U.S. patent application number 14/877225 was filed with the patent office on 2016-01-28 for fluorosurfactants having improved biodegradability.
The applicant listed for this patent is HONEYWELL INTERNATIONAL INC.. Invention is credited to Haridasan K. Nair, David Nalewajek, Andrew J. Poss, Rajiv R. Singh, Yian Zhai.
Application Number | 20160023973 14/877225 |
Document ID | / |
Family ID | 52584128 |
Filed Date | 2016-01-28 |
United States Patent
Application |
20160023973 |
Kind Code |
A1 |
Nair; Haridasan K. ; et
al. |
January 28, 2016 |
FLUOROSURFACTANTS HAVING IMPROVED BIODEGRADABILITY
Abstract
To address the problem of insufficient biodegradability of
perfluorinated surfactants, the present invention provides
biodegradable fluorosurfactants derived from olefins having --CHR,
--CHRf, --CHF, and/or --CH.sub.2 groups, where R is an alkyl group
and Rf is a perfluoro or fluroroalkyl group. Preferably, the --CHR,
--CHRf, --CHF, and/or --CH.sub.2 groups are contained within
partially fluorinated alkenes.
Inventors: |
Nair; Haridasan K.;
(Williamsville, NY) ; Zhai; Yian; (Williamsville,
NY) ; Poss; Andrew J.; (Kenmore, NY) ; Singh;
Rajiv R.; (Getzville, NY) ; Nalewajek; David;
(West Seneca, NY) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
HONEYWELL INTERNATIONAL INC. |
MORRISTOWN |
NJ |
US |
|
|
Family ID: |
52584128 |
Appl. No.: |
14/877225 |
Filed: |
October 7, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
PCT/US2014/051807 |
Aug 20, 2014 |
|
|
|
14877225 |
|
|
|
|
61873675 |
Sep 4, 2013 |
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Current U.S.
Class: |
568/74 ; 568/35;
568/677; 570/137 |
Current CPC
Class: |
C08F 214/18 20130101;
C07C 43/137 20130101; C07C 41/03 20130101; C07C 19/16 20130101;
C07C 21/18 20130101; C07C 57/03 20130101; C07C 41/03 20130101; C08F
14/18 20130101; C07C 43/1786 20130101; C07C 309/06 20130101; C07C
229/12 20130101; C07C 43/137 20130101; C07C 323/03 20130101; C07C
323/25 20130101 |
International
Class: |
C07C 19/16 20060101
C07C019/16; C07C 323/03 20060101 C07C323/03; C07C 43/13 20060101
C07C043/13; C07C 309/06 20060101 C07C309/06 |
Claims
1. A fluorosurfactant having the general formula Rf--X--Y, wherein
Rf is a perfluorinated alkyl group, X is a fluoroolefin, Y is a
neutral group or a hydrophilic group, and wherein the surfactant is
biodegradable.
2. The fluorosurfactant of claim 1, wherein X is derived from a
partially fluorinated alkene.
3. The fluorosurfactant of claim 3, wherein the partially
fluorinated alkene is selected from the group consisting of
CF.sub.2.dbd.CFCl, CH.sub.2.dbd.CHF, CHF.dbd.CHF,
CH.sub.2.dbd.CF.sub.2, CF.sub.3CH.dbd.CHCF.sub.3,
CF.sub.3CF.dbd.CFCF.sub.3, CF.sub.3C.dbd.H, and
(CF.sub.3).sub.2CF--CF.dbd.CFCF.sub.3 (HFP dimer).
4. The fluorosurfactant of claim 2, wherein X is derived from a
partially fluorinated propene.
5. The fluorosurfactant of claim 3, wherein the partially
fluorinated propene is selected from the group consisting of
CF.sub.3CF.dbd.CH.sub.2 (HFO-1234yf), CF.sub.3CH.dbd.CHF
(HFO-1234ze), CF.sub.3CF.dbd.CHF (HFO-1225yf), CF.sub.3CH.dbd.CHCl
(HCFO 1233zd), CF.sub.3CH.dbd.CH.sub.2, CF.sub.3CH.dbd.CF.sub.2,
CF.sub.3CF.dbd.CF.sub.2, CF.sub.3CH.ident.CH,
(CF(CF.sub.3)(CF.sub.2H)H, and hexafluoropropene trimer.
6. The fluorosurfactant of claim 1, which is an anionic
surfactant.
7. The fluorosurfactant of claim 6, wherein the anionic surfactant
is selected from the group consisting of carboxylates, sulfonates,
sulfates, phosphates, and mixtures thereof.
8. The fluorosurfactant of claim 1, which is a cationic
surfactant.
9. The fluorosurfactant of claim 8, wherein the cationic surfactant
is selected from the group consisting of amino, amido, ammonio,
sulfonamido salts, and mixtures thereof.
10. The fluorosurfactant of claim 1, which is an amphoteric
surfactant.
11. The fluorosurfactant of claim 10, wherein the amphoteric
surfactant is selected from the group consisting of carboxybetaine,
sulfobetaine, sulfatobetaine, and mixtures thereof.
12. The fluorosurfactant of claim 1, which is a nonionic
surfactant.
13. The fluorosurfactant of claim 12, wherein the nonionic
surfactant is selected from the group consisting of oxyethylated
phenols, oxyethylated alcohols, polyhydric alcohols, and mixtures
thereof.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application is a continuation of PCT Application No.
PCT/US14/051807, filed Aug. 20, 2014, which application claims
priority from U.S. Provisional Application Ser. No. 61/873,675
filed Sep. 4, 2013, the disclosure of each which is hereby
incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to the production of
fluorosurfactants having improved biodegradability. More
specifically, the present invention relates to biodegradable
fluorosurfactants produced from olefins comprising --CHR, --CHRf,
--CHF, and/or --CH.sub.2 groups, wherein R is an alkyl group and Rf
is a perfluoro or fluroroalkyl group.
BACKGROUND OF THE INVENTION
[0003] Fluorosurfactants have many unique properties, and are
useful as soil and water repellents, airplane hydraulic fluids,
additives in firefighting foams, paints, coatings, clothing,
carpets, leather, waxes, polishes, and the like. Fluorosurfactants
like perfluorooctanoic acid (PFOA) are also used as surfactants in
aqueous media for the polymerization of hydrophobic monomers,
especially fluorinated monomers such as tetrafluoroethylene. See
Erik Kissa, Fluorinated Surfactants and Repellents, Surfactant
Science Series, Vol. 97, 2nd edition (2001) ("Kissa"). The most
commonly used fluorosurfactants are perfluorooctanoic acid (PFOA,
C.sub.7F.sub.15CO.sub.2H) and perfluorooctane sulfonate (PFOS,
C.sub.8F.sub.17SO.sub.3X, X.dbd.K, Na, H).
[0004] Typically, fluorosurfactants are compounds having a
hydrophobic (generally a perfluoroalkyl chain) and a hydrophilic
moiety (generally carboxylate/sulfate/quaternary ammonium moiety,
or the like). When the hydrophobic chain is a perfluoroalkyl group,
such as the C.sub.7F.sub.15 or C.sub.8F.sub.17, groups of PFOA and
PFOS, respectively, such compounds are highly resistant to
biodegradation. However, the fluorosurfactants having such
perfluoroalkyl hydrophobic chains are persistent, toxic,
bioaccumulable, and accordingly are found in blood of many animals
and humans all over the world. See, e.g., M. Houde et al., Environ.
Sci. Tech. 40, (2006), 3463-3473; Boutevin, et al., J. Fluorine
Chem. 134, (2012), 77-84. Accordingly, it is even possible that the
United States Environmental Protection Agency (EPA) may eliminate
the use of PFOA and PFOS in the near future owing to environmental
concerns. There is thus a significant and urgent need in developing
alternate fluorosurfactants that are biodegradable and
environmentally friendly (see H. J. Lehmler, Chemosphere, 58,
(2005), 1471-1496; G. Kostov et al., J. Fluorine Chem. 130, (2009),
1192-1199).
SUMMARY OF THE INVENTION
[0005] To address the problem of insufficient biodegradability, the
present invention provides biodegradable fluorosurfactants derived
from commercially available raw materials, i.e., from olefins
comprising --CHR, --CHRf, --CHF, and/or --CH.sub.2 groups.
[0006] Thus, one embodiment of the invention is a fluorosurfactant
having the general formula Rf--X--Y, wherein Rf is a perfluorinated
alkyl group, X is a fluoroolefin, Y is a neutral group, such as OH,
or a hydrophilic group, and wherein the surfactant is
biodegradable.
[0007] In certain embodiments, the fluorosurfactant of formula
Rf--X--Y includes X which is derived from a partially fluorinated
alkene.
[0008] In certain embodiments, the fluorosurfactant of formula
Rf--X--Y includes a partially fluorinated alkene which is selected
from the group consisting of CF.sub.2.dbd.CFCl, CH.sub.2.dbd.CHF,
CHF.dbd.CHF, CH.sub.2.dbd.CF.sub.2, CF.sub.3CH.dbd.CHCF.sub.3,
CF.sub.3CF.dbd.CFCF.sub.3, CF.sub.3C.dbd.H, and
(CF.sub.3).sub.2CF--CF.dbd.CFCF.sub.3 (HFP dimer).
[0009] In certain embodiments, the fluorosurfactant of formula
Rf--X--Y includes X which is derived from a partially fluorinated
propene.
[0010] In certain embodiments, the fluorosurfactant of formula
Rf--X--Y includes a partially fluorinated propene which is selected
from the group consisting of CF.sub.3CF.dbd.CH.sub.2 (HFO-1234yf),
CF.sub.3CH.dbd.CHF (HFO 1234ze), CF.sub.3CF.dbd.CHF (HFO-1225yf),
CF.sub.3CH.dbd.CHCl (HCFO-1233zd), CF.sub.3CH.dbd.CH.sub.2,
CF.sub.3CH.dbd.CF.sub.2, CF.sub.3CF.dbd.CF.sub.2,
CF.sub.3CH.ident.CH, (CF(CF.sub.3)(CF.sub.2H)H, and
hexfluoropropene trimer.
[0011] In certain embodiments, the fluorosurfactant is an anionic
surfactant.
[0012] In certain embodiments, the anionic surfactant is selected
from the group consisting of carboxylates, sulfonates, sulfates,
phosphates, and mixtures thereof.
[0013] In certain embodiments, the fluorosurfactant is a cationic
surfactant.
[0014] In certain embodiments, the cationic surfactant is selected
from the group consisting of amino, amido, ammonio, sulfonamido
salts, and mixtures thereof.
[0015] In certain embodiments, the fluorosurfactant is an
amphoteric surfactant.
[0016] In certain embodiments, the amphoteric surfactant is
selected from the group consisting of carboxybetaine, sulfobetaine,
sulfatobetaine, and mixtures thereof.
[0017] In certain embodiments, the fluorosurfactant is a nonionic
surfactant.
[0018] In certain embodiments, the nonionic surfactant is selected
from the group consisting of oxyethylated phenols, oxyethylated
alcohols, polyhydric alcohols, and mixtures thereof.
DETAILED DESCRIPTION OF THE INVENTION
[0019] As described above, in order to address the problem of
insufficient biodegradability of perfluorinated surfactants, the
present invention provides biodegradable fluorosurfactants derived
from olefins having --CHR, --CHRf, --CHF, and/or --CH.sub.2 groups,
where R is an alkyl group and Rf is a perfluoro or fluroroalkyl
group. Preferably, the --CHR, --CHRf, --CHF, and/or --CH.sub.2
groups are contained within partially fluorinated alkenes.
[0020] In accordance with the present invention, each of the four
major classes of Surfactants--anionic, cationic, amphoteric and
nonionic--may be prepared. Example anionic surfactants include
carboxylates, sulfonates, sulfates, and phosphates; example
cationic surfactants include amino, amido, ammonio, and sulfonamido
salts; example amphoteric surfactants include carboxybetaine,
sulfobetaine, and sulfatobetaine; and example nonionic surfactants
include oxyethylated phenols, as well as oxyethylated and
polyhydric alcohols. General examples for each of these surfactants
are provided below:
RfCO.sub.2.sup.-Na.sup.+/RF SO.sub.3.sup.-Na.sup.+, 1)
RfC(O)NH(CH.sub.2).sub.3 N.sup.+CH.sub.3I.sup.-, 2)
RfXYN.sup.+(CH.sub.3).sub.2(CH.sub.2).sub.nCO.sub.2.sup.-/SO.sub.3.sup.--
/OSO.sub.3.sup.-, and 3)
RfCH.sub.2O(CH.sub.2CH.sub.2O).sub.nH, respectively. 4)
wherein n is an integer and Rf is F-alkyl group comprising at least
one hydrogen, and having a straight or branched chain.
[0021] Preferably, the above fluorosurfactants are derived from a
number of fluoroolefins (X) that are available at Honeywell or from
commercial vendors. Examples include CF.sub.3CF.dbd.CH.sub.2
(HFO-1234yf), CF.sub.3CH.dbd.CHF (HFO-1234ze), CF.sub.3CF.dbd.CHF
(HFO-1225yf), CF.sub.3CH.dbd.CHCl (HCFO 1233zd),
CF.sub.3CH.dbd.CH.sub.2, CF.sub.3CH.dbd.CF.sub.2,
CF.sub.2.dbd.CFCl, CH.sub.2.dbd.CHF, CHF.dbd.CHF,
CH.sub.2.dbd.CF.sub.2, CF.sub.3CH.dbd.CHCF.sub.3,
CF.sub.3CF.dbd.CF.sub.2, CF.sub.3CF.dbd.CFCF.sub.3,
CF.sub.3C.dbd.H, (CF.sub.3).sub.2CF--CF.dbd.CFCF.sub.3 (HFP dimer),
CF.sub.3CH.ident.CH, (CF(CF.sub.3)(CF.sub.2H)H, and
hexfluoropropene trimer. Such surfactants can be prepared using
procedures similar to those detailed on pages 1-21 of Kissa, which
is incorporated herein by reference.
[0022] In accordance with one embodiment of the present invention,
alcohols derived from the above olefins for example,
CF.sub.3CFHCF.sub.2CH.sub.2OH and
(CF.sub.3).sub.2CF--CFH--CF(CF.sub.3)CH.sub.2OH, can also be
employed. As shown in Equation 1, short chain perfluoroalkyl
iodides Rf-I (Rf.dbd.CF.sub.3, C.sub.2F.sub.5, C.sub.3F.sub.7,
C.sub.4F.sub.9) can be added to these olefins in the presence of a
radical initiator such as ditertiary butyl peroxide, AIBN, benzoyl
peroxide or UV light to afford the adduct:
Rf--I+X.fwdarw.Rf--[X].sub.n--I (Eq. 1)
wherein Rf=CF.sub.3, C.sub.2F.sub.5, C.sub.3F.sub.7 or
C.sub.4F.sub.9 and X=CF.sub.3CF.dbd.CH.sub.2 (HFO-1234yf),
CF.sub.3CH.dbd.CHF (HFO-1234ze), CF.sub.3CF.dbd.CHF (HFO-1225yf),
CF.sub.3CH.dbd.CHCl (HCFO 1233zd), CF.sub.3CH.dbd.CH.sub.2,
CF.sub.3CH.dbd.CF.sub.2, CF.sub.2.dbd.CFCl, CH.sub.2.dbd.CHF,
CHF.dbd.CHF, CH.sub.2.dbd.CF.sub.2,
(CF.sub.3).sub.2CF--CF.dbd.CF(CF.sub.3), CF.sub.3CF.dbd.CF.sub.2,
CF.sub.3CH.dbd.CH (CF(CF.sub.3)(CF.sub.2H)H, or hexfluoropropene
trimer. X includes all isomers.
[0023] In accordance with a second embodiment of the present
invention, a useful class of precursors for surfactants is
alcohols. Alcohol derivatives of X compounds can be made by the
addition of methanol to olefins (see Equation 1a) or from compounds
of formula
Rf[X].sub.n--[(CH.sub.2--CH.sub.2)].sub.mI:
X+CH.sub.3OH.fwdarw.H--X--CH.sub.2OH (Eq. 1a)
wherein X is as defined in Equation 1.
[0024] In accordance with a third embodiment of the present
invention, ethylene can be added to compounds of formula
Rf--[X].sub.n--I to afford ethylenated product as given below in
Equation 2:
Rf--[X].sub.n--I+CH.sub.2.dbd.CH.sub.2.fwdarw.Rf--[X].sub.n--[(CH.sub.2--
-CH.sub.2)].sub.mI (Eq. 2)
wherein m=1 or 2. Various conditions can be employed to get the
desired number of m.
[0025] Compounds of formula
Rf--[X].sub.n--[(CH.sub.2--CH.sub.2)].sub.mI can be converted to
various classes of surfactants by functionalizing with various
hydrophilic groups (Y) including carboxylates, sulfonates,
phosphates, ammonium salts, various betaines, ethoxylated alcohol
and the like as shown in Equation 2a, and as described on pages
29-79 of Kissa, which is incorporated herein by reference:
Rf--[X].sub.n--[(CH.sub.2-CH.sub.2)].sub.mI.fwdarw.Rf--[X].sub.n--CH.sub-
.2--Y (Eq. 2a)
wherein Y=a carboxylate, sulfate, sulfonate, phosphate, quaternary
ammonium, carboxybetaine, sulfobetaines, sulfatobetaine,
phosphatobetaine, or alcohol group.
[0026] Representative examples include:
Rf--[X].sub.n--CH.sub.2--CO.sub.2H;
Rf--[X].sub.n--CH.sub.2--CO.sub.2Na;
Rf--[X].sub.n--CH.sub.2--SO.sub.3H;
Rf--[X].sub.n--CH.sub.2--SO.sub.3Na;
Rf--[X].sub.n--CH.sub.2--OP(O)(OH).sub.2;
Rf--[X].sub.n--CH.sub.2--CH.sub.2--N.sup.+(CH.sub.3).sub.3 I.sup.-;
Rf[X].sub.n--CH.sub.2CH.sub.2SO.sub.2NH(CH.sub.2).sub.3N.sup.+(CH.sub.3).-
sub.3 I.sup.-;
Rf--[X].sub.n--CH.sub.2CH.sub.2N.sup.+
(CH.sub.3).sub.2CH.sub.2CO.sub.2.sup.-;
Rf--[X].sub.n--CH.sub.2CH.sub.2SCH.sub.2CH.sub.2N(CH.sub.3).sub.2.sup.+CH-
.sub.2CO.sub.2.sup.-;
Rf--[X].sub.n--CH.sub.2--O(CH.sub.2CH.sub.2O).sub.nH; and,
Rf--[X].sub.n--CONH(CH.sub.2).sub.3N(CH.sub.2CH.sub.2O).sub.nH,
wherein n in the above formulae denotes an integer.
[0027] In accordance with a fourth embodiment of the present
invention, preparation of carboxylic acids can be achieved by
converting the F-alkyl iodides to the respective alcohol, which is
then oxidized to carboxylic acid (see Equation 3) with a suitable
reagent such HNO.sub.3, and alternatively, the iodides can also be
converted to acid with a reagent combination of
K.sub.2Cr.sub.2O.sub.7/H.sub.2SO.sub.4 (see Equation 4):
Rf--[X]--CH.sub.2CH.sub.2I.fwdarw.Rf--[X]--CH.sub.2CH.sub.2OH.fwdarw.Rf--
-[X]--CH.sub.2CO.sub.2H (Eq. 3)
Rf--[X]--CH.sub.2CH.sub.2I
(K.sub.2Cr.sub.2O.sub.7/H.sub.2SO.sub.4).fwdarw.Rf--[X]--CH.sub.2CO.sub.2-
H (Eq. 4)
[0028] Respective salts can be obtained by treating the acids with
sodium or potassium hydroxide, and F-alkyl iodides can be converted
to sulfonic acids by many well established methods in the art.
[0029] In accordance with a fifth embodiment of the present
invention, as shown in Equations 5 and 6, cationic surfactants are
prepared by different methods known in the art, e.g., by treating
sulfonyl chloride halide with an amine and then quaternizing with
an alkyl halide.
Rf--[X]--CH.sub.2CH.sub.2SO.sub.2Cl+(CH.sub.3).sub.2N(CH.sub.2).sub.3NH.-
sub.2.fwdarw.
Rf--[X]--CH.sub.2CH.sub.2SO.sub.2NH(CH.sub.2).sub.3N(CH.sub.3).sub.2
(Eq. 5)
Rf--[X]--CH.sub.2CH.sub.2SO.sub.2NH(CH.sub.2).sub.3N(CH.sub.3).sub.2+CH.-
sub.3I.fwdarw.
Rf--[X]--CH.sub.2CH.sub.2SO.sub.2NH(CH.sub.2).sub.3N.sup.+
(CH.sub.3).sub.3I.sup.- (Eq. 6)
[0030] In accordance with a sixth embodiment of the present
invention, amphoteric surfactants such as betaines are prepared as
shown in Equations 7 and 8. For example, carboxy betaines may be
prepared by treating F-alkyl tertiaryamine with chloro acetic acid
or its sodium salt. Carboxy-betaines with sulfide linkage may be
prepared by treating F-alkyl iodide with
(2-mercaptoethyl)dimethylammonium chloride and subsequent
quaternization with chloroacetic acid.
Rf--[X]--CH.sub.2CH.sub.2I+HSCH.sub.2CH.sub.2N(CH.sub.3).sub.2.HCl+NaOH.-
fwdarw.
Rf--[X]--(CH.sub.2).sub.2SCH.sub.2CH.sub.2N(CH.sub.3).sub.2 (Eq.
7)
Rf--[X]--(CH.sub.2).sub.2SCH.sub.2CH.sub.2N(CH.sub.3).sub.2+ClCH.sub.2CO-
.sub.2H.fwdarw.
Rf--[X]--(CH.sub.2).sub.2SCH.sub.2CH.sub.2N.sup.+
(CH.sub.3).sub.2CH.sub.2CO.sub.2.sup.- (Eq. 8)
[0031] As shown in Equation 9, nonionic F-alkyl surfactants can be
prepared by straight forward oxyethylenation in the presence of
catalyst, for example, boron trifluoride (BF.sub.3 cat).
Rf--[X]--CH.sub.2CH.sub.2OH+Ethylene oxide+(BF.sub.3
cat).fwdarw.
Rf--[X]--CH.sub.2CH.sub.2O(CH.sub.2CH.sub.2O).sub.nH (Eq. 9)
EXAMPLES
Example 1
Addition of C.sub.2F.sub.5I to CF.sub.3CH.dbd.CHF
[0032] Into a clean, dry and evacuated 650 ml autoclave (Parr.RTM.
reactor) was added ditertiarybutyl peroxide (10.5 g) and
C.sub.2F.sub.5I (75 g). The autoclave was then cooled with dry ice
and condensed 65 g CF.sub.3CH.dbd.CHF. The reactor was brought to
room temperature and heated to and maintained at 145.degree. to
150.degree. C. for 6 hrs; the reactor was then brought to room
temperature, vented of volatile materials, and the contents in the
autoclave were poured into cold water. The separated organic phase
was washed with 5% aq. sodium bisulphite (20 mL), water(20 mL) and
brine (20 mL), dried (MgSO.sub.4), and distilled to afford
CF.sub.3CF.sub.2[CHF--CH(CF.sub.3)].sub.n--I (n=1).
Example 2
[0033] The reaction was conducted in the same manner as in Example
1, except that CF.sub.3CF.dbd.CHF was used instead of
CF.sub.3CH.dbd.CFH to afford
CF.sub.3CF.sub.2[CHF--CF(CF.sub.3)].sub.n--I (n=1).
Example 3
[0034] The reaction of C.sub.2F.sub.5I with
CF.sub.3CF.dbd.CH.sub.2, CF.sub.3H.dbd.CH.sub.2, CF.sub.2.dbd.CFCl,
CF.sub.3CF.dbd.CF.sub.2, (CF.sub.3).sub.2CF--CF.dbd.CF(CF.sub.3),
CF.sub.3CH.dbd.CH(CH(CF.sub.3)(CF.sub.2H)) were carried out as in
example 1, and the following compounds were obtained:
CF.sub.3CF.sub.2[CF.sub.3CF--CH.sub.2].sub.n--I,
CF.sub.3CF.sub.2[CF.sub.3CH--CH.sub.2].sub.n--I,
CF.sub.3CF.sub.2[CF.sub.2--CFCl].sub.n--I,
CF.sub.3CF.sub.2[CF.sub.2--CF(CF.sub.3)].sub.n--I,
CF.sub.3CF.sub.2[(CF.sub.3)CF--C(C.sub.2F.sub.5)--CF(CF.sub.3).sub.2](iso-
mers), and
CF.sub.3CF.sub.2[(CF.sub.3)CH--CH--(CF(CF.sub.3)(CF.sub.2H))].sub.n--I
(all n=1).
Example 4
Insertion of Ethylene into C--I Bond in
CF.sub.3CF.sub.2[CHF--CH(CF.sub.3)].sub.n--I (n=1)
[0035] A 400 mL autoclave was charged with
CF.sub.3CF.sub.2[CHF--CH(CF.sub.3)].sub.n--I (n=1) (72 g, 0.2 mol),
ethylene (6.25 g, 0.13 mol) and D (+)-limonene (0.4 g) and the
reactor was heated at 240.degree. C. for 12 hours. The product
formed was then transferred and distilled under reduced pressure to
afford
CF.sub.3CF.sub.2[CHF--CH(CF.sub.3)].sub.n--(CH.sub.2--CH.sub.2).sub.m--I
(n=m=1) as the major product (60%).
Example 5
[0036] In a similar manner, ethylenated compounds were prepared for
CF.sub.3CF.sub.2[CF.sub.3CF--CH.sub.2].sub.n--I,
CF.sub.3CF.sub.2[CF.sub.3CH--CH.sub.2].sub.n--I,
CF.sub.3CF.sub.2[CF.sub.2--CFCl].sub.n--I,
CF.sub.3CF.sub.2[CF.sub.2--CF(CF.sub.3)].sub.n--I,
CF.sub.3CF.sub.2[(CF.sub.3)CF--C(C.sub.2F.sub.5)--CF(CF.sub.3).sub.2].sub-
.n--I (isomers),
CF.sub.3CF.sub.2[(CF.sub.3)CH--CH--(CF(CF.sub.3)--(CF.sub.2H))].sub.n--I
by following the procedure of Example 4.
Example 6
Conversion of
CF.sub.3CF.sub.2[CHF--CH(CF.sub.3)].sub.n--(CH.sub.2--CH.sub.2).sub.m--I
(n=m=1) to
CF.sub.3CF.sub.2[CHF--CH(CF.sub.3)].sub.n--(CH.sub.2--CH.sub.2).sub.m--SO-
.sub.3Na.
[0037] A 500 mL flask equipped with a stirrer, condenser, a mixture
of
CF.sub.3CF.sub.2[CHF--CH(CF.sub.3)].sub.n--(CH.sub.2--CH.sub.2).sub.m--I
(n=m=1) (0.2 mol), ethanol (100 mL), water (100 mL), sodium sulfite
(0.4 mol) and copper powder (4.8 g) was refluxed under nitrogen for
a week. After this, 250 mL water was added, mixed well and
filtered. The filtrate was cooled and crystallized/precipitated
using sodium salt, and
CF.sub.3CF.sub.2[CHF--CH(CF.sub.3)].sub.n--(CH.sub.2--CH.sub.2).sub.m--SO-
.sub.3Na was separated by filtration and dried (0.15 mol, 75%).
Example 7
Conversion of CF.sub.3CF.sub.2[CHF--(CF.sub.3)CH].sub.n--I to
CF.sub.3CF.sub.2[CHF--(CF.sub.3)CH].sub.n--CH.sub.2CO.sub.2H/Na
(n=1)
[0038] Conversion of CF.sub.3CF.sub.2[CHF--(CF.sub.3)CH].sub.n--I
to CF.sub.3CF.sub.2[CHF--(CF.sub.3)CH].sub.n--CH.sub.2CO.sub.2H was
effected as described in J. Fluorine Chem. 66, (1994), 249-252,
incorporated herein by reference. Thus,
CF.sub.3CF.sub.2[CHF--(CF.sub.3)CH].sub.n--I was reacted with vinyl
acetate to
CF.sub.3CF.sub.2[CHF--(CF.sub.3)CH].sub.n--CH.sub.2CHIOCOCH.sub.3,
which was then hydrolyzed to aldehyde,
CF.sub.3CF.sub.2[CHF--(CF.sub.3)CH].sub.n--CH.sub.2CHO, and finally
oxidized to the desired acid,
CF.sub.3CF.sub.2[CHF--(CF.sub.3)CH].sub.n--CH.sub.2CO.sub.2H. The
acid was converted to its sodium salt by treating with equimolar
amount of NaOH in water. In a similar fashion, by employing the
above procedure other iodides were converted to the respective
acids/salts.
Example 8
Conversion of
CF.sub.3CF.sub.2[CHF--(CF.sub.3)CH].sub.n--[CH.sub.2CH.sub.2].sub.mI
(n=m=1) to betaine derivative
CF.sub.3CF.sub.2[CHF--(CF.sub.3)CH].sub.n--[CH.sub.2CH.sub.2].sub.mN.sup.-
+(CH.sub.3).sub.2CH.sub.2CO.sub.2HCl.sup.-
[0039] Part A: A solution of dimethylamine (0.025 mol) (33% in
ethanol) and
CF.sub.3CF.sub.2[CHF--(CF.sub.3)CH].sub.n--[CH.sub.2CH.sub.2].sub.mI
(0.02 mol) was added to sodium carbonate (0.2 mol) in ethanol and
water (60 mL+15 mL) solution and refluxed for 24 hours. After this
the reaction mixture was filtered, the filtrate was washed with
water (10 ml), extracted in ether (50 mL), and dried
(Na.sub.2SO.sub.4) to afford the crude amine derivative which was
distilled to afford
CF.sub.3CF.sub.2[CHF--(CF.sub.3)CH].sub.n--[CH.sub.2CH.sub.2].sub.mN(CH.s-
ub.3).sub.2.
[0040] Part B: Subsequently, a stirred mixture of
CF.sub.3CF.sub.2[CHF--(CF.sub.3)CH].sub.n--[CH.sub.2CH.sub.2].sub.mN(CH.s-
ub.3).sub.2 (0.01 mol) and monochloro acetic acid (0.01 mol) was
slowly heated (120.degree. to 130.degree. C.) for an hour in an oil
bath to afford the product
CF.sub.3CF.sub.2[CHF--(CF.sub.3)CH].sub.n--[CH.sub.2CH.sub.2].sub.mN.sup.-
+(CH.sub.3).sub.2CH.sub.2CO.sub.2HCl.sup.-.
Example 9
Preparation of
CF.sub.3CF.sub.2[CHF--(CF.sub.3)CH].sub.n--CH.sub.2CH.sub.2].sub.mSCH.sub-
.2CH.sub.2N.sup.+(CH.sub.3).sub.2CH.sub.2CO.sub.2HCl.sup.-
(n=m=1)
[0041] Part A: To a stirred solution of NaOH (4.0 g, 0.1 mol) in
absolute ethanol (50 mL) was added 0.05 mol of
2-dimethylaminoethylthiohydrochloride, and the mixture was heated
to 50.degree. C. for 15 minutes. This solution was then added to a
solution of CF.sub.3CF.sub.2[CHF--(CF.sub.3)CH].sub.nI (0.05 mol)
in 100 mL tertiaryamyl alcohol and the mixture was refluxed for 6
hours. After cooling to room temperature, the reaction mixture was
filtered, concentrated on a rotavap, and the residue extracted with
ether (2.times.150 mL). The combined ether extracts were washed
with 150 ml 5% aqueous NaOH, 100 mL water, dried (MgSO.sub.4), and
concentrated under reduced pressure to give a liquid residue--the
crude
CF.sub.3CF.sub.2[CHF--(CF.sub.3)CH].sub.nSCH.sub.2CH.sub.2N(CH.sub.3).sub-
.2--which could be purified via distillation.
[0042] Part B: The reaction was conducted exactly the same manner
as described in Example 8, part B, except that
CF.sub.3CF.sub.2[CHF--(CF.sub.3)CH].sub.nSCH.sub.2CH.sub.2N(CH.sub.3).sub-
.2 was used in place of
CF.sub.3CF.sub.2[CHF--(CF.sub.3)CH].sub.n--[CH.sub.2CH.sub.2].sub.mN(CH.s-
ub.3).sub.2 to afford
CF.sub.3CF.sub.2[CHF--(CF.sub.3)CH].sub.n--[CH.sub.2CH.sub.2].sub.mSCH.su-
b.2CH.sub.2N.sup.+ (CH.sub.3).sub.2CH.sub.2CO.sub.2HCl.sup.-.
Example 10
Conversion of (CF.sub.3).sub.2CF--CFH--(CF.sub.3)CF--CH.sub.2OH to
(CF.sub.3).sub.2CF--CFH--(CF.sub.3)CF--CH.sub.2O--CH.sub.2CH.sub.2OH
[0043] Part A: Ethylene oxide (12.1 mmol) was allowed to react in
diethyl ether with 32 mmol
(CF.sub.3).sub.2CF-CFH-(CF.sub.3)CF-CH.sub.2OH in ether with
BF.sub.3 etherate complex (3.0 g) as the catalyst for 10 min at
room temperature. The reaction mixture was concentrated, extracted
in ether, washed with 2% NaOH, washed with water, and dried to
afford
(CF.sub.3).sub.2CF--CFH--(CF.sub.3)CF--CH.sub.2O--CH.sub.2CH.sub.2OH.
[0044] Part B: Ethylene oxide (12.1 mmol) was allowed to react in
diethyl ether with dehydrated alumina (10 g) and 32 mmol
(CF.sub.3).sub.2CF--CFH--(CF.sub.3)CF--CH.sub.2OH for 10 min at
room temperature. Filtration and work up afforded
(CF.sub.3).sub.2CF--CFH--(CF.sub.3)CF--CH.sub.2O--CH.sub.2CH.sub.2OH.
[0045] From the foregoing, it will be appreciated that although
specific examples have been described herein for purposes of
illustration, various modifications may be made without deviating
from the spirit or scope of this disclosure. It is therefore
intended that the foregoing detailed description be regarded as
illustrative rather than limiting, and that it be understood that
it is the following claims, including all equivalents, that are
intended to particularly point out and distinctly claim the claimed
subject matter.
* * * * *