U.S. patent number 3,893,962 [Application Number 05/431,160] was granted by the patent office on 1975-07-08 for telephone cable filling composition (ii).
Invention is credited to Basil Vivian Edwin Walton, William Edward John Wannamaker.
United States Patent |
3,893,962 |
Walton , et al. |
July 8, 1975 |
**Please see images for:
( Certificate of Correction ) ** |
Telephone cable filling composition (II)
Abstract
A composition suitable for filling telephone cables if
described, which comprises: 1. a liquid polybutene of average
molecular weight in the range of 500 -3500; 2. microcrystalline
slackwax; or an equivalent thereof, comprising a mixture of a
microcrystalline wax with brightstock oil or a high viscosity
mineral oil of comparable physical properties; 3. polyethylene, of
average molecular weight in the range of 10,000 - 20,000; 4. at
least one wax different from (2) above, chosen from (a) paraffin
waxes having melting points in the range of 37.8.degree. -
79.5.degree.C, (b) synthetic Fischer-Tropsch type waxes having
melting points in the range of 71.1.degree. - 115.degree.C., and
(c) natural waxes selected from the group: Beeswax, Carnauba wax,
Chinese insect wax, Japan wax, Myrtle wax and Spermaceti wax; and
(5) finely divided silica. The amount of finely divided silica used
ranges from about 0.5% to about 8.0%, and preferably 0.5% - 5%, by
weight of the composition. A larger proportion of polybutene is
employed in the composition than that of any other ingredient. The
polybutene, microcrystalline slackwax, polyethylene and The
second-mentioned wax are blended together and heated to about
125.degree.C. and the batch stirred until the waxes and
polyethylene are completely dissolved. Then the finely divided
silica (silica flour) is added in small increments and thoroughly
dispersed with high speed, high shear stirring until complete
uniformity of the composition is attained.
Inventors: |
Walton; Basil Vivian Edwin
(Belleville, Ontario, CA), Wannamaker; William Edward
John (Belleville, Ontario, CA) |
Family
ID: |
23710742 |
Appl.
No.: |
05/431,160 |
Filed: |
January 7, 1974 |
Current U.S.
Class: |
523/173; 524/275;
524/491; 524/277 |
Current CPC
Class: |
C08L
23/06 (20130101); H01B 3/441 (20130101); H01B
7/285 (20130101); C08L 23/20 (20130101); C08K
3/36 (20130101); C08L 91/06 (20130101); C08L
93/00 (20130101); C08L 23/20 (20130101); C08L
2666/02 (20130101); C08L 23/20 (20130101); C08L
23/06 (20130101); C08L 91/06 (20130101); C08L
93/00 (20130101); C08K 3/36 (20130101) |
Current International
Class: |
C08L
23/00 (20060101); H01B 7/285 (20060101); C08L
23/20 (20060101); H01B 3/44 (20060101); H01B
7/17 (20060101); C08f 045/52 () |
Field of
Search: |
;260/28.5A |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
877,895 |
|
Sep 1961 |
|
GB |
|
955,348 |
|
Apr 1964 |
|
GB |
|
Other References
Modern Plastics Encyclopedia for 1968, Sept. 1967, Vol. 45, No. 1A,
pp. 426 and 427..
|
Primary Examiner: Liebman; Morris
Assistant Examiner: Michl; Paul R.
Attorney, Agent or Firm: Kenyon & Kenyon Reilly Carr
& Chapin
Claims
What we claim is:
1. A composition suitable for use in filling telecommunication
cables and the like, comprising:
1. 50.0% - 65.0% poly(butene-1), of average molecular weight in the
range of 500 - 3500;
2. 25.0% - 45.0% microcrystalline slackwax; or of an equivalent of
said microcrystalline slackwax, said equivalent consisting
essentially of a mixture of at least one microcrystalline wax with
a high viscosity mineral oil meeting the following general
specification:
Viscosity/98.8.degree.C -- 120 SUS -- 220 SUS
Viscosity/37.8.degree.C. -- 2000 SUS -- 3500 SUS
Flash Point -- 204.4.degree.C Minimum
Specific Gravity/15.6.degree.C -- 01875 - 0.925
Colour ASTM 2 -- ASTM 8
Boiling Range (at atmospheric pressure) -
260.degree.-704.5.degree.C;
3. 1.0% - 8.0% polyethylene, of average molecular weight in the
range of 10,000 to 20,000;
4. 1.0% - 10.0% of at least one wax selected from the group
consisting of
a. paraffin waxes having melting points in the range of
37.8.degree. - 79.5.degree.C., (b) synthetic Fischer-Tropsch type
waxes having melting points in the range of 71.1.degree. -
115.degree.C., and (c) natural waxes selected from the group:
Beeswax, Carnauba wax, Chinese insect wax, Japan wax, Myrtle wax
and Spermaceti wax; and
5. from about 0.5% to about 8.0% finely divided silica, said
percentages of ingredients being by weight, based on the entire
composition.
2. A composition as defined in claim 1 wherein the finely divided
silica is present in an amount ranging from about 0.5% to about
5.0% by weight of said composition.
3. A composition as defined in claim 2 wherein the finely divided
silica is present in an amount ranging from about 1.0% to about
3.0% by weight of said composition.
4. A composition as defined in claim 1 wherein the wax constituent
is a crude or refined paraffin wax having a melting point in the
range of 37.8.degree. - 79.5.degree.C.
5. A composition as defined in claim 1 wherein the wax constituent
is a crude or refined synthetic Fisher-Tropsch type wax having a
melting point in the range of 71.1.degree. - 115.degree.C.
6. A composition as defined in claim 1 wherein the second-mentioned
ingredient is microcrystalline slackwax.
7. A composition as recited in claim 1 wherein the second-mentioned
ingredient is a mixture of at least one microcrystalline wax and
brightstock oil, said brightstock oil meeting the following general
specification:
Viscosity/98.8.degree.C. -- 120 SUS -- 220 SUS
Viscosity/37.8.degree.C -- 2000 SUS -- 3500 SUS
Flash Point -- 204.4.degree.C Minimum
Specific Gravity/15.6.degree.C -- 0.875 - 0.925
Colour ASTM 2 -- ASTM 8
Boiling Range (at atmospheric pressure) -- 260.degree. --
704.5.degree.C.
8. A composition as set forth in claim 1, said composition meeting
the following specifications:
9. A composition as defined in claim 1 which includes also an
antioxidant in an amount of up to about 1.0% by weight of said
composition.
10. A composition according to claim 1, wherein the poly(butene-1)
is of average molecular weight 920, and the wax constituent is a
synthetic Fischer-Tropsch type wax.
11. A composition as in claim 1 wherein the silica flour has an
average particle size in the range of 0.007 - 0.05 microns.
12. A composition as in claim 11 wherein the silica flour has an
average particle size of 0.012 microns.
13. A composition as in claim 1 wherein the polyethylene has an
average molecular weight of about 19,500.
14. A composition as defined in claim 1, having the following
formulation:
said percentages of ingredients being by weight based on said
composition.
15. A composition as in claim 1 wherein the poly(butene-1)
constituent comprises a mixture of low molecular weight
poly(butenes-1) of varying molecular weights and viscosities, said
mixture having an average molecular weight within the range of 500
to about 3500.
16. A composition according to claim 1 wherein the poly(butene-1)
constituent is one which meets the following specifications:
17. A composition according to claim 1 wherein the poly(butene-1)
constituent is one which meets the following specifications:
18. Process of preparing a composition suitable for use in filling
telecommunication cables and the like, comprising the following
steps, in sequence:
a. mixing together, with heating, the following ingredients:
i. poly(butene-1) of average molecular weight in the range of from
500 to 3500;
ii. microcrystalline slackwax; or an equivalent of said
microcrystalline slackwax, consisting essentially of a mixture of
at least one microcrystalline wax with a high viscosity mineral oil
meeting the following general specification:
Viscosity/98.8.degree.C. -- 120 SUS -- 220 SUS
Viscosity/37.8.degree.C. -- 2000 SUS -- 3500 SUS
Flash Point -- 204.4.degree.C. Minimum
Specific Gravity/15.6.degree.C. -- 0.875 - 0.925
Colour ASTM 2 -- ASTM 8
Boiling Range (at atmospheric pressure) -- 260.degree. -
704.5.degree.C;
iii. polyethylene, of average molecular weight in the range of
10,000 to 20,000; and
iv. at least one wax selected from the group consisting of (1)
paraffin waxes having melting points in the range of 37.8.degree. -
79.5.degree.C., (2) synthetic Fischer-Tropsch type waxes having
melting points in the range of 71.1.degree. - 115.degree.C., and
(3) natural waxes selected from the group: Beeswax, Carnauba wax,
Chinese insect wax, Japan wax, Myrtel wax and Spermaceti wax, until
a homogeneous, liquid Myrtle is obtained; said ingredients being
employed in the following relative proportions:
b. adding finely divided silica in small increments to the mixture
while subjecting the latter to high velocity, high shear mixing
until complete dispersion of said silica in the mixture is achieved
and a completely uniform product is obtained, each increment of
said finely divided silica being thoroughly dispersed in the
mixture before a succeeding increment is added, the amount of said
finely divided silica used ranging from about 0.5% to about 8.0% by
weight of the composition.
19. A process as in claim 18, wherein in step (a) the
second-mentioned ingredient is microcrystalline slackwax.
20. A process as in claim 18 wherein the amount of finely divided
silica used is in the range of about 0.5% to about 5.0% by weight
of the composition.
21. A process as in claim 18 wherein the amount of finely divided
silica used is in the range of about 1.0% to about 3.0% by weight
of the composition.
22. A process as in claim 19 wherein the wax constituent is a
synthetic Fisher-Tropsch type wax having a melting point in the
range of 71.1.degree. - 115.degree.C.
23. A process as in claim 22 wherein, in step (a), the
poly(butene-1), microcrystalline slackwax, polyethylene and
synthetic wax are heated together at a temperature of approximately
120.degree.C. until a homogeneous mixture is obtained.
24. A process as set forth in claim 23 wherein, after said
homogeneous mixture is obtained, it is cooled to about
110.degree.C. at which temperature step (b) is carried out.
25. A process as defined in claim 18, wherein there is included
also an antioxidant, in an amount up to about 1.0% by weight of the
composition, said antioxidant being incorporated into the
composition together with said poly(butene-1), microcrystalline
slackwax or equivalent thereof, polyethylene and wax, in the first
step.
26. A process as defined in claim 18, wherein the poly(butene-1) is
of average molecular weight 920, and the wax constituent of the
composition is a synthetic Fischer-Tropsch type wax.
27. A process as in claim 18 wherein the silica flour has an
average particle size in the range of 0.007 - 0.05 microns.
28. A process as in claim 27 wherein the silica flour has an
average particle size of 0.012 microns.
29. A process as in claim 18 wherein the polyethylene has an
average molecular weight of about 19,500.
30. A process as in claim 18 wherein the ingredients used and their
relative proportions, are as follows:
said percentages of ingredients being by weight, based on the
composition.
31. A process according to claim 18 wherein the poly(butene-1)
constituent is one which meets the following specifications:
32. A process according to claim 18 wherein the poly(butene-1)
constituent is one which meets the following specifications:
Description
This invention relates to compositions for the filling of
telecommunications cables, particularly of buried cables which are
subject to the ingress of water, or to entry and condensation of
water vapor. Such water might flow through the cable and degrade
its electrical properties.
The telecommunications cables to which the compositions of this
invention are applicable are of the type comprising a multiplicity
of conductors each having a dielectric of plastic material, a
waterproof sheath enclosing the insulated conductors and, filling
the interstices between these insulated conductors and between them
and the cable sheath from end to end of the cable length, a
water-impermeable medium which will not drain under the influence
of gravity or such hydrostatic pressure as may arise in the event
of damage to the cable sheath but which will permit relative
sliding movement of the plastic insulated conductors over one
another during such bending of the cable as occurs during
manufacture and installation of the cable.
Water or water vapor often enters a cable through punctures in the
cable's outer jacket. These punctures may be the result of
lightning strikes, mechanical damage to the cable sheath, or of
initial defects incurred during production or laying of cable. One
way which has been employed to minimize water ingress is to sheath
the cable interior with water and vapor barriers. Such barriers,
however, are expensive. Also, such barriers, once they are
penetrated, permit the entry of water which flows along the cable
through interstices between the cable's conductors, fills the
cable, and deteriorates its electrical qualities. Such
deterioration manifests itself as an increase in the capacitance
between cable conductors and results in increased losses. In
telephone communication cables such losses can seriously degrade
the operating performance of a telephone system. As will be
appreciated, water (with a dielectric constant of 80) in the cable
would increase signal losses to such an extent that transmission
would virtually cease or alternatively the signals would become so
garbled as to become meaningless. Ultimately, the water in the
cable may corrode the conductors so as to cause open circuits.
It is known to fill the interstices of multiconductor telephone
cables with water blocking compounds in order to prevent water
introduced into the cables which are installed in ducts or directly
buried in the ground, as a result of damage to the cable sheath,
travelling along the interior of the cable from the point of entry
and thus adversely affecting its electrical characteristics along
its whole length. Various blocking compounds are known for this
purpose, among them being heavy bodied mastic materials and
jelly-like substances, such as petroleum jelly.
The material used in the substance filling the interstices is
preferably of such a consistency that when applied to the cable,
the substance adheres to the conductors and the sheath well enough
to prevent the formation of water passages along the surfaces of
the conductors or the inner surfaces of the sheath and also does
not significantly reduce the flexibility of the cable. It is also
important that the water-blocking compound be of such a consistency
at the cable operating temperature that in the event of damage to
the cable sheath it will not exude from the cable thus permitting
the entry of water into the cable.
Various compositions for filling telecommunications cables to
inhibit or prevent the ingress of water thereinto are known.
Examples of such compositions are those comprising mixtures of a
mineral oil and microcrystalline wax and/or synthetic hydrocarbon
waxes, as described, for instance, in Albert King's U.S. Pat. Nos.
2,914,430 and 2,956,036, and in British Pat. Specifications Nos.
877,895 and 955,348 of Sargent et al. These and other known cable
filling compositions do work reasonably well in fulfilling their
intended purpose and have been widely used; but nevertheless have
certain drawbacks.
More specifically, previously known telecommunications cable
filling compositions have one or more of the following
drawbacks:
a. Poor compatibility with the plastic materials used for
insulating the cable pairs.
b. Frequently previous compounds were of low melting point and poor
cohesive (internal) strength which render them unsuitable for use
in cables where high temperatures could be met in service.
c. Excessive hardness at low temperature with the concomitant
difficulty of handling filled telephone cables during cold weather
installation.
d. Poorly chosen ingredients, some or all of which often exhibit
exceptionally harmful effects on the plastic materials used to
insulate the cable pairs (see (a) above).
e. The tendency for the components to separate (i.e. syneresis) due
to poorly chosen base oils/polymers or improper blending
techniques.
f. Low resistance to manual working resulting in a physical
degradation of the composition to the point where its high
temperature characteristics, especially drainage and water barrier
characteristics, are adversely affected.
The ideal characteristics one should look for in a telephone cable
filling composition for use in conditions where the cable may be
subjected to a wide range of temperature during operation can be
listed as follows:
1. It should have a high melting point, that is, above
80.degree.C.; so that, when it is subjected to high ambient
temperatures such as may be encountered during operation of the
cable, it will not liquefy and thus tend to exude from the
cable.
2. It should exhibit plasticity at very low temperatures, for
example, at -40.degree.C.
3. It should exhibit a minimum degree of syneresis, i.e. separation
of liquid components from solid components.
4. It should exhibit minimum void formation on contraction.
5. It should exhibit a minimum change in dielectric constant with
increase in frequency.
6. It should have a low value for the dielectric constant
(permittivity) -between 2.0 and 2.4.
7. It should have maximum compatibility with primary insulating
materials, such as plastics which are used for the cable sheathing
and for enclosing the conductors.
8. It should have a liquid viscosity low enough that the cable
interstices can be readily impregnated during the cable
manufacturing operation, yet sufficiently high that the material
would not exude from the cable during manufacture or in the event
of damage to the cable sheath.
9. It should be free from moisture and other polar contaminants,
all of which have an adverse effect on the performance of the
finished telephone cable.
10. It should have sufficient internal strength or "internal
cohesive force" to withstand the pressure effect of a moderately
high head of water at elevated temperatures, i.e. significantly
above ambient temperatures, e.g. 50.degree. - 80.degree.C.
Known filling materials for use in cables, and in particular, those
heretofore used in multiconductor telecommunications cables are
deficient in one or more of the above characteristics. Thus there
has been a continuing search for improved cable filling
compositions which would overcome the deficiencies of known
compositions of this type, and have characteristics more nearly
approaching the ideal characteristics noted above.
An objective of the present invention is to provide cable filling
compositions which substantially eliminate, or at least minimize,
the ingress of water into telecommunications cables in the event of
mechanical or electrical damage to the cable sheaths.
Another objective of the invention is to provide cable filling
compositions which are an improvement over known cable filling
compounds, in that they are free from at least some of the
drawbacks of the known compounds, and which at least approach the
ideal for compositions of this type.
We have found that these objectives can be fulfuilled by providing
a composition which comprises, broadly, a mixture of (1) a low
molecular weight, liquid polybutene; (2) microcrystalline slackwax,
or an equivalent thereof comprising a mixture of microcrystalline
wax with a high viscosity mineral oil such as brightstock oil; (3)
polyethylene; (4) at least one wax of a type different from that in
(2) above; and (5) finely divided silica; the silica being present
in an amount ranging from about 0.5% to about 8.0% by weight of the
composition. The finely divided silica serves as a filler and also
as a gelling agent for binding the other ingredients into a gel
structure.
Thus in one broad aspect the present invention resides in a
composition suitable for use in filling telecommunications cables
and te like, commprising: (1) polybutene, of average molecular
weight in the range of 500-3500; (2) microcrystalline slackwax; or
an equivalent thereof, comprising a mixture of at least one
mcrocrystalline wax with a high viscosity mineral oil having the
following characteristics:
Viscosity/98.8.degree.C (ASTM D2161) -- 120 SUS -- 220 SUS
Viscosity/37.8.degree.C (ASTM D2161) -- 2000 SUS -- 3500 SUS
Flash Point -- 204.4.degree.C. Minimum
Specific Gravity/15.6.degree.C -- 0.875 - 0.925
Colour ASTM 2 -- ASTM 8
Boiling Range (at atmospheric pressure) -- 260.degree. -
704.5.degree.C.; (3) polyethylene, of average molecular weight in
the range of 10,000 to 20,000; (4) at least one wax selected from
the group consisting of (a) paraffin waxes having melting points in
the range 37.8.degree. - 79.5.degree.C. (b) synthetic
Fischer-Tropsch type waxes having melting points in the range of
71.7.degree. - 115.degree.C, and (c) natural waxes selected from
the group: Beeswax, Carnauba wax, Chinese insect wax, Japan wax,
Myrtle wax and Spermaceti wax; and (5) finely divided silica, said
silica being present in an amount ranging from about 0.5% to about
8.0% by weight of said composition; said composition containing a
larger proportion by weight of said polybutene than that of any
other ingredient.
The telephone cable filling compositions of this invention are
designed to fill the cable in such a manner that in the event of
sheath failure water will not penetrate into the interior of the
cable, thereby damaging or even destroying completely the
transmission characteristics of the cable. The compositions of the
present invention are designed to have sufficiently high structural
"internal cohesive strength" to resist a 3 ft. head of water
pressure. This is an important feature, for as will be appreciated
it would not be of much value to fill a buried telephone cable with
a composition of the type disclosed herein if that composition, at
the ambient temperatures involved, could be extruded from the cable
by dint of external water pressure applied following sheath
damage.
The polybutene constituent of our compositions is poly(butene-1) as
opposed to polyisobutylene. The average molecular weight of the
polybutene we use is in the range of 500-3500, and desirably is in
the range of 70-1100. A mixture of polybutenes may be used, as long
as the average molecular weight is within the aforesaid range of
500-3500, and the product has the appropriate viscosity. Such
polybutenes are viscous, oily liquids, and are prepared by the
polymerization of n-butene in the presence of a halide olefin
polymerizing catalyst, or by other methods well known to those
skilled in the art.
Polybutenes which are suitable for use in the composition of this
invention are those having a viscosity in the range of 850-1150
SUS/98.8.degree.C.
One preferred polybutene for use in the present invention is one
meeting the following specifications:
Specific Gravity/15.6/15.6.degree.C. 0.890 Viscosity/37.8.degree.C.
38,400 SUS Colour APHA 10 Flash Point (C.O.C.) 204.4.degree.C Fire
Point 232.2.degree.C Pour Point -1.1.degree.C Total Chlorides ppm 5
Total Sulphur ppm 5 Water Content Nil
Another preferred polybutene for use in the compositions of this
invention is one having the following characteristics:
Average molecular weight 920
Viscosity SU/37.8.degree.C. (ASTM D 2161) 35,944
Viscosity SUS/98.8.degree.C (ASTM D 2161) 985
Viscosity index (ASTM D 567) 109
Evaporation loss (10 hr. at 98.8.degree.C), wt. % (ASTM D972)
0.0
Pour Point, (ASTM D 97) --6.7.degree.C.
Acidity, mg. KOH/gm (ASTM D974) 0.01
Specific Gravity (15.6.degree.C) 0.882
Microcrystalline slackwax, one of the ingredients of our inventive
composition, is a material of variable composition; however,
normally such a material would have a mineral oil content of 15% -
40% and have a congealing point of 54.5.degree. - 79.5.degree.C,
the waxes present being of microcrystalline structure.
Microcrystalline waxes, as is well known, are composed of saturated
hydrocarbon compounds of 40-50 carbon atoms with average molecular
weights of 500 to 800. In contrast to the paraffinic waxes,
microcrystalline waxes cannot be distilled at atmospheric pressure
without some decomposition. The compounds are largely branched
chain molecules with the branches occuring at random along the
carbon chain. These waxes have a crystal structure much smaller
than that of paraffin wax. The melting point of refined
microcrystalline waxes is typically in the range of 62.8.degree.
-90.5.degree.C.
As previously indicated, there may be used as a substitute for the
microcrystalline slackwax constituent, a mixture of brightstock
oil, or other mineral oil such as a neutral or pale oil having
equivalent physical properties, with microcrystalline waxes.
Brightstock oils are high V.I. (viscosity index) mineral oils which
meet the general specification for high viscosity mineral oils
previously listed, namely:
Viscosity/98.8.degree.C - 120 SUS -- 220 SUS
Viscosity/37.8.degree.C - 2000 SUS -- 3500 SUS
Flash Point -- at least 204.4.degree.C
Specific Gravity/15.6.degree.C - 0.875 - 0.925
colour -- ASTM 2 -- ASTM 8
Boiling Range (at atmospheric pressure) -- 260.degree. -
704.5.degree.C.
(the abbreviation SUS signifies Saybolt Universal seconds).
Other mineral oils besides brightstock oil, e.g. neutral and pale
oils, may also be used in the aforesaid mixtures with
microsrystalline waxes, provided they have physical chracteristics
similar to those given above.
More particularly the present invention, in one aspect, resides in
a composition suitable for use in filling telecommunications cables
or the like, having the following formulation:
Polybutene, of average molecular weight 920 50.0% - 65.0%
Microcrystalline slackwax 25.0% - 45.0% Polyethylene of average
molecular weight in the range of 10,000 to 20,000 1.0% - 8.0%
Synthetic paraffinic wax 1.0% - 10.0% Silica flour 0.50 - 8.0%
The percentages of ingredients given above are by weight, relative
to the entire composition.
In another broad aspect, this invention resides in a process for
preparing a composition suitable for use in filling
telecommunications cables and the like, comprising the following
steps, in sequence;
a. mixing together, with heating, the following ingredients:
i. polybutene, of average molecular weight in the range of from 500
to about 3,500;
ii. either (a) microcrystalline slackwax; or (b) an equivalent
thereof, comprising a mixture of at least one microcrystalline wax
with a high viscosity mineral oil meeting the following general
specifications:
Viscosity/98.8.degree.C. -- 120 SUS -- 220 SUS
Viscosity/37.8.degree.C. -- 2000 SUS -- 3500 SUS
Flash Point -- 204.4.degree.C Minimum
Specific Gravity/15.6.degree.C. -- 0.875 -- 0.925
Colour ASTM 2 -- ASTM 8
Boiling Range (at atmospheric pressure) -- 260.degree. -
704.5.degree.C.;
iii. polyethylene, of average molecular wieght in the range of
10,000 to 20,000; and
iv. at least one wax selected from the group consisting of (1)
paraffin waxes having melting points in the range of 37.8.degree. -
79.5.degree.C., (2) synthetic Fischer-Tropsch type waxes having
melting points in the range of 71.1.degree. - 115.degree.C., and
(3) natural waxes selected from the group: Beeswax, Carnauba wax,
Chinese insect wax, Japan wax, Myrtle wax and Spermaceti wax, until
a homogeneous liquid mixture is obtained; and
b. adding finely divided silica in small increments to the mixture
while subjecting the latter to high velocity, high shear mixing,
until complete dispersion of said silica in the mixture is achieved
and a completely uniform product is obtained, each increment of
said finely divided silica being thoroughly dispersed in the
mixture before a succeeding increment is added, the amount of said
finely divided silica used ranging from about 0.5% to about 8.0% by
weight of the composition, and said polybutene being employed in an
amount greater than that of any other constituent in the
composition.
The compositions of the present invention have the following
physical characteristics:
Viscosity(Brookfield)/98.8.degree.C (ASTM D2669) 150 - 400
c.p.s.
Cone Penetration/25.degree.C (ASTM D937) 80 - 120-1/10 mm units
Drop Point (ASTM D127 Method) 85.degree.-95.degree.C
Dissipation Factor/100.degree.C/60 Hz 0.005 Maximum
Volume Resistivity/100.degree.C (ASTM D257) 1 .times. 10.sup.10
ohms. metre Minimum
Our compositions are also characterized by being thixotropic. The
term "thixotropic" is used herein to denote the property of certain
materials to change rapidly, on standing, from a liquid into a
gel-like solid mass or body having sufficient cohesive strength to
withstand distortion by gravitational force when suspended freely
in an inverted receptable or on a coated object. The gel is also of
such a nature that it can be fluidized by the application of
mechanical agitation as by shaking, stirring, vibrating, and the
like. The property of thixotropy as understood herein is thus
characterized by a reversible isothermal sol .revreaction. gel
transition.
As to the wax component in our composition there may be used any of
the following: 1. Crude and refined paraffin waxes having melting
points in the range of 37.8.degree. to 79.5.degree.C. 2. Crude and
refined microcrystalline waxes having melting points in the range
of 62.8.degree. - 90.5.degree.C. 3. Synthetic Fischer-Tropsch type
waxes, both crude and refined, having melting points in the range
of 71.1.degree. - 115.degree.C.
Certain vegetable, insect and animal waxes may also be used in our
compositions in place of one or more of the above categories of
waxes. Suitable vegetable, insect and animal waxes for this purpose
are as follows:
Beeswax (Apis Mellifera)
Carnauba Wax (Corypha Cerifera)
Chinese Insect Wax (Coccus Cerifera)
Japan Wax (Rhus Succedaneum)
Myrtle Wax (Myrica Cerifera)
Spermaceti Wax (Physeter Macrocephalus)
Of the above animal, insect, vegetable waxes, the most useful are
Beeswax, Carnauba Wax, Chinese Insect Wax and Spermaceti Wax;
however, the other waxes listed will produce acceptable end
products if used within the range we have specified for the wax
content of our telephone cable filling compositions and after
suitable refining processes.
Another component of our composition is polyethylene, of molecular
weight in the range of 10,000 to 20,000. A preferred polyethylene
for use in the compositions of this invenntion is one having a
molecular weight of approximately 19,500. This substance, which is
produced by either high pressure or low pressure polymerization of
ethylene, is a white thermoplastic material readily obtainable from
a variety of plastics manufacturers.
In the compositions of this invention the
polybutene/microcrystalline slackwax/polyethylene/synthetic
paraffin wax blend produces a soft, rather viscous "petrolatum"
type material which, of its own accord, is not completely
satisfactory for the purpose being considered, i.e. for filling
telecommunication cables. By dispersing the correct grade of finely
divided silica (i.e. silica flour), under the appropriate
conditions, a gel-like structure is formed, which structure is
sufficiently stable to preclude the separation of any of the
components during storage, filling and/or use. The silica flour,
i.e. gelling agent, produces a gel such that although the gel
structure is lost on liquefaction, it is regenerated on cooling.
The polybutene/microcrystalline slackwax/polyethylene/synthetic wax
blend may be considered as one major component, formulated to
introduce inherent strength into the final gel structure, with the
silica flour acting as the second major component, the gelling
agent.
As previously stated the gelling agent used in the compositions of
the present invention is finely divided silica. This material may
also be considered as a filler in the composition. The filler used
is variously known as: silica flour, fumed silica, pulverized
silica, atomized silica or micronized silica. The porportion of
filler to gel-like substance required depends (a) on the desired
end, liquid viscosity characteristic, (b) on the degree of hardness
desired and (c) on the character and particle size of the filler
itself. The character of the filler includes the shape and surface
properties of the individual particles; the character of the
particles determines the end, liquid viscosity and hardness
characteristics. Plateshaped or needle-like particles will reduce
the viscosity of the jelly-like substance more than spheroid
particles. The smaller the particle size the smaller the amount of
filler required.
Such a composition has thixotropic properties: that is when it is
caused to move or is agitated, for example by pumping, its
viscosity is reduced. In the case of flat or needle-like particles
this viscosity reduction is assisted by the alignment of the
particles with the direction of motion. When the compound is
substantially at rest the particles will be randomly directed, and
thus assist in increasing the viscosity.
The particle size range of finely divided silica (silica flour) may
vary very considerably; however, that used in the compositions of
the present invention range anywhere frm 0.007 to 0.050 microns.
Silica flours we have found quite satisfactory for use in the
present invention are those designed by the trademark CAB-O-SIL.
The following is a description of this particular material.
CAB-O-SIL is one of the purest silicas commercially available. On a
dry basis, it is 99% silicon dioxide and is practically free frm
contaminating metallic oxide. It contains no calcium, sodium or
magnesium. CAB-O-SIL is so pure it meets the requirements of the
FDA for use in foods in concentrations up to 2%.
Particles of CAB-O-SIL range in size from 70 to 500 angstroms or
0.007 to 0.050 microns. The physical appearance is that of a
fluffy, snow white, super fine powder of extermely low bulk
density. CAB-O-SIL particles are finer than those of the finest
grades of rubber re-inforcing carbon blacks. They are as fine as
cigarette smoke.
When thoroughly dispersed and mixed with clear liquids such as
mineral oil and turpentine, a transparent product is obtained. When
dispersed and mixed with liquids such as alkyd vehicles, polyester
resins, dioctyl phthalate and other plasticisers and varnishes, a
translucent product is produced. The refractive index of 1.46 is
close to that of many organic liquids and therefore dispersions are
relatively transparent or translucent. For example, a dispersion of
CAB-O-SIL in butyl alcohol results in a perfectly clear suspension.
CAB-O-SIL is made by a vapour phase process. It is produced by the
hydrolysis of silicon tetrachloride at 1100.degree.C. This process
produces a colloidal silica of exceptional purity. CAB-O-SIL,
because it is produced at a high flame temperature, is generally
classified as a "fumed" silica.
From the physical properties and surface characteristics stems the
ability of CAB-O-SIL fumed silica to impart thickening and
thixotropic control to liquids.
When CAB-O-SIL is dispersed in a liquid system, the chain-like
formulations join each other an form a network type of structure.
This reduces the ability of the liquid to flow and results in
increased viscosity or thickening. Upon agitation or shear, the
network structure breaks down and reforms after agitation stops.
When a gel reverts to a liquid upon agitation and reforms as a gel
when agitation stops, the liquid is commonly known as being
thixotropic. When very small amounts of CAB-O-SIL are dispersed in
a liquid system, there is a limited amount of hydrogen-bonding,
because the chains are generally too far apart to bond in a closely
knit formation. By increasing the concentration of CAB-O-SIL to a
point where there is a sufficient number of CAB-O-SIL chains which
have hydrogen-bonded to each other, the desired thickening or
thixotropy can be obtained.
A particularly suitable silica flour for the purposes of the
present invention is that known under the Trademark "Cabosil M5"
which has a particle size of 0.012 microns. Other silica flours
which have been found satisfactory are those known under the
Trademarks "Syloid 224," "Syloid 308," "Gasil 23," "Tixosil 38A,"
"Zeosil 39" and "Cabosil M7." The use of the proper grade of finely
divided silica, plus the correct incorporating techniques, are the
key to the manufacture of an acceptable composition according to
this invention.
The amount of finely divided silica employed may range from about
0.5% to about 8.0% by weight of the composition. Preferably,
however, we employ an amount of finely divided silica ranging from
about 0.5% to about 5.0% by weight of the composition. Still more
preferably, the finely divided silica is used in an amount ranging
from about 1.0% to about 3.0% by weight of the composition.
The ingredients of our telephone cable filling compositions are
obtainable from various sources. For instance, microcrystalline
slackwaxes, microcrystalline and paraffin waxes, which are
by-products of petroleum refining, are readily obtainable from
petroleum refineries. Brightstock oil, if used in our product, may
be obtained from similar sources. A synthetic paraffin wax we have
found to be particularly useful in formulating our compositions is
one obtained from SASOL Ltd. of South Africa and sold under the
trademark "PARAFLINT V.I.," Other suitable waxes of this general
type, known in the trade as "Fishcer-Tropsch" waxes, are available
from BASF in Germany and from other sources.
As an optional ingredient there may be included up to about 1.0% by
weight of an antioxidant. Any of the well known antioxidants for
stabilizing organic substances and materials may be used; for
instance, suitable antioxidants for use in the compositions of this
invention are those disclosed in British Pat. Specification
1,117,771 of Union Carbide Corporation, published June 26, 1968,
and in U.S. Pat. No. 3,156,728 of Orloff et al, granted Nov. 10,
1964; and also in the reference "Autoxidation and Antioxidants,"
Lundberg (1962), Interscience Publishers, Inc., New York.
If desired, there may be added to our compositions as an optional
ingredient, minor amounts of "a tackiness" agent: this could be
either a resinous material or a material such as high molecular
weight polyisobutylene.
The cable filling compositions of the present invention are
prepared according to the following procedure:
a. The polybutene, microcrystalline slackwax, polyethylene and
second wax component (e.g. synthetic paraffinic wax) are blended
together, and are heated to approximately 125.degree.C and the
batch stirred until the wax and polyethylene constituents are
complete dissolved. If any antioxidant is to be included in the
composition, it is added at this stage. The order of addition of
the various components mentioned above is not particularly
important.
b. The finely divided silica (e.g. silica flour) is then added in
small increments and thoroughly dispersed with high speed, high
shear stirring until complete uniformity has been achieved as
determined by drop point and viscosity measurements.
As previously stated the key to making an acceptable cable filling
composition according to this invention is the proper dispersion of
the finely divided silica, as well as the use of the proper grade
of finely divided silica.
As suitable equipment for effecting the high speed, high shear
stirring there may be used any high speed stirrer known to those
skilled in the art, as long as it can impart sufficient shear
energy to the composition. For insntance, mixers such as the
"Lightning Mixer" (trade mark), the "Cowles Dissolver" (trade
mark), the "Twin Daysolver" (trade mark) and various types of
turbine mixers such as described in pages 1210-1211 of Perry,
"Chemical Engineers' Handbood" 3rd Ed. (1950), McGraw-Hill Book
Co., New York, are suitable. Also suitable are high speed high
shear dispersing devices such as are described in Chapter 6 of the
book "Practical Emulsions," 3rd Edition, Vol. 1, Bennett et al.
(1968), Chemical Publishing Company, Inc., New York.
A typical batch of approximately 5 tons of the composition
according to this invention is produced in a 24 hours period; this
includes also the period required for testing of the
composition.
The following example represents a preferred composition and method
of preparation in accordance with the present invention. The
percentages given are by weight, relative to that of the whole
composition.
Example
55.5% Polybutene -- Average Molecular Weight -- 920
35.0% Microcrystalline Slackwax
4.0% Polyethylene, Molecular Weight -- 19,500
3.0% Synthetic Paraffin Wax, m.p. in range of 71.1.degree. -
115.degree.C.
2.5% Silica Flour
The polybutene, microcrystalline slackwax, polyethylene and
synthetic paraffin wax are heated together and blended at a
temperature of 125.degree.C. (An antioxidant, if desired, is also
incorporated into the composition at this stage.) The mixture is
allowed to cool to 110.degree.C. at which temperature the silica
flour is added in small increments with high speed/high shear
stirring, until a completely uniform and consistent viscosity
product is obtained. It is vital that the silica flour be added in
small increments and thoroughly dispersed before the next increment
is added and that sufficient shear energy be imparted to the
composition during this process.
The compositions of this invention may be used to fill telephone
cables by means known in the art. Generally speaking, the
composition is heated until molten although it may also be used in
the plastic solid state, and is then applied to preformed, plastic
insulated telephone wires, at one or more filling points during the
cable's manufacture, the composition being maintained at such a
temperature (a) as not to "set-off" on contact with the cold cable
and (b) as not to exude from the interior of the cable after it has
been filled. Arrangements such as disclosed, for example, in
British Pat. Specification No. 1,120,011 published Jul. 17, 1968;
British Pat. Specification No. 1,136,344 published Dec. 11, 1968;
U.S. Pat. No. 3,607,487 Biskeborn et al granted Sept. 21, 1971, or
British Pat. Specification No. 1,293,942 published Oct. 25, 1972,
may be used for the application of our inventive filling
compositions.
Our compositions were evaluated as follows:
(a) High Temperature Melting Point -- ASTM D127 and ASTM D566. (The
minimum desired temperature for compositions of the type with which
this invention is concerned, is 80.degree.C. as measured by ASTM
D566 and 85.degree.C. as measured by ASTM D127). (b) Syneresis --
i.e. the tendency to separation of oil/polymers from a formulation.
There is no standardized test that is known for determining this
property; however, it has been found that compounds held at
20.degree. - 30.degree.C. below their ASTM D127 drop points for
periods of 7-14 days will show signs of liquid separation, if this
is a characteristic of the compound. (c) Plasticity at Low
Temperature (-40.degree.C. - /-40.degree.F.) - A Company devised
test which consists of placing a quantity of the composition in a
suitable container -- usually 750 grams of the composition in a
1000 ml metal container, and chilling to the required test
temperature in 3 stages over a 6 our period and meauring the
hardness of the material at the final temperature by means of Cone
Penetration. Additionally thin layers of the composition (5-10
mils) may be coated onto thin metal plates (20-30 mil) and cooled
to the required test temperature, at which temperature the
plate/compound is flexed and signs of cracking/fissuring noted. Our
compositions were test using both the above methods. (d) Void
Formation - A company devised test which is related to the
Coefficient of Expansion of the composition as measured at
different temperatures over a given temperature range, the specific
expansion values obtained being plotted as a curve on linear graph
paper. In general terms, the flatter the Coefficient of Expansion
curve for a given composition produced during the test cycle, the
more desirable is the composition for this particular end use; this
is particularly so the closer the curve is to a continuous value of
0.0007.degree.C which is the average coefficient of expansion value
for petroleum oils. The test method used to measure the compound's
coefficient of expansion is a Company devised test in which a small
sample (approximately 50 grams) of compound is cooled under applied
pressure to the lower test temperature and is temperated at this
temperature for 12 hours. The sample is then raised in temperature,
at a controlled rate, the expansion undergone by the compound
during the heating cycle being mechanically transmitted to a
recording chart. (e) Dielectric Constant and Change in Dielectric
Constant with Increase in Frequency - ASTM D150 In the case of
telephone cable filling compositions it is desirable that there be
a minimum change in the Dielectric constant of the filling
composition with change in test frequency. The Dielectric Constant
of air is 1. Ideally any filling compound should have this value
for Dielectric Constant; however, most petroleum based compositions
have Dielectric Constants in the range of 2.0 - 2.4. The cable
filling compositions of this invention fall within this range at
all measured frequency levels. (f) Compatibilty with Insulating
Materials - a Company devised test. Plastic coated telephone cable
wires are immersed in the compositions to be tested at a prescribed
temperature for a prescribed period of time and are subsequently
air aged after which air aging the physical changes which have
occurred in the plastic insulation, as the result of its immersion
in the compound, and subsequent air againg are noted. (g)
Penetration/25.degree. and 65.degree.C - ASTM D937 - It is vital
that the compositions for use as telephone cable filling compounds
have acceptable penetration values, not only at the standard test
temperature of 25.degree.C. but also at an elevated temperature.
For this purpose a temperature of 65.degree.C was selected as being
both a realistic and meaningful temperature. It is possible to
formulate a composition having an acceptable penetration at
25.degree.C. only to have this composition disintegrate at
65.degree.C. The meeting of acceptable cone penetration values at
both temperatures is of prime importance in formulating
compositions of this general type. (h) Volume
Resistivity/100.degree.C. - ASTM D257 - This test relates to the
freedom of the composition from moisture and polar contaminants
which have an adverse effect on the performance of the finished
telephone cable, particularly at high frequencies. Resistivity is
also recommended as a test to determine when a cable filling
composition has deteriorated beyond an acceptable point for
continued in-plant usage. (i) Viscosity - Brookfield Viscosimeter
Method - To produce compositions having an acceptable viscosity is
a prime requirement. It is possible to produce compositions of such
a viscous consistency that full filling of the cable interstices is
not possible in the time period allowed in plant production.
Formulating to an acceptable viscosity, and for the composition to
have such a viscosity, is of critical importance in producing
"fully filled" cables.
The following typical test data were obtained for the composition
of the Example, previously described:
Viscosity (Brookfield) /98.8.degree.C. (ASTM D2669) 250 cps Drop
Point (ASTM D127) 92.degree.C Plasticity/-40.degree.C No cracking
observed Dielectric Constant/100.degree.C (ASTM D150) 2.3 Volume
Resistivity/100.degree.C (ASTM D257) 15 .times. 10.sup.10 ohms
Meter Cone Penetration/25.degree.C (ASTM D937) 100 Cone
Penetration/65.degree.C (ASTM D937) 170 Dissipation
Factor/100.degree.C/60 Hz 0.0020
While certain embodiments of this invention have been particularly
described herein, it is to be understood that the invention is not
to be limited to specific embodiments, since for example variations
in the ingredients of the compositions, and/or the proportions of
ingredients, and/or processing conditions for the manufacture of
these compositions, will be contemplated by those skilled in the
art, without departing from the broadest aspects of the invention.
It is therefore intended that the invention be limited only by the
claims which follow.
* * * * *