U.S. patent application number 10/553217 was filed with the patent office on 2006-11-30 for partially fluorinated lubricants for solid surfaces.
This patent application is currently assigned to CLARIANT GMBH. Invention is credited to Ralf Grottenmueller, Anton Probst, Robert Schmid, Norbert Schmitt.
Application Number | 20060270570 10/553217 |
Document ID | / |
Family ID | 33103380 |
Filed Date | 2006-11-30 |
United States Patent
Application |
20060270570 |
Kind Code |
A1 |
Grottenmueller; Ralf ; et
al. |
November 30, 2006 |
Partially fluorinated lubricants for solid surfaces
Abstract
Lubricants intended for solid surfaces, and particularly for
skis, and comprising a partially fluorinated compound of formula 1
RF--(A).sub.a--(O).sub.b--(B).sub.c--(D).sub.d--(RF).sub.e (1)where
RF is a perfluorinated radical of formula F(CF.sub.2).sub.n-, n is
a number from 1 to 20, A is C.sub.1-C.sub.30, preferably
C.sub.1-C.sub.18, alkylene. B is arylene having 6 to 14 carbon
atoms or is a saturated or unsaturated monocyclic or polycyclic
hydrocarbon having 3 to 30, preferably 3 to 18 carbon atoms, D is
hydrogen or C.sub.1-C.sub.30, preferably C.sub.1-C.sub.18, alkyl, a
is zero or 1, b, c, and d are zero, 1 or 2 and e is zero or 1, with
the proviso that b and c are not simultaneously zero.
Inventors: |
Grottenmueller; Ralf;
(Wiesbaden, DE) ; Schmitt; Norbert; (Burgkirchen,
DE) ; Probst; Anton; (Erlbach, DE) ; Schmid;
Robert; (Neuotting, DE) |
Correspondence
Address: |
CLARIANT CORPORATION;INTELLECTUAL PROPERTY DEPARTMENT
4000 MONROE ROAD
CHARLOTTE
NC
28205
US
|
Assignee: |
CLARIANT GMBH
Frankfurt am Main
DE
|
Family ID: |
33103380 |
Appl. No.: |
10/553217 |
Filed: |
April 8, 2004 |
PCT Filed: |
April 8, 2004 |
PCT NO: |
PCT/EP04/03755 |
371 Date: |
August 15, 2006 |
Current U.S.
Class: |
508/582 ;
508/588; 570/123 |
Current CPC
Class: |
C10M 105/52 20130101;
C10M 2211/0225 20130101; C10M 2211/0425 20130101; C10M 2211/0245
20130101; C10M 105/54 20130101; C09G 3/00 20130101 |
Class at
Publication: |
508/582 ;
508/588; 570/123 |
International
Class: |
C10M 131/08 20060101
C10M131/08; C10M 131/02 20060101 C10M131/02 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 15, 2003 |
DE |
103 17 198.3 |
Claims
1. A lubricant intended comprising a partially fluorinated compound
of formula 1
RF--(A).sub.a--(O).sub.b--(B).sub.c--(D).sub.d--(RF).sub.e (1)
wherein RF is a perfluorinated radical of formula
F(CF.sub.2).sub.n-, n is a number from 1 to 20, A is
C.sub.1-C.sub.30, B is arylene having 6 to 14 carbon atoms or is a
saturated or unsaturated monocyclic or polycyclic hydrocarbon
having 3 to 30, carbon atoms, D is hydrogen, and a=1, b=0, c=1,
d=1, and e=0.
2. (canceled)
3. The process of waxing a ski comprising the step of applying the
lubricant according to claim 1 to a surface of the ski.
4. A solid, a solution or a dispersion comprising the lubricant
according to claim 1.
5. The lubricant according to claim 1, further comprising at least
one second lubricant.
6. The process of reducing the friction of a solid surface
comprising the step of coating the solid surface with the lubricant
according to claim 1.
7. The lubricant according to claim 1, wherein A is a
C.sub.1-C.sub.18 alkylene.
8. The lubricant according to claim 1, wherein B is a saturated or
unsaturated monocyclic or polycyclic hydrocarbon having 3 to 18
carbon atoms.
9. The lubricant according to claim 5, wherein the at least one
second lubricant is fluorinated or nonfluorinated.
10. A ski wax comprising the lubricant according to claim 1.
Description
[0001] The invention relates to the use of partially fluorinated
compounds as ski lubricants.
[0002] Ski waxes are used in order to enhance the sliding
properties of skis. Conventional ski waxes generally include
relatively high molecular mass hydrocarbons such as paraffins,
fatty acids, fatty acid esters, and fatty alcohols or mixtures of
these and similar compounds. Certain fluorinated compounds have
proven extremely effective ski waxes and are employed particularly
in the high-performance sport. The reason for the great
effectiveness of fluorinated waxes is the coating of the ski with a
fluorinated surface possessing very low surface tension, thereby
greatly reducing the friction. By coating with fluorochemicals it
is possible to lower the surface tension of, say, polyethylene (31
dyn/cm) to levels of 6-18 dyn/cm. The value of 6 dyn/cm is achieved
for a surface composed of perfectly oriented CF3 groups.
[0003] Some fluorinated compounds which can be used as ski
lubricants are already known. WO 89/10950, for example, describes
the addition of PTFE micropowder to unfluorinated ski waxes. The
molar weight of the PTFE is preferably 50 000-400 000 g/mol and the
particle size is less than 15 .mu.m. EP 0 132 879 describes the
synthesis of relatively long-chain perfluoroalkanes of the formula
F(CF.sub.2).sub.nF and also their use as lubricants for surfaces.
EP 0 444 752 describes the use of fluorinated diblock compounds of
the formula F(CF.sub.2).sub.n--(CH.sub.2).sub.mH, where n=3-15 and
m=5-23, as ski wax. These compounds have the advantage of
compatibility with unfluorinated paraffin waxes, owing to the
hydrocarbon block. DE 4 139 765 describes oligomers of fluorinated
olefins of the formula F(CF.sub.2).sub.n--CH.dbd.CH.sub.2. The
product can be prepared by free-radical oligomerization of said
olefins and is suitable as a lubricant for a variety of surfaces.
U.S. Pat. No. 5,502,225 and DE 100 29 623 describe fluorinated
oligomeric urethanes which are obtained by addition reaction of
fluorine-free isocyanates and fluorinated alcohols as essential
components. EP 0 421 303 describes the use of partially fluorinated
polyacrylates. The preparation takes place by free-radical
copolymerization of fluorinated acrylates such as
2-perfluoroalkylethyl acrylate, for example, with nonfluorinated
monomers such as long-chain fatty alcohol acrylates, for example.
Ski waxes may also be provided with a variety of additives in order
to prevent the friction-induced electrostatic charging, which can
lead to the adherence of a water film. CH 660 018, for example,
describes the use of graphite for the purpose of increasing the
conductivity.
[0004] It has now been found that certain partially fluorinated
compounds can surprisingly likewise be used as ski waxes. These
compounds are coupling products of one or more perfluoroalkyl
radicals with a fluorine-free alkyl or aryl radical. Apart from
oxygen atoms in the form of ether bonds, the coupling product must
be composed exclusively of the elements fluorine, carbon, and
hydrogen. Absent an ether bond, the fluorine-free alkyl or aryl
radical must have at least one monocyclic or polycyclic structural
element, which may be saturated, unsaturated, aromatic, possibly
branched, and monofunctional or bifunctional.
[0005] The invention provides lubricants intended for solid
surfaces and comprising a partially fluorinated compound of formula
1 RF--(A).sub.a--(O).sub.b--(B).sub.c--(D).sub.d--(RF).sub.e (1)
where
[0006] RF is a perfluorinated radical of formula
F(CF.sub.2).sub.n-,
[0007] n is a number from 1 to 20,
[0008] A is C.sub.1-C.sub.30, preferably C.sub.1-C.sub.18,
alkylene.
[0009] B is arylene having 6 to 14 carbon atoms or is a saturated
or unsaturated monocyclic or polycyclic hydrocarbon having 3 to 30,
preferably 3 to 18 carbon atoms,
[0010] D is hydrogen or C.sub.1-C.sub.30, preferably
C.sub.1-C.sub.18, alkyl,
[0011] a is zero or 1,
[0012] b, c, and d are zero, 1 or 2 and e is zero or 1, with the
proviso that b and c are not simultaneously zero.
[0013] Preference is given to compounds of the above formula in
which a=1, b=0, c=1, d=1, D=H, and e=0, the remaining symbols
having the definitions given above.
[0014] The compounds of formula above can be synthesized in
principle in a number of ways. The most common is the addition
reaction of perfluoroalkyl iodides with olefinic double bonds,
free-radically or metal-catalyzed, for example, and substitution
reaction of perfluoroalkyl iodides on aromatic systems, which are
carried out with metal catalysis, for example. It will be
appreciated that other methods, not specified here but sufficiently
well known to the skilled worker, of linking perfluoroalkyl
radicals to fluorine-free compounds are also possible.
[0015] Surprisingly it has now been found that the compounds
described above are outstandingly suitable for coating skis for the
purpose of improving the sliding properties. The effect is
presumably attributable to the fact that the fluorine radicals
orient themselves toward the air and, as a result of the CF.sub.3
surface coating thus formed, a low-energy surface is produced which
has a very low surface tension and also good sliding
properties.
[0016] The requirements imposed on the physical and chemical
properties of a ski wax differ greatly according to snow and
weather conditions. Through a suitable choice of the fluorinated
moiety and of the fluorine-free moiety of the active compound it is
readily possible to vary the physicochemical properties of the
active compound within wide limits and to adapt them to the
requirements. It is also possible to use combinations of two or
more of the active compounds described. Long-chain perfluoroalkyl
radicals.gtoreq.C.sub.8F.sub.17, for example, increase the hardness
of the active compound. As a result of the fluorine-free moiety
present, moreover, it is possible to achieve miscibility or
compatibility with fluorine-free ski waxes.
[0017] The compounds described can be applied in conventional
manner to the sliding surface of the ski, by means for example of
the melting of these compounds, where present in solid form, with a
hot iron and their application to the ski. As alternative to this
the compounds described can be applied in the form of a solution in
one or more organic solvents, preferably in a concentration of
0.5%-5%, or in the form of a solid, to the ski. Where the wax is
used in the form of a solution it is necessary to select a suitable
solvent, depending on the fluorine content. At high fluorine
content it may be necessary to use fluorinated solvents such as
perfluorohexane, 1H-perfluorohexane or Frigen products, for
example. At a low fluorine content, nonfluorinated solvents are
suitable as well, such as ethyl acetate, butyl acetate or THF, for
example. It is also possible to use mixtures of two or more
solvents. A further possibility is to employ the active compound in
the form of a suspension or dispersion. The fluorinated compounds
described can be combined, alone or in a mixture, with other
fluorinated or nonfluorinated ski waxes.
[0018] The fluorinated active compounds described are suitable not
only as ski waxes but also for coating surfaces of a wide variety
of kinds such as metal, plastic, and glass, for example. The
coating applies a hydrophobic and oleophobic film to the surface in
question, and said film greatly reduces the friction.
EXAMPLES
Synthesis
[0019] Compounds 1-6 were synthesized by free-radical addition
reaction of perfluoroalkyl iodide with C--C double bonds and
subsequent hydrodehalogenation, in accordance with reaction scheme
I and the following general instructions. ##STR1##
[0020] General instructions for the synthesis of compounds 1-6:
[0021] Perfluoroalkyl iodide and olefin component are reacted in a
molar ratio of 1:1 with 5 mol % of percarbonate and/or peroxide
free-radical initiator (e.g., dilauryl peroxide) at 100-110.degree.
C. for 2 h. Then a further 5 mol % of free-radical initiator are
added and reaction continues at 100-110.degree. C. for 2 h. After
the reaction mixture has cooled to room temperature, 1.5 times the
mass of isopropanol, 0.5 times the mass of acetic acid, and 150 mol
% of zinc powder are added and the mixture is stirred for 1 h.
Reaction then takes place under reflux conditions for a further 3
h. Following filtration to remove insoluble fractions, the solvent
is stripped off and the residue is freed under a high vacuum from
unreacted starting materials and byproducts. The purity of the
product is between 85% and 95%.
Synthesis of Compound 7
[0022] Compound 7 was prepared in accordance with a set of
instructions from J. Org. Chem. 6, (2002), 7185-7192 by coupling 2
mol of RFI and one mole of biphenyl with copper in DMSO as
solvent.
Synthesis of Compound 8
[0023] Compound 8 was prepared by a set of instructions from
Organikum, Wiley-VCH, 21.sup.st edition, 2001, p. 375 by
Friedel-Crafts alkylation of perfluoroalkylpropyl chloride
(prepared by reacting 3-perfluoroalkyl-1-propanol and thionyl
chloride) and decylbenzene, with catalysis by aluminum
chloride.
Synthesis of Compound 9
[0024] Compound 9 was prepared by a set of instructions following
the general procedure of Organikum, Wiley-VCH, 21.sup.st edition,
2001, p. 239 by reacting perfluoroalkylpropyl tosylate (prepared by
reacting 3-perfluoroalkyl-1-propanol with p-toluenesulfonyl
chloride) and dodecylphenol in acetone with potassium
carbonate.
Examples
Compound 1:
[0025] Product of RFI (RF=F(CF.sub.2).sub.n, n=63% 10, 30% 12,
7%.gtoreq.14) and styrene ##STR2##
[0026] 1 RF--CH.sub.2--CH.sub.2--C.sub.6H.sub.5
Compound 2:
[0027] Product of RFI (RF=F(CF.sub.2).sub.n, n=63% 10, 30% 12,
7%.gtoreq.14) and 4-phenyl-1-butene ##STR3##
[0028] 2 RF--(CH.sub.2).sub.4--C.sub.6H.sub.5
Compound 3:
[0029] Product of RFI (RF=F(CF.sub.2).sub.n, n=8) and 3-butenyl
dodecyl ether
[0030] 3 RF--(CH.sub.2).sub.4--O--C.sub.12H.sub.25 ##STR4##
Compound 4:
[0031] Product of RFI (RF=F(CF.sub.2).sub.n, n=63% 10, 30% 12,
7%.gtoreq.14) and .beta.-pinene ##STR5##
[0032] 4 RF-.beta.-pinene
Compound 5:
[0033] Product of RFI (RF=F(CF.sub.2).sub.n, n=63% 10, 30% 12,
7%.gtoreq.14) and cyclooctene ##STR6##
[0034] 5 RF-cyclooctene
Compound 6:
[0035] Product of RFI (RF=F(CF.sub.2).sub.n, n=8) and 3-butenyl
dodecylphenyl ether ##STR7##
[0036] 6
RF--(CH.sub.2).sub.4--O--C.sub.6H.sub.4--C.sub.12H.sub.25
Compound 7:
[0037] Product of 2 mol of RFI (RF=F(CF.sub.2).sub.n, n=8) and 1
mol of biphenyl ##STR8##
[0038] 7 RF--C.sub.6H.sub.4--C.sub.6H.sub.4--RF
Compound 8:
[0039] Product of perfluoroalkyloropyl chloride and decylbenzene
(RF=F(CF.sub.2).sub.n, n=7% 6, 63% 8, 28% 10, 2%.gtoreq.12).
##STR9##
[0040] 8 RF--(CH.sub.2).sub.3--C.sub.6H.sub.4--C.sub.10H.sub.21
Compound 9:
[0041] Product of perfluoroalkylpropyl tosylate and dodecylphenol
(RF=F(CF.sub.2).sub.n, n=7% 6, 63% 8, 28% 10, 2%.gtoreq.12).
##STR10##
[0042] 9
RF--(CH.sub.2).sub.3--O--C.sub.6H.sub.4--C.sub.12H.sub.25
* * * * *