FIELD OF THE INVENTION
[0001] This invention relates to a cable comprising a flooding composition a polyolefin
elastomer and a bio-based fluid.
BACKGROUND OF THE INVENTION
[0002] US-A-5,940,570 relates to a method for encapsulating segments of signal transmission devices such
as splices, pressure blocks and end blocks with a room-temperature curable composition
comprising: (1) a hydroxyl-functional compound having a molecular weight of greater
than 500 and a hydroxyl functionality of 2 or more; (2) an epoxy-functional compound
having an epoxy functionality of 2 or more; and (3) a curative catalyst, in an amount
effective to crosslink the epoxy and hydroxyl components of the respective epoxy-functional
and hydroxyl-functional compounds.
[0003] Flooding compositions are materials designed to occupy void spaces in telecommunication
cables, such as the void spaces typically found around and between buffer tubes commonly
used in fiber optic cables. Additionally, these compositions can be used as filling
materials to suspend and protect optical fibers inside buffer tubes. Flooding compositions
are free-flowing at elevated temperatures (such as those temperatures used when filling
a telecommunication cable), and easily gel at lower temperatures to avoid dripping
at room temperature. Additionally, easy-to-clean and non-messy flooding compositions
are desirable for ease of installation and prevention of environmental contamination.
Although advances have been made in the art of flooding compounds, improvements are
still desired.
[0004] Another important property of a flooding composition is its compatibility with polymer
materials used in cable constructions such as polyolefin, i.e., low gel pickup for
good property retention and cable longevity. Current commercial flooding compounds
are based on synthetic hydrocarbons; they are messy, grease/wax-like materials that
stick to surfaces that come in contact with them. In case of a spill, they are not
environmentally friendly. The wire and cable industry has a continuing interest in
flooding compositions that exhibit reduced stickiness, reduced absorption into materials
used in the manufacture of cable components such as buffer tubes, jackets, etc., and
more environmental friendly.
SUMMARY OF THE INVENTION
[0005] In one embodiment the invention is a cable comprising (A) at least one optical fiber;
(B) a plurality of buffer tubes; and (C) a flooding composition comprising in weight
percent (wt%) based on the weight of the composition:
(1) 10-80 wt% of a first component comprising a polyolefin elastomer consisting of
only α-olefin residues, the polyolefin elastomer selected from the group consisting
of ethylene/α-olefin copolymers, propylene/α-olefin copolymers, and combinations thereof;
and
(B) 20-90 wt% of a second component comprising a bio-based fluid.
[0006] In one embodiment, the flooding composition further comprises one or more additives,
e.g., an antioxidant, a thixotropic agent, etc. In one embodiment, the second component
is a mixture of a bio-based fluid and a petroleum-based oil.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007]
Figure 1 is a cross-sectional view of a loose buffer tube fiber optic cable.
Figure 2 is a chart reporting oil absorption in weight percent by HDPE and cPP.
Figure 3 is a chart reporting oil absorption in weight percent by HDPE and cPP versus
the total unsaturation percent of the oil.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Definitions
[0008] Any reference to the Periodic Table of Elements is that as published by CRC Press,
Inc., 1990-1991. Reference to a group of elements in this table is by the new notation
for numbering groups.
[0009] Unless stated to the contrary, implicit from the context, or customary in the art,
all parts and percents are based on weight and all test methods are current as of
the filing date of this disclosure.
[0010] The numerical ranges in this disclosure include all values from, and including, the
lower and upper value. For ranges containing explicit values (e.g., 1 or 2; or 3 to
5; or 6; or 7), any subrange between any two explicit values is included (e.g., 1
to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6; etc.).
[0011] The terms "comprising," "including," "having," and their derivatives, are not intended
to exclude the presence of any additional component, step or procedure, whether or
not the same is specifically disclosed. In order to avoid any doubt, all compositions
claimed through use of the term "comprising" may include any additional additive,
adjuvant, or compound, whether polymeric or otherwise, unless stated to the contrary.
In contrast, the term, "consisting essentially of" excludes from the scope of any
succeeding recitation any other component, step, or procedure, excepting those that
are not essential to operability. The term "consisting of" excludes any component,
step, or procedure not specifically delineated or listed. The term "or," unless stated
otherwise, refers to the listed members individually as well as in any combination.
Use of the singular includes use of the plural and vice versa.
[0012] "Bio-based fluid" and like terms mean a fluid derived from a biological source, such
as a plant, animal, bacteria, yeast, algae, and the like. Bio-based fluids can comprise
a single bio-based fluid, i.e., a fluid derived from a single biological source, or
a blend of two or more bio-based fluids, i.e., a fluid derived from two or more biological
sources. Bio-based fluids are liquid under ambient conditions (23°C and atmospheric
pressure), or have a wax-like consistency under ambient conditions (23°C and atmospheric
pressure) and become liquid upon heating.
[0013] "Wire" and like terms mean a single strand of conductive metal, e.g., copper or aluminum,
or a single strand of optical fiber.
[0014] "Cable," "power cable" and like terms mean at least one wire or optical fiber within
a sheath, e.g., an insulation covering or a protective outer jacket. Typically, a
cable is two or more wires or optical fibers bound together, typically in a common
insulation covering and/or protective jacket. The individual wires or fibers inside
the sheath may be bare, covered or insulated. Combination cables may contain both
electrical wires and optical fibers. The cable can be designed for low, medium, and/or
high voltage applications. Typical cable designs are illustrated in USP
5,246,783;
6,496,629 and
6,714,707.
[0015] "Residue," when referring to a monomer, means that portion of a monomer molecule
which resides in a polymer molecule as a result of being polymerized with another
monomer or comonomer molecule to make the polymer molecule.
[0016] "Composition" and like terms mean a mixture or blend of two or more components.
[0017] In one embodiment the invention is a cable comprising: (A) at least one optical fiber;
(B) a plurality of buffer tubes; and (C) a flooding composition comprising in weight
percent (wt%) based on the weight of the composition:
- (A) 10-80 wt% of a first component comprising a polyolefin elastomer consisting of
only α-olefin residues, the polyolefin elastomer selected from the group consisting
of ethylene/α-olefin copolymers, propylene/α-olefin copolymers, and combinations thereof;
and
- (B) 20-90 wt% of a second component comprising a bio-based fluid.
Polyolefin Elastomer
[0018] The first component of the flooding compositions of this invention is a polyolefin
elastomer. As known in the art, an "elastomer" is a polymer that experiences large
reversible deformations under relatively low stress. Elastomers can either be thermoplastic
or thermoset. "Thermoplastic elastomers" are elastomers having thermoplastic properties.
That is, thermoplastic elastomers are optionally molded or otherwise shaped and reprocessed
at temperatures above their melting or softening point. The polyolefin elastomers
suitable for use herein are thermoplastic elastomers.
[0019] A "polyolefin elastomer" is an elastomeric polymer containing residues of alpha-olefin
("α-olefin") monomers. In the present invention the polyolefin elastomers consist
of only α-olefin monomer residues, including ethylene. Such polyolefin elastomers
are interpolymers. As used herein, "polymer" means a macromolecular compound prepared
by reacting (i.e., polymerizing) monomers of the same or different type, and includes
homopolymers and interpolymers. "Interpolymer" means a polymer prepared by the polymerization
of at least two different monomer types. This generic term includes copolymers (usually
employed to refer to polymers prepared from two different monomer types), and polymers
prepared from more than two different monomer types (e.g., terpolymers (three different
monomer types) and tetrapolymers (four different monomer types), etc.). As used herein,
"homopolymer" denotes a polymer comprising repeating units derived from a single monomer
type, but does not exclude residual amounts of other components used in preparing
the homopolymer, such as chain transfer agents.
[0020] Polyolefin elastomers can include both polyolefin homopolymers and interpolymers.
Examples of polyolefin homopolymers are homopolymers of ethylene and propylene. Examples
of polyolefin interpolymers are ethylene/α-olefin interpolymers and propylene/α-olefin
interpolymers. In such embodiments, the α-olefin can be a C
3-20 linear, branched or cyclic α-olefin (for the propylene/α-olefin interpolymers, ethylene
is considered an α-olefin). Examples of C
3-20 α-olefins include propene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene,
1-dodecene, 1-tetradecene, 1-hexadecene, and 1-octadecene. The α-olefins can also
contain a cyclic structure such as cyclohexane or cyclopentane, resulting in an α-olefin
such as 3-cyclohexyl-1-propene (allyl cyclohexane) and vinyl cyclohexane. Illustrative
polyolefin copolymers include ethylene/propylene, ethylene/butene, ethylene/1-hexene,
ethylene/1-octene, and the like. Illustrative terpolymers include ethylene/propylene/1-octene,
ethylene/propylene/butene, and ethylene/butene/1-octene. In an embodiment, the polyolefin
propylene homopolymer available from Eastman Chemical Company); and combinations thereof.
In various embodiments, the polyolefin elastomers are the homogeneously branched linear
and substantially linear ethylene copolymers. The substantially linear ethylene copolymers
are especially preferred, and are more fully described in USP
5,272,236;
5,278,272 and
5,986,028. In another embodiment, the polyolefin elastomers are amorphous polyolefins, such
as those more fully described in
US Pub. No. 2004/0081795.
[0021] The polyolefin elastomers useful herein also include propylene. Such copolymers comprise
a majority (i.e., greater than 50 weight percent ("wt%")) of units derived from the
alkene (e.g., propylene) and a minority of units derived from another α-olefin (including
ethylene). In an embodiment, the polyolefin elastomer includes a propylene-based copolymer.
In further embodiments, the polyolefin elastomer comprises a propylene-ethylene copolymer.
Exemplary propylene-based copolymers useful herein include VERSIFY
™ polymers available from The Dow Chemical Company, and VISTAMAXX
™ polymers available from ExxonMobil Chemical Company.
[0022] Polyolefin elastomers can also include ethylene-propylene-diene monomer ("EPDM")
elastomers and chlorinated polyethylenes ("CPE"). Commercial examples of suitable
EPDMs include NORDEL
™ EPDMs, available from The Dow Chemical Company. Commercial examples of suitable CPEs
include TYRIN
™ CPEs, available from The Dow Chemical Company.
[0023] In one or more embodiments, the polyolefin elastomer is selected from the group consisting
of ethylene-based polyolefin elastomers, propylene-based polyolefin elastomers, and
combinations thereof. In such embodiments, the ethylene-based polyolefin elastomer
can have an ethylene content of greater than 50 wt%, or greater than 60 wt%, based
on the entire weight of the ethylene-based polyolefin elastomer, with the balance
consisting of one or more alpha-olefin monomers. Additionally, the ethylene-based
polyolefin elastomer can have an ethylene content ranging from greater than 50 wt%
to 90 wt%, or from 60 wt% to 75 wt%, based on the entire weight of the ethylene-based
polyolefin elastomer, with the balance consisting of one or more alpha-olefin monomers.
In various embodiments, the alpha-olefin monomer is octene.
[0024] Furthermore, when the polyolefin elastomer is propylene-based, it can have a propylene
content of greater than 50 wt%, greater than 70 wt%, or greater than 90 wt%, based
on the entire weight of the propylene-based polyolefin elastomer, with the balance
consisting of one or more alpha-olefin monomers (including ethylene). Additionally,
the propylene-based polyolefin elastomer can have a propylene content ranging from
greater than 50 to 99 wt%, from 70 to 98 wt%, or from 90 to 97 wt%, based on the entire
weight of the propylene-based polyolefin elastomer, with the balance consisting of
one or more alpha-olefin monomers (including ethylene). In various embodiments, when
the polyolefin elastomer is propylene-based, the alpha-olefin comonomer is ethylene.
Nonlimiting examples of a suitable propylene-based polyolefin elastomer include propylene
copolymer and propylene homopolymer.
[0025] In one or more embodiments, the polyolefin elastomer includes an ethylene/octene
copolymer and an amorphous propylene homopolymer.
[0026] In one or more embodiments, the polyolefin elastomer includes a propylene/ethylene
copolymer and an amorphous propylene homopolymer.
[0027] In one or more embodiments, the polyolefin elastomers suitable for use herein can
have a degree of crystallinity in the range of from 0.01 to less than 50 wt%, from
0.5 to 40 wt%, or from 10 to 35 wt%, or from 11 to 32 wt%. In other embodiments, the
polyolefin elastomers can have a degree of crystallinity in the range of from 10 to
less than 50 wt%, from 10 to 40 wt%, or from 20 to 35 wt%. The degree of crystallinity
of the polyolefin elastomer is measured by the method described in the Test Methods
section, below.
[0028] Polyolefin elastomers suitable for use herein can have a Brookfield viscosity of
500 g/cm-s (50,000 centipoise ("cps" or "cP")) or less, or in the range of from 10
g/cm-s (1,000) to 500 g/cm-s (50,000 cps), from 10 g/cm-s (1,000) to 400 g/cm-s (40,000
cps), or from 10 g/cm-s (1,000) to 300 g/cm-s (30,000 cps), or from 10 g/cm-s (1,000)
to 100 g/cm-s (10,000 cps). Brookfield viscosity for polyolefin elastomers is determined
in accordance with the procedure provided in the Test Methods, below, at 176.6°C (350°F)
using a Brookfield viscometer with an SC-31 hot-melt spindle.
[0029] Polyolefin elastomers suitable for use herein can have a number-average molecular
weight ("Mn") of greater than 2,000 g/mol, at least 4,000 g/mol, or at least 5,000
g/mol. Additionally, the polyolefin elastomers can have an Mn in the range of from
2,000 to 60,000 g/mol, or from 4,000 to 50,000 g/mol, or from 5,000 to 35,000 g/mol,
or from 7,000 to 20,000 g/mol, or from 7,000 to 15,000 g/mol. Mn is determined according
to the gel-permeation-chromatography method described in the Test Methods section,
below.
[0030] Polyolefin elastomers suitable for use herein can have a weight-average molecular
weight ("Mw") ranging from 1,000 to 100,000 g/mol, or from 5,000 to 50,000 g/mol,
or from 8,000 to 30,000 g/mol. Mw is determined according to the gel-permeation-chromatography
method described in the Test Methods section, below.
[0031] Polyolefin elastomers suitable for use herein can have a polydispersity index ("PDI"
or "Mw/Mn") ranging from 0.2 to 20, from 0.5 to 10, or from 1 to 5. PDI is determined
according to the gel-permeation-chromatography method described in the Test Methods
section, below.
[0032] Polyolefin elastomers suitable for use herein can have a density of less than 0.930
g/cm
3, or less than 0.920 g/cm
3, or less than 0.910 g/cm
3, or less than 0.900 g/cm
3. Additionally, the polyolefin elastomers can have a density of at least 0.850 g/cm
3, or at least 0.860 g/cm
3, or at least 0.870 g/cm
3, or at least 0.880 g/cm
3, or at least 0.890 g/cm
3. Density is determined according to ASTM D 792.
[0033] Polyolefin elastomers suitable for use herein can have a melting point of at least
50°C, or at least 55°C, or at least 60°C, or at least 65°C, or at least 70°C, or at
least 75°C, or at least 80°C, or at least 85°C, or at least 90°C, or at least 95°C,
or at least 100°C. The melting point of suitable polyolefin elastomers can be as high
as 120°C, or as high as 150°C, or as high as 155°C, or as high as 160°C. Melting point
is determined according to the method described in the Test Methods section, below.
[0034] Polyolefin elastomers suitable for use herein can have a B value in the range of
from 0.1 to 2.0, from 0.5 to 1.5, or from 0.7 to 1.0. B value is determined according
to the method described in the Test Methods section, below.
[0035] Polyolefin elastomers suitable for use herein can have a crystallization temperature
("Tc") in the range of from 30 to 100°C, or 35 to 80°C, or from 50 to 75°C. Crystallization
temperature is determined according to the method described in the Test Methods section,
below.
[0036] Polyolefin elastomers suitable for use herein can have one, some, or all of the following
properties:
- (a) a degree of crystallinity from 0.01, or 10 to 35, or less than 50 wt%;
- (b) a Brookfield viscosity from 10 g/cm-s (1,000) to 70 g/cm-s (7,000), or 500 g/cm-s
(50,000 cps);
- (c) a Mn from 2,000, or 7,000 to 55,000, or 60,000 g/mol;
- (d) a Mw from 1,000 to 100,000 g/mol;
- (e) a Mw/Mn from 0.2 to 20;
- (f) a density from 0.850, or 0.860 to 0.890, or 0.930 g/cm3;
- (g) a melting point (Tm) from 50, or 55 to 155, or 160°C;
- (h) a B value from 0.1 to 2.0; and/or
- (i) a crystallization temperature (Tc) from 30 to 75, or 100°C.
[0037] A specific example of a suitable ethylene-based polyolefin elastomer is an ethylene/octene
copolymer having a Brookfield viscosity of 82 g/cm-s (8,200 cps) and a density of
0.889 g/cm
3. A specific example of a suitable propylene-based polyolefin elastomer is a propylene/ethylene
copolymer having a Brookfield viscosity of 10 g/cm-s (1,000 cps) and a density of
0.884 g/cm
3.
Bio-Based Fluid
[0038] The second component of the flooding compositions of this invention is a bio-based
fluid (also referred to as an oil). While any bio-based fluid can be used in the practice
of this invention, fluids derived from vegetable or algae are preferred. Common sources
of the bio-based fluids used in the practice of this invention include, but are not
limited to, coconut, corn, cottonseed, rapeseed (of which Canola oil is one variety),
olive, peanut, safflower, sesame, soybean, sunflower, mustard and algae. The oil is
extracted and processed from the biological material using known techniques and equipment.
[0039] In one embodiment, all or some of the bio-based fluid is functionalized by a known
process to produce a functionalized oil, such as a fatty acid methyl ester (FAME)
or an epoxidized fatty acid methyl ester (eFAME). A "fatty acid methyl ester" ("FAME")
is a fatty acid ester typically formed by transesterifying an oil, such as with methanol.
An "epoxidized fatty acid methyl ester" ("eFAME") is a fatty acid ester with at least
one epoxide group. An "epoxide group" is a three-member cyclic ether (also called
oxirane or an alkylene oxide) in which an oxygen atom is joined to each of two carbon
atoms that are already bonded to each other. Epoxidation reactions are typically performed
with percarboxylic acids or other peroxy compounds. In one or more embodiments, the
bio-based fluid contains a functionalized bio-based fluid. In an embodiment, when
the bio-based fluid contains a functionalized bio-based fluid, the bio-based fluid
contains from greater than 0 to 100 wt%, or from 20 to 80 wt%, or from 40 to 60 wt%,
or 50 wt% of the functionalized bio-based fluid, and from 0 to less than 100 wt%,
or from 20 to 80 wt%, or from 40 to 60 wt%, or 50 wt% of a non-functionalized bio-based
fluid, based on the total weight of bio-based fluid. In another embodiment, the bio-based
fluid excludes functionalized bio-based fluids.
[0040] In one or more embodiments, the bio-based oil can have a flash point from 200°C,
or 220°C, or 240°C, or 250°C, or 270°C, or 280°C, or 285°C to 300°C, or 315°C, or
320°C, or 350°C, measured according to ASTM D92. In one or more embodiments, the bio-based
oil can have a flash point that is greater than 200°C, or greater than 250°C, or greater
than 280°C, or greater than 285°C, or greater than 290°C, or greater than 300°C, or
greater than 310°C, or equal to or greater than 315°C, measured according to ASTM
D92.
[0041] In one or more embodiments, the bio-based oil can have a kinematic viscosity of 500
mm
2/s (500 centistokes ("cSt")) or less, or 200 mm
2/s (200 cSt) or less, or 100 mm
2/s (100 cSt) or less, or 50 mm
2/s (50 cSt) or less at 40°C. In one embodiment, the bio-based oil has a kinematic
viscosity from 10 mm
2/s (10 cSt), or 15 mm
2/s (15 cSt), or 20 mm
2/s (20 cSt), or 30 mm
2/s (30 cSt) to 40 mm
2/s (40 cSt), or 50 mm
2/s (50 cSt), or 100 mm
2/s (100 cSt), or 200 mm
2/s (200 cSt), or 50 mm
2/s (500 cSt) at 40°C. Viscosity of the bio-based oil is measured according to ASTM
D445.
[0042] Bio-based fluid suitable for use herein can have one, some, or all of the following
properties:
- (a) a total unsaturation level from 30%, or 40%, or 45% to 95%, or 99%;
- (b) a flash point from 200, or 250, or 280 to 315, or 320, or 350°C; and/or
- (c) a kinematic viscosity from 10 mm2/s (10 cSt), or 30 mm2/s (30 cSt) to 50 mm2/s (50 cSt), or 500 mm2/s (500 cSt).
[0043] In one embodiment, the bio-based oil is an oil extracted from a single biological
source, e.g., soybean, or corn, or algae, etc. In one embodiment the bio-based oil
is a blend of oils extracted from two or more sources, e.g., soybean and corn, or
soybean and algae, etc. Algae oil typically has a total unsaturation level of 90%
or greater.
[0044] In one embodiment, the second component is a blend or mixture of a bio-based fluid
and a petroleum-based oil. These petroleum-based oils are hydrocarbon oils known in
the art of flooding compositions. Typical examples of hydrocarbon oils include mineral
oils (e.g., paraffinic oils, naphthenic oils, and aromatic oils) and low-molecular-weight
polyolefin oils (e.g., polybutene oil). In an embodiment, the hydrocarbon oil is a
paraffinic oil.
[0045] The hydrocarbon oil, if present, can have a number-average molecular weight ("Mn")
of 2,000 g/mol or less, or 1,000 g/mol or less, or 800 g/mol or less.
[0046] The hydrocarbon oil, if present, can have a kinematic viscosity of 500 mm
2/s (500 centistokes ("cSt")) or less, or 200 mm
2/s (200 cSt) or less, or 100 mm
2/s (100 cSt) or less, or 50 mm
2/s (50 cSt) or less at 40°C. In one embodiment, the hydrocarbon oil, if present, has
a kinematic viscosity from 10 mm
2/s (10 cSt), or 15 mm
2/s (15 cSt), or 20 mm
2/s (20 cSt) to 30 mm
2/s (30 cSt), or 40 mm
2/s (40 cSt), or 50 mm
2/s (50 cSt), or 100 mm
2/s (100 cSt), or 200 mm
2/s (200 cSt), or 500 mm
2/s (500 cSt) at 40°C. Viscosity of the hydrocarbon oil is measured according to ASTM
D445.
[0047] An example of a suitable commercially available hydrocarbon oil is SUNPAR
™ 110, which has a kinematic viscosity of 21.2 mm
2/s (21.2 cSt) at 40 °C, available from Sunoco Inc., Pittsburgh, PA, USA.
[0048] If a petroleum-based oil is used in combination with the bio-based fluid, then typically
the bio-based fluid comprises at least 5, more typically greater than 10, or greater
than 30, or 40, or 50 wt% of the blend of bio-based fluid and petroleum-based oil.
In one embodiment, if a petroleum-based oil is used in combination with the bio-based
fluid, then typically the bio-based fluid comprises from 5, or 10, or 30, or 40, or
50 to 60, or 70, or 80, or 90, or 95, or 99 wt% of the blend of bio-based fluid and
petroleum-based oil.
[0049] In one embodiment, the second component is a blend or mixture of a bio-based fluid
and a polyα-olefin oil. A "polyα-olefin oil" ("PAO oil") is a synthetic compound produced
by polymerizing at least one α-olefin and is a liquid at 22°C and 1 atmosphere of
pressure. The α-olefin may be any α-olefin disclosed herein, such as C
2, C
6, C
8, C
10, C1
2, C
14, and C
20 α-olefins. These are PAO oils known in the art of flooding compositions. Typical
examples of PAO oils include hydrogenated dec-1-ene homopolymer (e.g., DURASYN
™ 180I and DURASYN
™ 180R, available from INEOS) and hydrogenated 1-tetradecene polymer with 1-dodecene
(e.g., DURASYN
™ 126, available from INEOS).
[0050] The PAO oil, if present, can have a kinematic viscosity of 1500 mm
2/s (1,500 centistokes ("cSt")) or less, or 1000 mm
2/s (1,000 cSt) or less, or 500 mm
2/s (500 cSt) or less, or 200 mm
2/s (200 cSt) or less, or 100 mm
2/s (100 cSt) or less, or 50 mm
2/s (50 cSt) or less, or 10 mm
2/s (10 cSt) or less at 40°C. In one embodiment, the PAO oil, if present, has a kinematic
viscosity from 10 mm
2/s (10 cSt), or 15 mm
2/s (15 cSt), or 20 mm
2/s (20 cSt), or 30 mm
2/s (30 cSt) to 40 mm
2/s (40 cSt), or 50 mm
2/s (50 cSt), or 100 mm
2/s (100 cSt), or 200 mm
2/s (200 cSt), or 500 mm
2/s (500 cSt), or 1000 mm
2/s (1,000 cSt), or 1300 mm
2/s (1,300 cSt), or 1500 mm
2/s (1,500 cSt) at 40°C. Viscosity of the PAO oil is measured according to ASTM D445.
[0051] If a PAO oil is used in combination with the bio-based fluid, then typically the
bio-based fluid comprises at least 5, more typically greater than 10, or greater than
20, or 30, or 40, or 50, or 60, or 70, or 75, or 80, or 85 wt% of the blend of bio-based
fluid and PAO oil. In one embodiment, if a PAO oil is used in combination with the
bio-based fluid, then typically the bio-based fluid comprises from 5, or 10, or 14,
or 20, or 30, or 40, to 50, or 60, or 70, or 75, or 80, or 90, or 95, or 99 wt% of
the blend of bio-based fluid and PAO oil. mineral inorganic compounds, polymeric fillers,
and the like. When employed, fillers can be present in any conventional amount, such
as an amount ranging from greater than 0 up to 60 wt%.
Flooding Composition
[0052] The flooding composition can be prepared by simple compounding techniques known in
the art. For instance, the polyolefin elastomer, the bio-based fluid (including any
petroleum-based oil) and any optional additives can be compounded in a liquid operational
mixer with temperature control. For instance, the ingredients can be compounded in
a batch or continuous mixer. Suitable batch mixers include, but are not limited to,
Banbury
™, Silverson
™, Dynamix
™ tank mixers and agitators, and Littleford
™ batch mixers. Continuous mixers include twin and single-screw extruders, Farrel
™ mixers, and Buss
™ co-kneaders.
[0053] The above-described polyolefin elastomer, or blends thereof, can be present in the
flooding compound in an amount ranging from 10 to 80 wt%, from 20 to 60 wt%, or from
20 to 40 wt%, or from 25 to 40 wt%, or from 20 to 30 wt%, or from 30 to 50 wt%, based
on the combined weight of the polyolefin elastomer and bio-based fluid (including
any petroleum-based oil).
[0054] The above-described bio-based fluid (including any petroleum-based oil and/or PAO
oil) can be present in the flooding composition in an amount ranging from 5 to 90
wt%, or from 20 to 80 wt%, or from 40 to 70 wt%, or from 50 to 80 wt%, or from 60
to 75 wt%, based on the combined weight of the polyolefin elastomer and bio-based
fluid. In one embodiment, if a PAO oil and/or petroleum-based oil is used in combination
with the bio-based fluid, then typically the bio-based fluid comprises from 5, or
10, or 14, or 20, or 30, or 40, to 50, or 60, or 70, or 75, or 80, or 90, or 95, or
99 wt% of the blend of bio-based fluid, and PAO oil and/or petroleum-based oil.
[0055] In one or more embodiments, the resulting flooding composition can have an apparent
viscosity in the range of from 0.2 g/cm-s (20) to equal to or greater than 10 g/cm-s
(1,000 centipoise ("cps")), from 0.5 g/cm-s (50) to 10 g/cm-s (1,000 cps), from 2
g/cm-s (200) to 8 g/cm-s (800 cps), or from 3 g/cm-s (300) to 6 g/cm-s (600 cps),
as measured at 150°C according to ASTM D3236. In one or more embodiments, the resulting
flooding composition can have an apparent viscosity from 0.2 g/cm-s (20 cps), or 0.3
g/cm-s (30 cps), or 0.4 g/cm-s (40 cps), or 0.45 g/cm-s (45 cps), or 0.5 g/cm-s (50
cps) to 0.6 g/cm-s (60 cps), or 0.7 g/cm-s (70 cps), or 0.8 g/cm-s (80 cps), or 0.9
g/cm-s (90 cps), or 1 g/cm-s (100 cps), or 1.1 g/cm-s (110 cps), or 1.2 g/cm-s (120
cps), or 1.3 g/cm-s (130 cps), or 1.4 g/cm-s (140 cps), or 1.5 g/cm-s (150 cps), or
1.6 g/cm-s (160 cps), or 1.7 g/cm-s (170 cps), or 1.8 g/cm-s (180 cps), or 1.9 g/cm-s
(190 cps), or 2 g/cm-s (200 cps), or 2.25 g/cm-s (225 cps), or 2.5 g/cm-s (250 cps),
or 2.8 g/cm-s (280 cps), or 3.0 g/cm-s (300 cps), as measured at 150°C according to
ASTM D3236.
[0056] In various embodiments, the flooding composition can have a drop point of at least
65°C, or at least 70°C, or at least 75°C, or at least 80°C, or at least 90°C, or at
least 100°C, or at least 110°C, or at least 120°C. In one or more embodiments, the
flooding composition has a drop point from greater than 90°C, or greater than 100°C,
or greater than 110°C to 120°C, or 130°C, or 140°C, or 150°C, or 160°C, or 200°C.
Drop point is determined according to ASTM D127.
[0057] In various embodiments, the flooding composition can have an oil separation when
aged for 24 hours at 21°C of less than 0.1, or less than 0.05, or less than 0.01.
In one or more embodiments, the flooding composition has an oil separation when aged
for 24 hours at 21°C from 0 to 0.01, or 0.05, or less than 0.1. In one or more embodiments,
the flooding composition has no (i.e., 0) oil separation when aged for 24 hours at
21°C. Oil separation is determined according to ASTM D1742.
[0058] In one or more embodiments, the flooding composition contains:
- (A) from 10, or 20 to 40, or 50, or 80 wt% of a first component comprising a polyolefin
elastomer; and
- (B) from 20, or 50, or 60 to 70, or 75, or 90 wt% of a second component comprising
a bio-based fluid, the bio-based fluid having a total unsaturation level from 30%,
or 40%, or 45% to 95%, or 99%; and
the flooding composition has one, some, or all of the following properties:
- (i) an apparent viscosity from 0.2 g/cm-s (20), or 0.5 g/cm-s (50) to 2.5 g/cm-s (250),
or 2.8 g/cm-s (280 cps), or 3.0 g/cm-s (300 cps) at 150°C;
- (ii) a drop point from greater than 90°C, or greater than 100°C, or greater than 110°C
to 120°C, or 130°C, 200°C; and/or
- (iii) an oil separation when aged for 24 hours at 21°C from 0 to 0.01, or less than
0.1.
[0059] It is understood that the sum of the components in the composition yields 100 weight
percent.
Fiber Optic Cable
[0060] In various embodiments, a fiber optic cable, also known as an optical fiber cable
is prepared that comprises at least one optical fiber, a plurality of buffer tubes,
and the above-described flooding composition.
Melt Index
[0061] Melt index, or I
2, is measured in accordance with ASTM D 1238, condition 190°C/2.16 kg, and is reported
in grams eluted per 10 minutes (g/10 min). The I
10 is measured in accordance with ASTM D 1238, condition 190°C/10 kg, and is reported
in grams eluted per 10 minutes (g/10 min).
Differential Scanning Calorimetry (Crystallinity, Melting Point, Crystallization Temperature)
[0062] Differential Scanning Calorimetry ("DSC") is used to measure crystallinity in the
polymers (e.g., ethylene-based (PE) polymers). About 5 to 8 mg of polymer sample is
weighed and placed in a DSC pan. The lid is crimped on the pan to ensure a closed
atmosphere. The sample pan is placed in a DSC cell, and then heated, at a rate of
approximately 10°C/min, to a temperature of 180°C for PE (230°C for polypropylene
or "PP"). The sample is kept at this temperature for three minutes. Then the sample
is cooled at a rate of 10°C/min to -60°C for PE (-40°C for PP), and kept isothermally
at that temperature for three minutes. The sample is next heated at a rate of 10°C/min,
until complete melting (second heat). The percent crystallinity is calculated by dividing
the heat of fusion (Hf), determined from the second heat curve, by a theoretical heat
of fusion of 292 J/g for PE (165 J/g, for PP), and multiplying this quantity by 100
(for example, % cryst. = (Hf / 292 J/g) x 100 (for PE)).
[0063] Unless otherwise stated, melting point(s) (T
m) of each polymer is determined from the second heat curve (peak Tm), and the crystallization
temperature (T
c) is determined from the first cooling curve (peak Tc).
Drop Point
[0064] Drop point is determined according to ASTM D127.
Viscosity
[0065] Apparent viscosity of the flooding compounds is determined according to ASTM D3236
at 150°C. Kinematic viscosity can be calculated by using apparent viscosity divided
by fluid density.
[0066] Brookfield viscosity of polymer components (i.e., polyolefin elastomers) is determined
in accordance with the following procedure using a Brookfield Laboratories DVII+Viscometer
in disposable aluminum sample chambers. The spindle used is an SC-31 hot-melt spindle,
suitable for measuring viscosities in the range of from 0.1 g/cm-s (10) to 1000 g/cm-s
(100,000 centipoise).
[0067] A cutting blade is employed to cut samples into pieces small enough to fit into the
2.5 cm (1-inch wide), 13 cm (5-inches) long sample chamber. The sample is placed in
the chamber, which is in turn inserted into a Brookfield Thermosel and locked into
place with bent needle-nose pliers. The sample chamber has a notch on the bottom that
fits the bottom of the Brookfield Thermosel to ensure that the chamber is not allowed
to turn when the spindle is inserted and spinning. The sample is heated to 176.6 °C
(350°F), with additional sample being added until the melted sample is about 2.5 cm
(1 inch) below the top of the sample chamber. The viscometer apparatus is lowered
and the spindle submerged into the sample chamber. Lowering is continued until brackets
on the viscometer align on the Thermosel. The viscometer is turned on and set to a
shear rate, which leads to a torque reading in the range of 30 to 60 percent. Readings
are taken every minute for about 15 minutes, or until the values stabilize, then the
final reading is recorded.
B Value
[0068] The B value is calculated as B=P
OE/(2xP
OP
E); where P
E is a molar fraction of the ethylene component in the copolymer, Po is a molar fraction
of the α-olefin component, and P
OE is a molar fraction of α-olefin-ethylene sequences in the all dyad sequences, where
the molar fraction of each component, except the terminal component, is a value calculated,
and the B value is calculated based on a chart of C-NMR(270 MHz).
Oil Absorption
[0069] A 1.9 mm (75-mil) thick compression-molded specimen ∼12.7 x 5.08 mm (-0.5 x 0.2 inches)
of jacket material (HDPE or polypropylene (e.g., cPP)) is immersed in the oil at 85°C.
After 4 days, the oil covering the surface of the jacket material is wiped out and
the weight gain of the jacket material plaque is calculated by comparing its weight
before and after aging.
Gel Permeation Chromatography
[0070] A high-temperature gel permeation chromatography ("GPC") system is employed, equipped
with Robotic Assistant Deliver ("RAD") system for sample preparation and sample injection.
The concentration detector is an Infra-red detector (IR4) from Polymer Char Inc. (Valencia,
Spain). Data collection is performed using Polymer Char DM 100 Data acquisition box.
The carrier solvent is 1,2,4-trichlorobenzene ("TCB"). The system is equipped with
an on-line solvent degas device from Agilent. The column compartment is operated at
150°C. The columns are four Mixed A LS 30-cm, 20 µm (20-micron) columns. The solvent
is nitrogen-purged TCB
Oil Separation
[0071] After mixing the samples as described above, 50 milliliters (ml) of the melted sample
is poured into a shallow aluminum pan and the sample is allowed to cool and solidify.
Any oil separation will be visible on the surface after sitting for 24 hours at room
temperature and the result is recorded.
[0072] By way of example, and not limitation, some embodiments of the present disclosure
will now be described in detail in the following Examples.
EXAMPLES
[0073] A key requirement for cable flooding/filling compounds is oil absorption by cable
components which are generally polyolefin based (e.g. buffer tube, jacket). For this
reason polyolefin-compatible filling/flooding materials are higher cost as they are
based on more expensive oils such as polyα-olefin oils (PAO) and polybutene (PIB,
also known as isobutylene/butene copolymer). Lower cost compounds based on mineral/paraffinic
oils have poor compatibility. The data in Table 2 shows that vegetable oils (e.g.
soybean oil, canola) have desirably low viscosity (e.g. 32 mm
2/s (32 cSt) at 40°C for soybean oil) suitable for viscosity modification of polyolefin
elastomers for the manufacture of flooding and filling compounds. Such viscosities
are comparable to that of paraffinic oil, as well as a higher cost PAO fluid (DURASYN
™ 126, DURASYN
™ 1801, and DURASYN
™ 180R) and PIB fluid (Indopol
™ L-14 and Indopol
™ H-100). The vegetable oils also have a desirably much higher flash point versus paraffinic
oils and PIB L-14.
Table 2. Selected Properties of Various Oils
| Oil |
Supplier |
Oil Type |
Kinematic Viscosity at 40°C (mm2/s)((cSt)) |
Flash Point (°C) |
Mn |
| SUNPAR™ 110 |
Sunoco |
Paraffinic |
21 (21) |
192 |
|
| DURASYN™ 126 |
Ineos |
PAO |
31 (31) |
254 |
|
| DURASYN™ 180I |
Ineos |
PAO |
1261 (1,261) |
290 |
|
| DURASYN™ 180R |
Ineos |
PAO |
928 (928) |
290 |
|
| Soybean oil |
Cargill |
Vegetable |
32 (32) |
288 |
|
| Canola |
|
Vegetable |
42 (42) |
315 |
|
| Indopol™ H-100 |
Ineos |
PIB |
215 (215) @ 100°C |
210 |
910 |
| Indopol™ L-14 |
Ineos |
PIB |
27 (27) |
>138 |
370 |
[0074] The data in Table 3 show some vegetable oils have surprisingly low pickup in both
high density polyethylene (HDPE) (DGDA-6318BK available from The Dow Chemical
| Oil/ Compound |
Supplier |
Oil Type |
Total Unsaturated Fatty Acids (%)˙ |
Oil Absorption in HDPE4 (wt%) |
Oil Absorption in cPP5 (wt%) |
| Algae |
Formulator Sample Shop |
Biomass |
|
2.12 |
4.03 |
| SUNPAR™ 110 |
Sunoco |
Paraffinic |
|
9.5 |
21.02 |
| DURASYN™ 126 |
Ineos |
PAO |
|
3.33 |
7.65 |
| DURASYN™ 1801 |
Ineos |
PAO |
|
-0.31 |
0.99 |
| DURASYN™ 180R |
Ineos |
PAO |
|
-0.14 |
1.23 |
| UCON™ OSP 32 |
Dow |
PAG2 |
|
0.64 |
3.08 |
| UCON™ OSP 680 |
Dow |
PAG3 |
|
-0.89 |
0.09 |
˙Total unsaturation data based on Table 1, above.
1INFO-GEL LA 444 is a thixotropic filling gel containing synthetic oil formulated with
polymers, thixotropic agents, and additives. 2UCON™ OSP 32 is a synthetic polyalkylene glycol (PAG) having a flash point of 216°C and
a kinematic viscosity of 32 mm2/sec at 40°C (measured in accordance with ASTM D445).
3UCON™ OSP 680 is a synthetic polyalkylene glycol (PAG) having a flash point of 243°C and
a kinematic viscosity of 680 mm2/sec at 40°C (measured in accordance with ASTM D445).
4DGDA-6318BK, available from The Dow Chemical Company, having a density of 0.954 g/cm3.
5ESCORENE™ 7132, an impact copolymer available from Exxon Chemical Company. |
[0075] Table 4 reports the properties of the polyolefin elastomers used in the compositions
reported in Table 5.
Table 4. Polyolefin Elastomer Properties
| Component |
Specification / Properties |
Source |
| propylene/ethylene copolymer (P/E 1) |
% crystallization = 32 wt% Brookfield Viscosity =10 g/cm-s (1,000 cP) (@ 176.6°C) |
density = 0.884 g/cc Tc = 72°C |
Internal Stock |
| |
Mn = 12,796 |
Tm = 106°C |
|
| |
C2 wt% = 5.1 wt% |
|
|
| propylene/ethylene copolymer (P/E 2) |
% crystallization = 11 wt% Brookfield Viscosity = 40 g/cm-s (4,000 cP) (@ 176.6°C) |
density = 0.8639 g/cc Tc = 30°C |
Internal Stock |
| |
Mn = 34,880 |
Tm = 64.6°C |
|
| |
C2 wt% = 13.1 wt% |
|
|
| AFFINITY™ GA 1875 |
ethylene/1-octene polyolefin plastomer crystallization = 21.7 wt% |
density = 0.870 g/cc |
The Dow Chemical Company |
| |
Brookfield Viscosity = 67 g/cm-s (6,700 cP) (@ 176.6°C) |
Tc = 57°C |
| |
Mn = 7,210 |
Tm = 70°C |
| |
C2 wt% = 63.7 wt% |
|
| ENGAGE™ 8130 |
ethylene/1-octene polyolefin elastomer % crystallization = 15.8 wt% |
density = 0.864 g/cc Tc = 38°C |
The Dow Chemical Company |
| |
Mn = 52,400 |
Tm = 56°C |
| |
C2 wt% = 61 wt% |
|
| EASTOFLEX™ P1010 |
amorphous propylene homopolymer (hPP) Brookfield Viscosity = 10 g/cm-s (1,000 cP)
(@190°C) |
Tm = 152.1°C |
Eastman |
[0076] Table 5 reports the properties of the compositions based on olefin elastomers. The
compositions are prepared using the following protocol: place all oils and the antioxidant
(IRGANOX
™ 1035, [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] available from BASF) into
a steel paint can and place can on a hot plate. Begin stirring at 15 rpm using a steel
paddle stirrer and lab stirrer such as Cole Parmer Digital Reversing Mixer EW-50004-00
and heat to about 100°C. Add the resins and continue stirring and heat to about 130-150°C
until all resins are melted. Maintain the temperature at 130-150°C and mix at 25 rpm
for 15 minutes after resins are melted. Take a sample out for Brookfield viscosity
testing at 150°C.
[0077] The inventive examples IE1 and IE3 through IE14 show the possibility of formulating
with select vegetable oils having a total unsaturation of greater than 40% (soybean
and canola oils, for example; and other possibilities of blending these oils with
PAO oil, as shown by Examples IE11 through IE14), to achieve desirably low compound
viscosity (in some cases, much lower than the target apparent viscosity of less than
(<) 10 g/cm-s (1,000 cP), or less than 4 g/cm-s (400 cP), or less than 3 g/cm-s (300
cP) at 150°C), thus the potential opportunity for additional fillers for low cost
or other property improvements. Also the inventive compositions exhibit a soft solid
to paste-like consistency and depending on the composition exhibits a low to no oil
separation at room temperature and adequate drop point.
