyl, and ii-f-2) a group having the where R and Rf are as defined above,
p9 is comprised between 2 and 10,
R5 is methyl;
- plO is comprised between 2 and 10;
p8 is comprised between 2 and 10;
3. The fluorinated compound having the formula (I) according to
claim 1, wherein A is zero.
4. The fluorinated compound having the formula (I) according to
claim 3, wherein A is zero, t=0, v=0, z=0, u=l, R8=-CpaH2p8, R7=CH3-.
5. The fluorinated compound having the formula (I) according to
claim 1, wherein A is 1.
6. The fluorinated compound having the formula (I) according to
claim 5, wherein A is 1 and Y is hydrogen.
7. The fluorinated compound having the formula (I) according to
claim 1 selected from the group that consists of:
Ib) C8F17CH2CHCH2-S CH2CHCH2SO3Na
OH S
Cr^CnCr^F-jyCg OH N -CH2CH2 COOLi
C8F17CH2CHCH2SCH2CH2SO3Na
2g) OH
CnF2n+1 CH2CHCH2SCH2C6H4SO3Li
2i) OH
21 ) CnF2n+1CH2CHCH2SC6H12SCH2CHCH2CnF2n+i
OH OH 2m)
3a)
CnF2n+1 CH2CHCH2OCH2CH2SO3Li
3b )
OH
C8F17CH2CHCH2OCH2CH2SO3Na
3c)
OH
3d)
3e ) CnF2n+iCH2CHCH2O(CH2CH2)17CH3
)H
4a) C8F17CH2CHCH2NH(CH2CH2)I ICH3
OH 4b) C8F17CH2CHCH2NH(CH2CH2)6NHCH2CHCH2(CF2)7CF3
OH OH
where when n is present, it can assume the values 4, 6, 8, 10, 12, 14,
16, 18.
8. A composition comprising at least one fluorinated compound
having the formula (I) according to one or more of claims 1 to 7 in a
mixture with a substance selected among:
- one or more solvents selected among water, alcohols, ketones,
glycols, esters, dioxane, n-methylpyrrolidinone, tetrahydrofuran, dimethylformamide, toluene, chloroform, methyl chloride, dichloromethane,
pure or in turn in a mixture,
- one or more fluorinated and non-fluorinated, amphoteric, anionic
and cationic surfactants,
- at least one among paraffins, mixtures of paraffins, mixtures of
paraffins and mineral oils, fluorinated compounds, PTFE, boron nitride,
molybdenum sulfide, fluorographite, and
- polyethylene powder.
9. A method for synthesizing a compound having the formula (I) as
' defined in any one of claims 1 to 7, comprising the step of adding a
fluorinated epoxide having the general formula . (AA) or a mixture of
fluorinated epoxides having the formula (AA) (AA) with
variable Rf to a compound having the general
(BB)
where the variables Rf, B, R1, T, R3, R4, A, t and b are defined as in any
one of claims 1 to 7, and
Z is hydrogen or a group having the formula (CC) :
"
(CC) where the variables are defined as in any one of claims 1 to 7,
wherein:
a) when B, and E if present, are both -S-, the reaction temperature
is comprised between 20°C and 1200C,
b) when B, and E if present, are both -0-, if present, Q is
selected among cations of alkaline metals and an ammonium ion
trisubstituted by alkyl groups; the reaction of addition occurs in the
presence of an inert solvent, in the reaction environment there is 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 is
comprised between 20°C and 120°C;
c) when B, and E if present, are both -N(R2)-, if present, Q is
selected among cations of alkaline metals and, if the reagent having the
formula (BB) contains acid groups, they must be first salified with an
equimolecular quantity of a strong base; the reaction temperature is
comprised between 200C and 120°C.
10. The method according to claim 9, wherein if B, and E if
present, are both -S- and if the compound having the formula (BB)
contains acid groups, the method comprises an additional step for
salifying said acid groups by adding inorganic bases such as NaOH, KOH,
LiOH, NH4OH and mixtures thereof or organic bases such as primary,
secondary or tertiary amines and mixtures thereof, said salification
occurring preferably before addition with the epoxide.
11. The method according to claim 10, wherein the bases are
inorganic bases or tertiary amines and said salification step occurs before the reaction of the reagent having the formula (BB) with the
fluorinated epoxide (AA) .
12. The method according to one or more of claims 9 to 11, further
comprising the step of functionalizing the hydroxyl group that derives
from the opening of the epoxide to obtain the molecules having the
formula (I) in which R is not hydrogen, said step occurring after the
reaction of addition.
13. The method according to one or more of claims '9 to 11, further
comprising the step of using the hydroxyl group that derives from the
opening of the epoxide as a reactive group for the synthesis of polymers,
said step occurring after the reaction of addition and being alternative
to the group functionalization reaction.
14. The use of a compound having the formula (I) according' to one
or more of claims 1 to 7, or of a composition according to claim 8, to
lower the surface tension of fluid or solid materials to which said
compounds or compositions are applied.
15. The use of a compound having the formula (I) according to one
or more of claims 1 to 7, or of a composition according to claim 8,
' - as nonspecific fluorinated surfactant,
- as solid lubricant 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 additive in polymerization processes in emulsion,
- as corrosion inhibitor, - as additive for coatings,
- as agent in processes for treating paper and fabrics,
- as additive in enamels and in waxes for floors, for furniture and
for shoes,
- as additive in cleaning products,
- as wetting agent,
■ - as additive in glass antifogging formulas,
- as additive for fire-resistant compositions
- as additive for bases of skis and snow gear.
16. The use according to claim 15, wherein, if it is in a
composition, the compound having the formula (I) is used as additive for
coatings in a quantity comprised between 0.001% and 10% by weight.
17. The use according to claim 15, wherein, if it is in a
composition, the compound having the formula (I) is used as additive for
fire-resistant compositions in a quantity comprised between 0.001% and
10% by weight.
18. The use according to claim 15, wherein the compound having the
formula (I) is used as solid lubricant for snow sports gear, in a
quantity comprised between 0.3% and 30% by weight if it is in a
composition.
19. The use according to claim 18, wherein the compound having the
formula (I) is used as an additive for bases of skis and snow sports gear
in combination with polyethylene powder in a quantity comprised between
2% and 10% by weight on the finished composition.
EP06755959A 2005-06-20 2006-06-16 New fluorinated compounds, their synthesis and use Withdrawn EP1904428A2 (en)

Priority Applications (1)

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Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT001155A ITMI20051155A1 (en) 2005-06-20 2005-06-20 NEW FLUORURED COMPOUNDS, THEIR SYNTHESIS AND USE.
PCT/IB2006/001678 WO2006136920A2 (en) 2005-06-20 2006-06-16 New fluorinated compounds, their synthesis and use

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CN103865362B (en) * 2014-03-31 2016-01-20 方倩 A kind of preparation method of abrasion resistant fire blocking swash plate
FI3310764T3 (en) 2015-06-19 2023-07-18 Massachusetts Inst Technology Alkenyl substituted 2,5-piperazinediones and their use in compositions for delivering an agent to a subject or cell
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WO2006136920A2 (en) 2006-12-28
WO2006136920A3 (en) 2007-06-14
EP2343270A3 (en) 2011-12-28
EP2343270A2 (en) 2011-07-13

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