Use of fluorinated liquids

Details Use of fluorinated liquids Use of fluorinated liquids

2002-12-31

2004-06-08

Green, Anthony J. (Department: 1755)

Compositions

Frost-preventing, ice-thawing, thermostatic, thermophoric,...

C165S104190, C252S071000, C252S078100

Reexamination Certificate

active

06746620

ABSTRACT:

The present invention relates to the use of fluorinated compounds liquid at room temperature, as dielectric working fluids in plants or circuits comprising parts formed by organic polymer material in contact with said working fluids or fluorinated liquids.
Specifically the invention compounds show an improved property combination compared with the known working fluids of the prior art or industrially used, as indicated hereafter:
reduced permeability and swelling of the polymer compounds with which they are in contact;
capability to dissipate the electrostatic charges generated by triboelectric effect when they come into contact with non conductive polymer compounds.
It is well known that dielectric fluids are fluids which act as electric insulator, or such that an electric field can be maintained therein with a minimum dissipation of power.
As known, in the manufacture of equipments used in the chemical, pharmaceutical industry, of the heat exchangers (refrigeration), and in particular in the electric and electronic industry, organic polymer compounds, both plastomeric and elastomeric, are used in substitution of metals. Depending on the parts of the plant, fluorinated or hydrogenated polymer compounds can be used. In the parts subjected to thermal or mechanical stress, such for example in the pipe bundles of heat exchanger, fluorinated compounds are generally used. Other parts of the plant, for example, gaskets, O-ring, are made by hydrogenated or (per)fluorinated elastomeric compounds.
The substitution of metals with polymer compounds in plants and circuits used in the industry allows to obtain various advantages among which, for example, the removal from the working fluid of the metal particulate which forms due to the particle separation from the welding points, for example of the pipe bundles, and from the bent parts or connections of equipments particularly subjected to mechanical stresses. The metal particulate circulating with the working fluid can compromise the plant functionality, for example obstructing the flow regulation valves. Or it can compromise the dielectric properties of the working fluid, which are critical in the plants used in the electronic semicon industry.
Even though the use of polymer compounds in plants has favoured the solution of various problems, it is known that the compounds used in the prior art as working fluids can in the time compromise the properties of the organic polymer compound with which they are in contact.
The most significant drawbacks are the following:
(1) swelling of polymer parts with consequent loss of the mechanical properties of the manufactured article;
(2) permeation of the fluid through the compound, making it necessary the monitoring of the amount of fluid circulating in the plant to refill the losses;
(3) when the used polymer compounds are not conductive, an accumulation of electrostatic charges takes place on the manufactured article owing to the triboelectric effect if the working fluid has dielectric properties; under these conditions electric discharges can take place, even of an entity such to perforate the polymer material.
Said drawbacks compromise the plant efficiency and safety.
For said reasons in the plant construction for example of heat transfers, the choice of the suitable combination polymer compound—working fluid results critical, considering the width of the thermal cycle and the possible state transformations to which the fluid is subjected during its use.
In the prior art processes to dissipate electrostatic charges are described. For example in U.S. Pat. No. 3,907,955 a process to dissipate electrostatic charges, generated by the flow of fluids at high speed in circuits which are used in the aeronautic sector is described. According to the process of said patent the polymer compound used to manufacture the circuits (PTFE) is made conductive by the addition of graphite. Said addition shows the drawback that if a dielectric working fluid is used in the plant, it can be polluted by conductive particulate coming from the graphite used in the preparation of pipes and therefore lose the insulating properties. The same drawback takes place by using elastomeric compounds, which as well known are charged with fillers to confer mechanical properties. Also in this case the fillers during the use are extracted from the working fluid.
The need was felt to have available a dielectric working fluid, to be used in industrial circuits or plants, for example heat transfers, comprising parts made by polymer material, showing the following improved combination of properties:
reduced permeability,
reduced swelling,
good dissipation of electrostatic charges.
The Applicant has surprisingly and unexpectedly found compounds usable as dielectric working fluids, liquid at room temperature, which solve the above technical problem.
An object of the invention is the use of one or more fluorinated compounds, liquid at room temperature, as dielectric working fluids in plants or heat transfer circuits comprising parts formed by polymer compound in contact with said fluids, said liquids having boiling point in the range 50° C.-250° C., preferably 70° C.-200° C., and having formula
R′—R
f
—R  (I)
wherein:
R′ is —(O)
n0
—C
n
F
2n
H, n being an integer from 1 to 4, preferably 1 or 2; n0 is equal to 0, 1;
R is: —C
n
F
2n
H, —C
m
F
2m+1
; wherein
in the end groups R, R′ one fluorine atom is optionally substituted with one chlorine atom; n in R is as defined in R′; m is an integer from 1 to 3;
R
f
is:
linear or branched perfluoroalkylene from 2 to 12 carbon atoms, containing at least one ether oxygen atom, when R
f
has said meaning n0 in R′ is preferably equal to zero;
perfluoropolyoxyalkylene comprising units statistically distributed along the chain, selected from the following:
(CFXO) wherein X=F or CF
3
;
(CF
2
(CF
2
)
d
O) wherein d is an integer comprised between 1 and 3;
(C
3
F
6
O);
when R
f
is perfluoropolyoxyalkylene n0 in R′ is preferably equal to 1.
The unit (C
3
F
6
O) in R
f
has the following meanings:
(CF
2
CF(CF
3
)O), (CF(CF
3
)CF
2
O).
Preferably in formula (I) R is a group selected from the following: —CF
2
H, —CF
2
CF
2
H, —CFHCF
3
.
The working fluids, the above described compounds of formula (I), generally have a number average molecular weight from 200 to 800.
In the fluids of the invention of formula (I) preferably R
f
=(per)fluoropolyether chain with n0 of R′ equal to 1, R
f
preferably has one of the following structures:
1) —(CF
2
O)
a
—(CF
2
CF
2
O)
b
—
when a is different from zero, then b/a is comprised between 0.3 and 10, extremes included; when a is equal to zero b is an integer as defined below;
R in formula (I)=—C
n
F
2n
H;
2) —(CF
2
—(CF
2
)
z′
—CF
2
O)
b′
—
wherein z′ is an integer equal to 1 or 2; b′ is as defined below;
3) —(C
3
F
6
O)
r
—(C
2
F
4
O)
b
—(CFL
0
O)
t
—
L
0
=—F, —CF
3
;
when b and t are different from zero r/b=0.5-2.0; (r+b)/t=10-30 and all the units with r, b and t indexes are present;
or b=t=0 and r satisfy the proviso indicated below;
or b=0 and r and t are different from zero; a, b, b′, r, t, are integers such that, or whose sum is such that the compound of formula (I) containing the bivalent radical R
f
has a boiling point in the above range.
The dielectric fluids, or compounds of the invention, can be for example the following:
HCF
2
O(CF
2
CF
2
O)
1.8
(CF
2
O)
1.4
CF
2
H;
HCF
2
O(CF
2
CF
2
O)
2
(CF
2
O)
0.7
CF
2
H;
HCF
2
O(CF
2
CF
2
O)
3
(CF
2
O)
0.4
CF
2
H;
HCF
2
O(CF
2
CF
2
O)
3
(CF
2
O)
1.6
CF
2
H;
HCF
2
O(CF
2
CF
2
O)
4
(CF
2
O)
0.9
CF
2
H;
CF
3
O(CF
2
CF
2
O)
2
CF
2
H;
CF
3
O(CF
2
CF
2
O)
2
(CF
2
O)CF
2
H;
CF
3
O(CF
2
CF(CF
3
)O)
2
CF
2
H;
CF
3
O(CF
2
CF(CF
3
)O)
3
CF
2
H;
CF
3
O(C
3
F
6
O)
2
(CF(CF
3
)O)CF
2
H;
HCF
2
CF
2
O(CF
2
CF
2
O)CF
2
CF
2
H;
HCF
2
CF
2
OCF
2
C(CF
3
)
2
OCF
2
CF
2
CF2H;
CF
3
(CF
2
)
5
OCF
2
CF
2
H;
CF
3
(CF
2
)
6
OCF
2
H;
C
5
F
11
OC
5
F
10
H.
Preferably the used compounds are the following:

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