U.S. patent application number 11/077670 was filed with the patent office on 2006-09-14 for oil gels of controlled distribution block copolymers and ester oils.
Invention is credited to David John St. Clair.
Application Number | 20060205904 11/077670 |
Document ID | / |
Family ID | 36441233 |
Filed Date | 2006-09-14 |
United States Patent
Application |
20060205904 |
Kind Code |
A1 |
St. Clair; David John |
September 14, 2006 |
Oil gels of controlled distribution block copolymers and ester
oils
Abstract
The present invention relates to oil gel compositions that
include at least one non-aromatic ester oil and an anionic block
copolymer of a mono alkenyl arene and a conjugated diene. The block
copolymer is selectively hydrogenated and has mono alkenyl arene
end blocks and a controlled distribution block of a mono alkenyl
arene and a conjugated diene midblock. The ester oil is a
non-aromatic, ester compound such as soybean oil, coconut oil, and
other like compounds.
Inventors: |
St. Clair; David John;
(Houston, TX) |
Correspondence
Address: |
SCULLY, SCOTT, MURPHY & PRESSER
400 GARDEN CITY PLAZA
GARDEN CITY
NY
11530
US
|
Family ID: |
36441233 |
Appl. No.: |
11/077670 |
Filed: |
March 11, 2005 |
Current U.S.
Class: |
526/284 ;
524/571; 525/63 |
Current CPC
Class: |
C08F 297/04 20130101;
C08F 297/044 20130101; C08L 2666/02 20130101; C08L 2666/04
20130101; C08L 53/025 20130101; C08L 53/025 20130101; C08F 297/046
20130101; C08L 53/025 20130101 |
Class at
Publication: |
526/284 ;
525/063; 524/571 |
International
Class: |
C08F 10/00 20060101
C08F010/00 |
Claims
1. An oil gel composition comprised of at least one hydrogenated
block copolymer and a non-aromatic ester oil or mixture of
non-aromatic ester oils, wherein said hydrogenated block copolymer
has at least one polymer block A and at least one polymer block B,
and wherein: a. prior to hydrogenation each A block is a mono
alkenyl arene homopolymer block and each B block is a controlled
distribution copolymer block of at least one conjugated diene and
at least one mono alkenyl arene; b. subsequent to hydrogenation
about 0-10% of the arene double bonds have been reduced, and at
least about 90% of the conjugated diene double bonds have been
reduced; c. each A block has a number average molecular weight
between about 3,000 and about 60,000 and each B block has a number
average molecular weight between about 20,000 and about 300,000; d.
each B block comprises terminal regions adjacent to the A blocks
that are rich in conjugated diene units and one or more regions not
adjacent to the A blocks that are rich in mono alkenyl arene units;
e. the total amount of mono alkenyl arene in the hydrogenated block
copolymer is about 20 percent weight to about 80 percent weight;
and f the weight percent of mono alkenyl arene in each B block is
between about 10 percent and about 75 percent.
2. The oil gel composition of claim 1 wherein said mono alkenyl
arene is styrene and said conjugated diene is selected from the
group consisting of isoprene and butadiene.
3. The oil gel composition of claim 2 wherein said conjugated diene
is butadiene, and wherein about 20 to about 80 mol percent of the
condensed butadiene units in block B have 1,2-configuration.
4. The oil gel composition of claim 1 wherein said polymer block B
has a mono alkenyl arene blockiness of less than about 40 mol
percent.
5. The oil gel composition of claim 2 wherein the polymer is an ABA
polymer and each block B has a center region with a minimum ratio
of butadiene units to styrene units.
6. The oil gel composition of claim 2 wherein the weight percent of
styrene in each B block is between about 10 percent and about 50
percent, and the styrene blockiness index of each block B is less
than about 10 percent, said styrene blockiness index being defined
to be the proportion of styrene units in the block B having two
styrene neighbors on the polymer chain.
7. The oil gel composition of claim 1 wherein said hydrogenated
block copolymer has a general configuration AB, ABA,
(A-B).sub.n,(A-B).sub.nA, (A-B).sub.n,X or mixtures thereof where n
is an integer from 2 to about 30, and X is the coupling agent
residue.
8. The oil gel composition of claim 7 wherein said hydrogenated
block copolymer is a linear hydrogenated ABA styrene/butadiene
block copolymer having a total molecular weight of about 80,000 to
about 200,000.
9. The oil gel composition of claim 1 wherein said hydrogenated
block polymer is a S-EB/S-S type polymer having a block molecular
weight of 29,000-80,000/50,000-29,000, a % weight S of 57.5%, a %
weight S in the EB/S block of 39% and a 1,2/1,4-butadiene ratio of
40/60.
10. The oil gel composition of claim 1 wherein said non-aromatic
ester oil is an ester compound having one of the following
formulas: ##STR5## wherein R.sub.1 and R.sub.2 are the same or
different and are hydrogen or a hydrocarbyl, said hydrocarbyl is
substituted or unsubstituted, and n has any value from 1 to 8.
11. The oil gel composition of claim 1 wherein said non-aromatic
ester oil is an ester compound having the formula: ##STR6## wherein
R.sub.1 comprises hydrogen or a substituted or unsubstituted
hydrocarbyl and R.sub.3 is a substituted or unsubstituted
alkylene.
12. The oil gel composition of claim 1 wherein said non-aromatic
ester oil is an ester compound having the formula: ##STR7## wherein
R.sub.4, R.sub.5 and R.sub.6 individually are a substituted or
unsubstituted alkylene, and R.sub.7, R.sub.8 and R.sub.9
individually include hydrogen or a substituted or unsubstituted
hydrocarbyl.
13. The oil gel composition of claim 1 wherein said non-aromatic
ester oil is a compound having the formula: ##STR8## wherein
R.sub.10, R.sub.11 and R.sub.12 are the same or different fatty
acid radicals containing from 8 to 22 carbon atoms.
14. The oil composition of claim 1 wherein said non-aromatic ester
oil is soybean oil, coconut oil, eicosyl erucate or a C.sub.12-15
alkyl octanoate.
15. The oil gel composition of claim 1 wherein the amount of
non-aromatic ester oil is between about 250 to about 2000 parts by
weight per 100 parts by weight of said at least one hydrogenated
block copolymer.
16. The oil gel composition of claim 15 wherein the amount of
non-aromatic ester oil is between about 400 to about 1000 parts by
weight per 100 parts by weight of said at least one hydrogenated
block copolymer.
17. The oil gel composition of claim 1 wherein said hydrogenated
block polymer is a S-EB/S-S type polymer having a block molecular
weight of 29,000-80,000/50,000-29,000, a % weight S of 57.5%, a %
weight S in the EB/S block of 39% and a 1,2/1,4-butadiene ratio of
40/60; and said non-aromatic ester oil is one of soybean oil,
coconut oil, eicosyl erucate or a C.sub.12-15 alkyl octanoate.
18. An article comprising at least the oil gel composition of claim
1.
19. An article comprising at least the oil gel composition of claim
17.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to an oil gel composition, and
more particularly to an oil gel composition including a controlled
distribution block copolymer and at least one non-aromatic ester
oil.
BACKGROUND OF THE INVENTION
[0002] The preparation of block copolymers of mono alkenyl arenes
and conjugated dienes is well known. One of the first patents on
linear ABA block copolymers made with styrene and butadiene is U.S.
Pat. No. 3,149,182. These polymers, in turn, could be hydrogenated
to form more stable block copolymers, such as those described, for
example, in U.S. Pat. No. 3,595,942 and U.S. Reexamination No.
27,145. Such polymers are broadly termed `Styrenic Block
Copolymers` or SBC's.
[0003] SBC's have a long history of use as adhesives, sealants and
gels. A recent example of such a gel can be found, for example, in
U.S. Pat. No. 5,879,694. With the increased use of oil gels, the
need for improved properties (expressed in terms of higher tensile
strength and higher elongation) exist. Such gels may also be used,
for example, as a water proofing encapsulant/sealant for
electronics and in wire and cable applications.
[0004] An anionic block copolymer based on mono alkenyl arene end
blocks and a controlled distribution mid block of a mono alkenyl
arene and a conjugated diene has been discovered and is described
in copending and commonly assigned U.S. patent application Ser.
No.10/359,981, filed Feb. 6, 2003 and entitled "NOVEL BLOCK
COPOLYMERS AND METHOD FOR MAKING SAME". Methods for making such
polymers are described in detail in the above-mentioned patent
application.
[0005] Copending and commonly assigned U.S. patent application Ser.
No. 10/359,462 filed Feb. 6, 2003 and Ser. No. 10/745,352 filed
Dec. 22, 2003, both entitled "GELS FROM CONTROLLED DISTRIBUTION
BLOCK COPOLYMERS" describe gel compositions that include the
anionic block copolymer of the '981 application and a mineral oil
such as, for example, a petroleum-based white oil. Examples of such
petroleum-based oils include paraffinic oil and naphthenic oil. It
is reported in the '462 and the '352 applications that such gel
compositions have improved properties including, for example, a
high softening point and melt viscosity, as compared to gel
compositions that include conventional hydrogenated anionic block
copolymers.
[0006] Although improved gel compositions are disclosed in the '462
and '352 applications, those gel compositions use mineral oils that
are not considered to be environmentally friendly. There is thus an
interest in gelling natural product oils, such as soybean oil,
because the natural product oils are considered to be more
environmentally friendly. One problem with using natural product
oils in the preparation of gel compositions is that such oils are
not always compatible with the polymer it is being gelled with. For
example, natural product oils are too polar to be used with most
conventional anionic block copolymers.
[0007] It has now been surprisingly discovered by the present
applicant that the anionic block copolymers of the '981 application
are compatible with natural product oils such as, for example,
soybean oil and other like ester compounds, and that substantially
clear blends, which do not exhibit any significant oil bleed can be
formulated.
SUMMARY OF THE INVENTION
[0008] The present invention provides a gel composition that
includes at least one non-aromatic ester oil and at least one
hydrogenated block copolymer having a controlled distribution block
of a mono alkenyl arene and a conjugated diene. The hydrogenated
block copolymer employed in the present invention has at least one
polymer block A and at least one polymer block B wherein: [0009]
(a) prior to hydrogenation each A block is a mono alkenyl arene
homopolymer block and each B block is a controlled distribution
copolymer block of at least one conjugated diene and at least one
mono alkenyl arene; [0010] (b) subsequent to hydrogenation about
0-10% of the arene double bonds have been reduced, and at least
about 90% of the conjugated diene double bonds have been reduced;
[0011] (c) each A block has a number average molecular weight
between about 3,000 and about 60,000 and each B block has a number
average molecular weight between about 30,000 and about 300,000;
[0012] (d) each B block comprises terminal regions adjacent to the
A blocks that are rich in conjugated diene units and one or more
regions not adjacent to the A blocks that are rich in mono alkenyl
arene units; [0013] (e) the total amount of mono alkenyl arene in
the hydrogenated block copolymer is about 20 percent weight to
about 80 percent weight; and [0014] (f) the weight percent of mono
alkenyl arene in each B block is between about 10 percent and about
75 percent.
[0015] The general configuration of the block copolymer employed in
the present invention is A-B, A-B-A, (A-B).sub.n, (A-B).sub.n-A,
(A-B-A).sub.nX, (A-B).sub.nX or a mixture thereof, where n is an
integer from 2 to about 30, preferably 2 to about 15, more
preferably 2 to about 6, and X is coupling agent residue.
[0016] The gel composition of the present invention typically
includes 100 parts by weight of said anionic block copolymer having
the controlled distribution mid-block and from about 250 to about
2000 parts by weight of said ester oil.
[0017] The inventive gels of the present invention can be used, for
example, as a water proofing encapsulant/sealant for electronics
and in wire and cable applications. The inventive gels can also be
used as a lubricating oil, as a grease or as an oil field drilling
fluid. Other uses for the gels of the present invention, include,
but are not limited to: a vibration damper, a vibration isolator, a
wrapper, a hand exerciser, dental floss, a crutch cushion, a
cervical pillow, a bed wedge pillow, a leg rest cushion, a neck
cushion, a mattress, a bed pad, an elbow pad, a dermal pad, a
wheelchair cushion, a helmet liner, a hot or cold compress pad, an
exercise weight belt, an orthopedic shoe sole, a splint, sling or
brace cushion for the hand, wrist, finger, forearm, knee, leg,
clavicle, shoulder, foot, ankle, neck, back and rib or a traction
pad, candles, toys, cables for power or electronic (telephone)
transmission, hydrophone cables for oil exploration at sea and
various other uses.
DETAILED DESCRIPTION OF THE INVENTION
[0018] As stated above, the present invention provides an oil gel
composition which includes, as essential components, at least one
hydrogenated anionic block copolymer (to be described in greater
detail herein below) and an ester oil (also to be described in
greater detail herein below) or a mixture of ester oils.
[0019] The oil gel compositions of the present invention are made
using conventional procedures well known in the art. Typically, the
gel compositions of the present invention are made by blending at
least the ester oil with a hydrogenated anionic block copolymer
having the controlled distribution block. The blends can be made
using any conventional mixing apparatus and mixing can occur at
room temperature or at a temperature that is elevated from room
temperature. For example, the mixing of the two essential
components, together with other optional components (to be
described in greater detail below), may be performed at a
temperature from about 120.degree. C. to about 175.degree. C.
[0020] As stated above, one of the essential components of the
inventive oil gel composition is a hydrogenated block copolymer
containing mono alkenyl arene end blocks and a unique mid block of
a mono alkenyl arene and a conjugated diene, such as described in
the '981 application mentioned above. The entire contents of the
'981 application, particularly the anionic polymerization method
described therein, are thus incorporated herein by reference.
Surprisingly, the combination of (1) a unique control for the
monomer addition, and (2) the use of diethyl ether or other
modifiers as a component of the solvent (which is referred to as a
"distribution agent") results in a certain characteristic
distribution of the two monomers (herein termed a "controlled
distribution" polymerization, i.e., a polymerization resulting in a
"controlled distribution" structure), and also results in the
presence of certain mono alkenyl arene rich regions and certain
conjugated diene rich regions in the polymer block.
[0021] For purposes hereof, "controlled distribution" is defined as
a molecular structure having the following attributes: (1) terminal
regions adjacent to the mono alkenyl arene homopolymer ("A") blocks
that are rich in (i.e., having a greater than average amount of)
conjugated diene units; (2) one or more regions not adjacent to the
A blocks that are rich in (i.e., having a greater than average
amount of) mono alkenyl arene units; and (3) an overall structure
having relatively low mono alkenyl arene, e.g., styrene,
blockiness. For the purposes hereof, "rich in" is defined as
greater than the average amount, preferably 5% greater than the
average amount. This relatively low mono alkenyl arene blockiness
can be shown by either the presence of only a single glass
transition temperature (Tg) intermediate between the Tg's of either
monomer alone, when analyzed using differential scanning
calorimetry ("DSC") thermal methods or via mechanical methods, or
as shown via proton nuclear magnetic resonance ("H-NMR") methods.
The potential for blockiness can also be inferred from measurement
of the UV-visible absorbance in a wavelength range suitable for the
detection of polystyryllithium end groups during the polymerization
of the B block. A sharp and substantial increase in this value is
indicative of a substantial increase in polystyryllithium chain
ends. In such a process, this will only occur if the conjugated
diene concentration drops below the critical level to maintain
controlled distribution polymerization. Any mono alkylene arene
monomer, such as, for example, styrene, that is present at this
point will add in a blocky fashion. The term "styrene blockiness",
as measured by those skilled in the art using proton NMR, is
defined to be the proportion of S (i.e., styrene) units in the
polymer having two S nearest neighbors on the polymer chain.
Although this discussion relates to styrene blockiness, it is
appreciated by those skilled in the art that the same holds for any
mono alkenyl arene monomer.
[0022] The styrene blockiness is determined after using H-1 NMR to
measure two experimental quantities as follows: First, the total
number of styrene units (i.e., arbitrary instrument units which,
when a ratio is taken, cancel out) is determined by integrating the
total styrene aromatic signal in the H-1 NMR spectrum from 7.5 to
6.2 ppm and dividing this quantity by 5 to account for the 5
aromatic hydrogens on each styrene aromatic ring. Second, the
blocky styrene units are determined by integrating that portion of
the aromatic signal in the H-1 NMR spectrum from the signal minimum
between 6.88 and 6.80 to 6.2 ppm and dividing this quantity by 2 to
account for the 2 ortho hydrogens on each blocky styrene aromatic
ring. The assignment of this signal to the two ortho hydrogens on
the rings of those styrene units which have two styrene nearest
neighbors was reported in F. A. Bovey, High Resolution NMR of
Macromolecules (Academic Press, New York and London, 1972), Chapter
6.
[0023] The styrene blockiness is simply the percentage of blocky
styrene to total styrene units: Blocky %=100 times (Blocky Styrene
Units/Total Styrene Units)
[0024] Expressed thus, Polymer-Bd-S--(S).sub.n--S-Bd-Polymer, where
n is greater than zero is defined to be blocky styrene. For
example, if n equals 8 in the example above, then the blockiness
index would be 80%. It is preferred in the present invention that
the blockiness index be less than about 40. For some polymers,
having styrene contents of ten weight percent to forty weight
percent, it is preferred that the blockiness index be less than
about 10.
[0025] This controlled distribution structure is very important in
managing the strength and Tg of the resulting copolymer, because
the controlled distribution structure ensures that there is
virtually no phase separation of the two monomers, i.e., in
contrast with block copolymers in which the monomers actually
remain as separate "microphases", with distinct Tg's, but are
actually chemically bonded together. This controlled distribution
structure assures that only one Tg is present and that, therefore,
the thermal performance of the resulting copolymer is predictable
and, in fact, predeterminable. Furthermore, when a copolymer having
such a controlled distribution structure is then used as one block
in a di-block, tri-block or multi-block copolymer, the relatively
higher Tg made possible by means of the presence of an
appropriately-constituted controlled distribution copolymer region
will tend to improve flow and processability. Modification of
certain other properties is also achievable.
[0026] In a preferred embodiment of the present invention, the
subject controlled distribution copolymer block has two distinct
types of regions--conjugated diene rich regions on the ends of the
block and a mono alkenyl arene rich region near the middle or
center of the block. In particular, a mono alkenyl arene/conjugated
diene controlled distribution copolymer block is desired, wherein
the proportion of mono alkenyl arene units increases gradually to a
maximum near the middle or center of the block and then decreases
gradually until the polymer block is fully polymerized.
[0027] It is noted that the controlled distribution block of the
anionic block copolymers employed in the present invention is not a
random block in which the distribution of the monomer unit is
statistical, nor is the controlled distribution block a tapered
block in which there is a gradual change in the composition of the
polymer chain from one monomer unit to another.
[0028] Starting materials for preparing the controlled distribution
copolymers employed in the present invention include the initial
monomers. The alkenyl arene can be selected from styrene,
alpha-methylstyrene, para-methylstyrene, vinyl toluene,
vinylnaphthalene, and para-butyl styrene or mixtures thereof. Of
these, styrene is most preferred and is commercially available, and
relatively inexpensive, from a variety of manufacturers. The
conjugated dienes that can be used in preparing the anionic block
copolymer employed in the present invention are 1,3-butadiene and
substituted butadienes, such as, for example, isoprene, piperylene,
2,3-dimethyl-1,3-butadiene, and 1-phenyl-1,3-butadiene, or mixtures
thereof. Of these, 1,3-butadiene is most preferred. As used herein,
"butadiene" refers specifically to "1,3-butadiene".
[0029] As discussed above, the controlled distribution polymer
block has diene rich region(s) adjacent to the A block and an arene
rich region not adjacent to the A block, and typically near the
center of the B block. Typically, the region adjacent to the A
block comprises the first 15 to 25% of the block and comprises the
diene rich region(s), with the remainder considered to be arene
rich. The term "diene rich" means that the region has a measurably
higher ratio of diene to arene than the arene rich region. Another
way to express this is the proportion of mono alkenyl arene units
increases gradually along the polymer chain to a maximum near the
middle or center of the block (assuming an ABA structure is being
described) and then decreases gradually until the polymer block is
fully polymerized. For the controlled distribution block B, the
weight percent of mono alkenyl arene is between about 10 percent
and about 75.
[0030] As used herein, "thermoplastic block copolymer" is defined
as a block copolymer having at least a first block of a mono
alkenyl arene, such as styrene, and a second block of a controlled
distribution copolymer of diene and mono alkenyl arene. The method
to prepare this thermoplastic block copolymer is via any of the
methods generally known for block polymerizations. The present
invention includes as an embodiment a thermoplastic copolymer
composition, which may be either a di-block, tri-block copolymer or
multi-block composition. In the case of the di-block copolymer
composition, one block is the alkenyl arene-based homopolymer block
and polymerized therewith is a second block of a controlled
distribution copolymer of diene and alkenyl arene. In the case of
the tri-block composition, it comprises, as end-blocks the glassy
alkenyl arene-based homopolymer and as a mid-block the controlled
distribution copolymer of diene and alkenyl arene. Where a
tri-block copolymer composition is prepared, the controlled
distribution diene/alkenyl arene copolymer can be herein designated
as "B" and the alkenyl arene-based homopolymer designated as
"A".
[0031] The A-B-A, tri-block compositions can be made by either
sequential polymerization or coupling. In the sequential solution
polymerization technique, the mono alkenyl arene is first
introduced to produce the relatively hard aromatic block, followed
by introduction of the controlled distribution diene/alkenyl arene
mixture to form the mid block, and then followed by introduction of
the mono alkenyl arene to form the terminal block. In addition to
the linear, A-B-A configuration, the blocks can be structured to
form a radial (branched) polymer, (A-B).sub.nX, or both types of
structures can be combined in a mixture. Some A-B diblock polymer
can be present, but preferably at least about 30 weight percent of
the block copolymer is A-B-A or radial (or otherwise branched so as
to have 2 or more terminal resinous blocks per molecule) so as to
impart strength.
[0032] It is also important to control the molecular weight of the
various blocks. For an AB diblock, desired block weights are 3,000
to about 60,000 for the mono alkenyl arene A block, and 30,000 to
about 300,000 for the controlled distribution conjugated diene/mono
alkenyl arene B block. Preferred ranges are 5,000 to 45,000 for the
A block and 50,000 to about 250,000 for the B block. For the
triblock, which may be a sequential ABA or coupled (AB).sub.2X
block copolymer, the A blocks should be 3,000 to about 60,000,
preferably 5,000 to about 45,000, while the B block for the
sequential block should be about 30,000 to about 300,000, and the B
blocks (two) for the coupled polymer half that amount. The total
average molecular weight for the triblock copolymer should be from
about 40,000 to about 400,000, and for the radial copolymer from
about 60,000 to about 600,000. These molecular weights are most
accurately determined by light scattering measurements, and are
expressed as number average molecular weights.
[0033] Another important aspect of the anionic block copolymer
employed in the present invention is to control the microstructure
or vinyl content of the conjugated diene in the controlled
distribution copolymer block. The term "vinyl content" refers to a
conjugated diene that is polymerized via 1,2-addition (in the case
of butadiene--it would be 3,4-addition in the case of isoprene).
Although a pure "vinyl" group is formed only in the case of
1,2-addition polymerization of 1,3-butadiene, the effects of
3,4-addition polymerization of isoprene (and similar addition for
other conjugated dienes) on the final properties of the block
copolymer will be similar. The term "vinyl" refers to the presence
of a pendant vinyl group on the polymer chain. When referring to
the use of butadiene as the conjugated diene, it is preferred that
about 20 to about 80 mol percent of the condensed butadiene units
in the copolymer block have 1,2 vinyl configuration as determined
by proton NMR analysis, preferably about 30 to about 70 mol percent
of the condensed butadiene units should have 1,2-vinyl
configuration. This is effectively controlled by varying the
relative amount of the distribution agent. As will be appreciated,
the distribution agent serves two purposes--it creates the
controlled distribution of the mono alkenyl arene and conjugated
diene, and also controls the microstructure of the conjugated
diene. Suitable ratios of distribution agent to lithium are
disclosed and taught in U.S. Pat. Reexamination No. 27,145, which
disclosure is incorporated by reference.
[0034] Another feature of the thermoplastic elastomeric di-block
and tri-block polymers of the anionic copolymer employed in the
present invention, including one or more controlled distribution
diene/alkenyl arene copolymer blocks and one or more mono alkenyl
arene blocks, is that they have at least two Tg's, the lower being
the combined Tg of the controlled distribution copolymer block
which is an intermediate of its constituent monomers' Tg's. Such Tg
is preferably at least about -60.degree. C., more preferably from
about -40.degree. C. to about +30.degree. C., and most preferably
from about -40.degree. C. to about +10.degree. C. The second Tg,
that of the mono alkenyl arene "glassy" block, is preferably more
than about 80.degree. C., more preferably from about +80.degree. C.
to about +110.degree. C. The presence of the two Tg's, illustrative
of the microphase separation of the blocks, contributes to the
notable elasticity and strength of the material in a wide variety
of applications, and its ease of processing and desirable melt-flow
characteristics.
[0035] In some embodiments of the present invention, a hydrogenated
block copolymer that is a linear hydrogenated ABA styrene/butadiene
block copolymer having a total molecular weight of about 80,000 to
about 200,000 is employed. In another embodiment of the present
invention, it is preferred to use an anionic block polymer of the
S-EB/S-S type. This formula indicates a polymer having a
polystyrene block (S) on both ends of a hydrogenated polybutadiene
(EB)/styrene (S) controlled distribution midblock. One example of a
preferred S-EB/S-S type polymer is one wherein the molecular weight
of the various blocks is 29,000-80,000/50,000-29,000, the % weight
styrene is 57.5%, the % weight styrene in the EB/S mid block is 39%
and the 1,2/1,4-butadiene ratio is 40/60. Another preferred anionic
polymer of the S-EB/S-S type is one wherein the molecular weight of
the various blocks is 9,500-60,000/20,000-9,500, the % weight
styrene is 39.5%, the % weight styrene in the EB/S mid block is 25%
and the 1,2/1,4-butadiene ratio is 40/60. Of these preferred
S-EB/S-S type polymers, the first one mentioned above is most
preferred.
[0036] The anionic block copolymer employed in the present
invention is selectively hydrogenated. Hydrogenation can be carried
out via any of the several hydrogenation or selective hydrogenation
processes known in the prior art. For example, such hydrogenation
has been accomplished using methods such as those taught in, for
example, U.S. Pat. Nos. 3,494,942, 3,634,594, 3,670,054, 3,700,633
and Reexamination No. 27,145. Typically, hydrogenation is carried
out under such conditions that at least about 90 percent of the
conjugated diene double bonds have been reduced, and between zero
and 10 percent of the arene double bonds have been reduced.
Preferred ranges are at least about 95 percent of the conjugated
diene double bonds reduced, and more preferably about 98 percent of
the conjugated diene double bonds are reduced. Alternatively, it is
possible to hydrogenate the polymer such that aromatic unsaturation
is also reduced beyond the 10 percent level mentioned above. In
that case, the double bonds of both the conjugated diene and arene
may be reduced by 90 percent or more.
[0037] In an alternative, the block copolymer employed in the
present invention may be functionalized in a number of ways. One
way is by treatment with an unsaturated monomer having one or more
functional groups or their derivatives, such as carboxylic acid
groups and their salts, anhydrides, esters, imide groups, amide
groups, and acid chlorides. The preferred monomers to be grafted
onto the block copolymers are maleic anhydride, maleic acid,
fumaric acid, and their derivatives. A further description of
fuctionalizing such block copolymers can be found in U.S. Pat. Nos.
4,578,429 and 5,506,299. In another manner, the selectively
hydrogenated block copolymer employed in the present invention may
be functionalized by grafting silicon or boron-containing compounds
to the polymer as taught, for example, in U.S. Pat. No. 4,882,384.
In still another manner, the block copolymer of the present
invention may be contacted with an alkoxy-silane compound to form
silane-modified block copolymer. In yet another manner, the block
copolymer of the present invention may be functionalized by
reacting at least one ethylene oxide molecule to the polymer as
taught in U.S. Pat. No. 4,898,914, or by reacting the polymer with
carbon dioxide as taught in U.S. Pat. No. 4,970,265. Still further,
the block copolymers of the present invention may be metallated as
taught in U.S. Pat. Nos. 5,206,300 and 5,276,101, wherein the
polymer is contacted with an alkali metal alkyl, such as a lithium
alkyl. And still further, the block copolymers of the present
invention may be functionalized by grafting sulfonic groups to the
polymer as taught in U.S. Pat. No. 5,516,831.
[0038] The other essential component of the inventive oil gel
composition is an ester oil. The term "ester oil" is used herein to
describe any non-aromatic ester compound including monoesters,
diesters or triesters. An ester as used herein is a compound that
includes at least one carboxylate group: R--COO--, where R is
hydrogen or a hydrocarbyl radical. The term "hydrocarbyl" is used
herein to denote aliphatic or cyclic groups that include elements
of C and H having from 1 to about 30 carbon atoms. Aliphatic groups
include, for example, alkyl groups, alkenyl groups or alkynyl
groups. The hydrocarbyl groups can be substituted with any group as
desired, except for, an aromatic group.
[0039] Suitable esters that can be employed in the present
invention include those of the following formulas: ##STR1## where n
has any value from 1 to about 8, and R.sub.1 and R.sub.2 are the
same or different and are hydrogen or a hydrocarbyl (including
substituted hydrocarbyls). It is noted that a suitable group for
R.sub.2 depends on the value of n. It is noted that the sugar
esters of fatty acids, such as sucrose esters of fatty acids, are
also contemplated herein.
[0040] In one embodiment of the present invention, n is 1, and the
ester has the formula R.sub.1C(O)OR.sub.2 where R.sub.1 is a
C.sub.10-C.sub.20, preferably a C.sub.15-C.sub.18, and even more
preferably a C.sub.17, alkyl, and R.sub.2 is a lower alkyl radical
containing from 1 to 10, preferably 8 carbon atoms.
[0041] Another class of suitable esters that may be employed in the
present invention is represented by the following formula: ##STR2##
where R.sub.1 is defined above and R.sub.3 includes alkylene or
substituted alkylene.
[0042] Still another class of suitable esters that may be employed
in the present invention is represented by the following formula:
##STR3## where R.sub.4, R.sub.5, and R.sub.6 individually include
alkylene or substituted alkylene; and R.sub.7, R.sub.8, and R.sub.9
individually include hydrogen or a hydrocarbyl.
[0043] Preferred esters of the type mentioned above are eicosyl
erucate ester or a C.sub.12-15 alkyl octanoate. Examples of other
suitable esters include, but are not limited to: acefylline
methylsilanol mannuronate; acetaminosalol; acetylated cetyl
hydroxyprolinate; acetylated glycol stearate; acetylated sucrose
distearate; acetylmethionyl methylsilanol elastinate; acetyl
tributyl citrate; acetyl triethyl citrate; acetyl trihexyl citrate;
aleurites moluccana ethyl ester; allethrins; allyl caproate; amyl
acetate; arachidyl behenate; arachidyl glycol isostearate;
arachidyl propionate; ascorbyl dipalmitate; ascorbyl palmitate;
ascorbyl stearate; aspartame; batyl isostearate; batyl stearate;
bean palmitate; behenyl beeswax; behenyl behenate; behenyl erucate;
behenyl isostearate; behenyl/isostearyl beeswax; borago officinalis
ethyl ester; butoxyethyl acetate; butoxyethyl nicotinate;
butoxyethyl, stearate; butyl acetate; butyl acetyl ricinoleate;
2-t-butylcyclohexyl acetate; butylene glycol dicaprylate/dicaprate;
butylene glycol montanate; butyl ester of ethylene/MA copolymer;
butyl ester of PVNI copolymer; butylglucoside caprate; butyl
isostearate; butyl lactate; butyl methacrylate; butyl myristate;
butyloctyl beeswax; butyloctyl candelillate; butyloctyl oleate;
butyl oleate; butyl PABA; butylparaben; butyl stearate; butyl
thioglycolate; butyroyl trihexyl citrate; C.sub.18-36 acid glycol
ester; C.sub.12-20 acid PEG-8 ester; calcium stearoyl lactylate;
C.sub.18-28 alkyl acetate; C.sub.18-38 alkyl beeswax; C.sub.30-50
alkyl beeswax; C.sub.20-40 alkyl behenate; C.sub.18-38 alkyl
C.sub.24-54 acid ester; C.sub.8 alkyl ethyl phosphate; C.sub.18-38
alkyl hydroxystearoyl stearate; C.sub.12-13 alkyl lactate;
C.sub.12-15 alkyl lactate; C.sub.12-13 alkyl octanoate; C.sub.12-15
alkyl octanoate; C.sub.18-36 alkyl stearate; C.sub.20-40 alkyl
stearate; C.sub.30-50 alkyl stearate; C.sub.40-60 alkyl stearate;
caproyl ethyl glucoside; caprylyl butyrate; C.sub.10-30
cholesterol/lanoster-ol esters; cellulose acetate; cellulose
acetate butyrate; cellulose acetate propionate; cellulose acetate
propionate carboxylate; Ceteareth-7 stearate; cetearyl behenate;
cetearyl candelillate; cetearyl isononanoate; cetearyl octanoate;
cetearyl palmitate; cetearyl stearate; cetyl acetate; acetyl
ricinoleate; cetyl caprylate; cetyl C.sub.12-15-Pareth-9
carboxylate; cetyl glycol isostearate; cetyl isononanoate; cetyl
lactate; cetyl laurate; cetyl myristate; cetyl octanoate; cetyl
oleate; cetyl palmitalte; cetyl PCA; cetyl PPG-2 Isodeceth-7
carboxylate; cetyl ricinoleate; cetyl stearate; C.sub.16-20 glycol
isostearate; C.sub.20-30 glycol isostearate; C.sub.14-16 glycol
palmitate; chimyl isostearate; chimyl stearate; cholesteryl
acetate; cholesteryl/behenyl/octyldodecyl lauroyl glutamate;
cholesteryl butyrate; cinoxate; citronellyl acetate;
coco-caprylate/caprate; coco rapeseedate; cocoyl ethyl glucoside;
corylus avellanna ethyl ester; C.sub.12-15 Pareth-9 hydrogenated
tallowate; C.sub.11-15 Pareth-3 oleate; C.sub.12-15 Pareth-12
oleate; C.sub.12-15 Pareth-3 stearate; C.sub.11-15 Pareth-12
stearate; decyl isostearate; decyl myristate; decyl oleate; decyl
succinate; DEDM hydantoin dilaurate; dextrin behenate; dextrin
laurate; dextrin myristate; dextrin palmitate; dextrin stearate;
diacetin; dibutyl adipate; dibutyl oxalate; dibutyl sebacate;
di-C.sub.12-15 alkyl adipate; di-C.sub.12-15 alkyl fumarate;
di-C.sub.12-13 alkyl malate; di-C.sub.12-13 alkyl tartrate;
di-C.sub.14-15 alkyl tartrate; dicapryl adipate; dicaprylyl
maleate; dicetearyl dimer dilinoleate; dicetyl adipate; dicetyl
thiodipropionate; dicocoyl pentaerythrilyl distearyl citrate;
diethoxyethyl succinate; diethyl acetyl aspartate;
diethylaminoethyl cocoate; diethylaminoethyl PEG-5 cocoate;
diethylaminoethyl PEG-5 laurate; diethylaminoethyl stearate;
diethyl aspartate; diethylene glycol diisononanoate; diethylene
glycol dioctanoate; diethylene glycol dioctanoate/diisononanoate;
diethyl glutamate; diethyl oxalate; diethyl palmitoyl aspartate;
diethyl sebacate; diethyl succinate; digalloyl trioleate;
diglyceryl stearate malate; dihexyl adipate; dihexyldecyl lauroyl
glutamate; dihydroabietyl behenate; dihydroabietyl methacrylate;
dihydrocholesteryl butyrate; dihydrocholesteryl isostearate;
dihydrocholesteryl macadamiate; dihydrocholesteryl nonanoate;
dihydrocholesteryl octyldecanoate; dihydrocholesteryl oleate;
dihydrophytosteryl octyldecanoate; dihydroxyethylamino
hydroxypropyl oleate; dihydroxyethyl soyamine dioleate; diisobutyl
adipate; diisobutyl oxalate; diisocetyl adipate; diisodecyl
adipate; diisopropyl adipate; diisopropyl dimer dilinoleate;
diisopropyl oxalate; diisopropyl sebacate; diisostearamidopropyl
epoxypropylmonium chloride; diisostearyl adipate; diisostearyl
dimer dilinoleate; diisostearyl fumarate; diisostearyl glutarate;
diisostearyl malte; dilaureth-7 citrate; dilauryl thiodipropionate;
dimethicone copolyol acetate; dimethicone copolyol adipate;
dimethicone copolyol almondate; dimethicone copolyol beeswax;
dimethicone copolyol behenate; dimethicone copolyol borageate;
dimethicone copolyol cocoa butterate; dimethiccne copolyol dhupa
butterate; dimethicone copolyol hydroxystearate; dimethicone
copolyol isostearate; dimethicone copolyol kokum butterate;
dimethicone copolyol lactate; dimethicone copolyol laurate;
dimethicone copolyol mango butterate; dimethicone copolyol
meadowfoamate; dimethicone copolyol mohwa butterate; dimethicone
copolyol octyldodecyl citrate; dimethicone copolyol olivate;
dimethicone copolyol sal butterate; dimethicone copolyol shea
butterate; dimethicone copolyol stearate; dimethicone copoly
undecylenate; dimethiconol beeswax; dimethiconol behenate;
dimethiconol borageate; dimethiconol dhupa butterate; dimethiconol
fluoroalcohol dillnoleic acid; dimethiconol hydroxystearate;
dimethiconol illipe butterate; dimethiconol isostearate;
dimethiconol kokum butterate; dimethiconol lactate; di methiconol
mohwa butterate; dimethiconol sal butterate; dimethiconol stearate;
dimethyl adipate; dimethylaminoethyl methacrylate; dimethyl
brassylate; dimethyl cystinate; dimethyl glutarate; dimethyl
maleate; dimethyl oxalate; dimethyl succinate; dimyristyl tartrate;
dimyristyl thiodipropionate; dinonoxynol-9 citrate; dioctyl
adipate; dioctyl butamido triazone; dioctyl dimer dilinoleate;
dioctyldodeceth-2 lauroyl glutamate; dioctyldodecyl adipate;
dioctyldodecyl dimer dilinoleate; dioctyldodecyl dodecanedioate;
dioctyldodecyl fluoroheptyl citrate; dioctyldodecyl lauroyl
glutamate; dioctyldodecyl stearoyl dimer dilinoleate; dioctydodecyl
stearoyl glutamate; diocty fumarate; dioctyl malate; dioctyl
maleate; dioctyl sebacate; dioctyl succinate; dioleoyl edetolmonium
methosulfate; dipalmitoyl hydroxyproline; dipentaerythrityl
hexacaprylate/hexacaprate; dipentaerythrityl
hexaheptanoate/hexacaprylate/hexacaprate; dipentaerythrityl
hexahydroxystearate; dipentaerythrityl
hexahydroxystearate/stearate/rosinate; dipentaerythrityl
hexaoctanoate/behenate; dipentaerythrityl
pentahydroxystearate/isostearat-e; dipropyl adipate; dipropylene
glycol caprylate; dipropylene dipropyl oxalate; disodium laureth-7
citrate; disodium PEG-5 laurylcitrate sulfosuccinate; disodium
PEG-8 ricinosuccinate; disodium succinoyl glycyrrhetinate; disodium
2-sulfolaurate; disteareth-2 lauroyl glutamate; disteareth-5
lauroyl glutamate; distearyl thiodipropionate; ditallowoylethyl
hydroxyethylmonium methosulfate; ditridecyl adipate; ditridecyl
dimer dilinoleate; ditridecyl thiodipropionate; dodecyl gallate;
erucyl arachidate; erucyl erucate; erucyl oleate; ethiodized oil;
ethoxydiglycol acetate; ethoxyethanol acetate; ethyl almondate;
ethyl apricot kemelate; ethyl arachidonate; ethyl aspartate; ethyl
avocadate; ethyl biotinate; ethyl butylacetylaminopropionate; ethyl
cyanoacrylate; ethyl cycolhexyl propionate; ethyl digydroxypropyl
paba; ethylene brassylate; ethylene carbonate; ethy ester of
hydrolyzed animal protein; ethyl ester of hydrolyzed keratin; ethyl
ester of hydrolyzed silk; ethyl ester of pvm/ma copolymer; ethyl
ferulate; ethyl glutamate; ethyl isostearate; ethyl lactate; ethyl
laurate; ethyl linoleate; ethyl linolenate; ethyl niethacrylate;
ethyl methylphenylglycidate; ethyl minkate; ethyl morrhuate; ethyl
myristate; ethyl nicotinate; ethyl oleate; ethyl olivate; ethyl
paba ethyl palmitate; ethylparaben; ethyl pelargonate; ethyl
persate; ethyl phenylacetate; ethyl ricinoleate; ethyl serinate;
ethyl stearate; ethyl thioglycolate; ethyl urocanate; ethyl wheat
germate; ethyl ximenynate; ltocrylene; famesyl acetate;
galactonolactone; galbanum (ferula galbaniflua) oil;
gamrnma-nonalacione; geranyl acetate; glucarolactone; glucose
glutamate; glucose pentaacetate; glucuronolactone; glycereth-7
diisononanoate; glycereth-8 hydroxystearate; glycereth-5 lactate;
glycereth-25 PCA isostearate; glycereth-7 triacetate; glyceryl
triacetyl hydroxystearate; glyceryl triacetyl ricinoleate;
glycolamide stearate; glycol/butylene glycol montanate; glycol
catearate; glycol dibehenate; glycol dilaurate; glycol dioctanoate;
glycol dioleate; glycol distearate; glycol ditallowate; glycol
hydroxystearate; glycol montanate; glycol octanoate; glycol oleate;
glycol palmitate; glycol ricinoleate; glycol stearate; glycol
stearate SE; glycyrrhetinyl stearate; hexacosyl glycol isostearate;
hexanediol beeswax; hexanediol distearate; hexanetriol beeswax;
hexyldecyl ester of hydrolyzed collagen; hexyldecyl isostearate;
hexyldecyl laurate; hexyldecyl octanoate; hexyldecyl oleate;
hexyldecyl palmitate; hexyldecyl stearate; hexyl isostearate; hexyl
laurate; hexyl nicotinate; homosalate; hydrogenated castor oil
hydroxystearate; hydrogenated castor oil isostearate; hydrogenated
castor oil lauirate; hydrogenated castor oil stearate; hydrogenated
castor oil triisostearate; hydrogenated methyl abietate;
hydrogenated rosin; hydroquinone pca; hydroxycetyl isostearate;
hydroxyoctacosanyl hydroxystearate; inositol hexa-pca; iodopropynyl
butylcarbamate; isoamyl acetate; isoamyl laurate; isobutylated
lanolin oil; isobutyl myristate; isobutyl palmitate;
isobutylparaben; isobutyl pelargonate; isobutyl stearate; isobutyl
tallowate; isoceteareth-8 stearate; isoceteth-10 stearate; isocetyl
behenate; isocetyl isodecanoate; isocetyl isostearate; isocetyl
laurate; isocetyl linoleoyl stearate; isocetyl myristate; isocetyl
octanoate; isocetyl palmitate; isocetyl stearate; isocetyl stearoyl
stearate; isodeceth-2 cocoate; isodecyl citrate; isodecyl cocoate;
isodecyl hydroxystearate; isodecyl isononanoale; isodecyl laurate;
isodecyl myristate; isodecyl neopentanoate; isodecyl octanoate;
isodecyl oleate; isodecyl palmitate; isodecylparaben; isodecyl
stearate; isohexyl laurate; isohexyl neopentanoate; isohexyl
palmitate; isolauryl behenate; isomerized jojoba oil; isononyl
ferulate; isooctyl thioglycolate; isopropyl arachidate; isopropyl
avocadate; isopropyl behenate; isopropyl citrate; isopropyl
C.sub.12-15-pareth-9 carboxylate; isopropyl hydroxystearate;
isopropyl isostearate; isopropyl jojobate; isopropyl lanolate;
isopropyl laurate; isopropyl linoleate; isopropyl myristate;
isopropyl oleate; isopropylparaben; isopropyl PPG-2-isodeceth-7
carboxylate; isopropyl ricinoleate; isopropyl sorbate; isopropyl
stearate; isopropyl tallowate; isopropyl thioglycolate; isosorbide
laurate; isosteareth-10 stearate; isostearyl avocadate; isostearyl
behenate; isostearyl erucate; isostearyl isononanoate; iscstearyl
isostearate; isostearyl isostearoyl stearate; isostearyl lactate;
isostearyl laurate; isostearyl myristate; isostearyl neopentanoate;
isostearyl octanoate; isostearyl palmitate; isostearyl stearoyl
stearate; isotridecyl isononanoate; isotridecyl laurate;
isotridecyl myristate; jojoba (buxus chinensis) oil; jojoba esters;
kojic dipalmitate; laneth-9 acetate; laneth-10 acetate; laneth-4
phosphate; lanolin linoleate; lanolin ricinoleate; laureth-2
acetate; laureth-6 citrate; laureth-7 citrate; laureth-2 octanoate;
laureth-7 tartrate; lauroyl ethyl glucoside; lauroyl lactylic acid;
lauryl behenate; lauryl cocoate; lauryl isostearate; lauryl
lactate; lauryl methacrylate; lauryl myristate; lauryl octanoate;
lauryl oleate; lauryl palmitate; lauryl stearate; linalyl acetate;
linoleyl lactate; madecassicoside; mannitan laurate; mannitan
oleate; menthyl acetate; menthyl anthranilate; menthyl lactate;
menthyl pca; methoxyisopropyl acetate; methoxy-PEG-7 rutinyl
succinate; methyl acetyl ricinoleate; methyl anthranilate; methyl
behenate; methyl caproate; methyl caprylate; methyl
caprylate/caprate; methyl cocoate; 6-methyl coumarin; methyl
dehydroabietate; methyl dihydroabietate; methyldihydrojasmonate;
methyl glucose dioleate; methyl glucose isostearate; methyl glucose
laurale; methyl glucose sesquicaprylate/sesquicaprate; methyl
glucose sesquicocoate; methyl glucose sesquiisostearate; methyl
glucose sesquilaurate; methyl glucose sesquioleate; methyl glucose
sesquistearate; methyl glycyrrhizate; methyl hydrogenated rosinate;
methyl hydroxystearate; methyl isostearate; methyl laurate; methyl
linoleate; methyl 3-methylresorcylate; methyl myristate; methyl
nicotinate; methyl oleate; methyl palmate; methyl palmitate;
methylparaben; methyl pelargonate; methyl ricinoleate; methyl
rosinate; methylsilanol acetylmethionate; methylsilaiaol
carboxymethyl theophylline; methylsilanol carboxymethyl
theophylline alginate; methylsilanol hydroxyproline; methylsilanol
hydroxyproline aspartate; methylsilanol mannuronate; methylsilanol
pca; methyl soyate; methyl stearate; methyl thioglycolate;
monosaccharide lactate condensata; myreth-3 caprate; myreth-3
laurate; myreth-2 myristate; myreth-3 myristate; myreth-3
octanoate; myreth-3 palmitate; myristoyl ethyl glucoside; myristoyl
lactylic acid; myristyl isostearate; myristyl lactate; myristyl
lignocerate; myristyl myristate; myristyl octanoate; myristyl
propionate; myristyl stearate; neopentyl glycol dicaprate;
neopentyl glycol dicaprylate/dicaprate; neopentyl glycol
dicaprylate/dipelargonate/dicaprate; neopentyl glycol diheptanoate;
neopentyl glycol diisostearate; neopentyl glycol dilaurate;
neopentyl glycol dioctanoate; nonyl acetate; nopyl acetate;
octacosanyl glycol isostearate; octocrylene; octyl acetoxystearate;
octyl caprylate/caprate; octyl cocoate; octyldecyl oleate;
octyldodecyl behenate; octyldodecyl erucate; octyldodecyl
hydroxystearate; octyldodecyl isostearate; octyldodecyl lactate;
octyldodecyl lanolate; octyldodecyl meadowfoamate; octyldodecyl
myristate; octyldodecyl neodecanoate; octyldodecyl neopentanoate;
octyldodecyl octanoate; octyldodecyl octyldodecanoate; octyldodecyl
oleate; octyldodecyl olivate; octyldodecyl ricinoleate;
octyldodecyl stearate; octyldodecyl steroyl stearate; octyl
gallate; octyl hydroxystearate; octyl isononanoate; octyl
isopalmitate; octyl isostearate; octyl laurate; octyl linoleayl
stearate; octyl myristate; octyl neopentanoate; octyl octanoate;
octyl oleate; octyl palmitate; octyl PCA; octyl pelagonate; octyl
stearate; oleoyl ethyl glucoside; oleyl acetate; oleyl arachidate;
oleyl erucate; oleyl ethyl phosphate; oleyl lactate; oleyl
lanolate; oleyl linoleate; oleyl myristate; oleyl oleate; oleyl
phosphate; oleyl stearate; oryzanol; ozonized jojoba oil; palmitoyl
carniline; palmitoyl inulin; palmitoyl myristyl serinate;
pantethine; panthenyl ethyl ester acetate; panthenyl triacetate;
pca glyceryl oleate; pea palmitate; PEG-18 castor oil dioleate;
PEG-S DMDM hydantoin oleate; PEG-15 dmdm hydantoin stearate; PEG-30
dipolyhydroxystearate; PEG-20 hydrogenated castor oil isostearate;
PEG-50 hydrogenated castor oil isostearate; PEG-20 hydrogenated
castor oil triisostearate; PEG-20 mannitan laurate; PEG-20 methyl
glucose distearate; PEG-80 methyl glucose laurate; PEG-20 methyl
glucose sesquicaprylate/sescquicaprate; PEG-20 methyl glucose
sesquilaurate; PEG-5 oleamide dioleate; PEG-150 pentaerythrityl
tetrastearate; PEG-3/PPG-2 glyceryl/sorbitol
hydroxystearate/isostearate; PEG-4 proline linoleate; PEG-4 proline
linolenate; PEG-8 propylene glycol cocoate; PEG-55 propylene glycol
oleate; PEG-25 propylene glycol stearate; PEG-75 propylene glycol
stearate; PEG-120 propylene glycol stearate; PEG-40 sorbitol
hexaoleate; PEG-50 sorbitol hexaoleate; PEG-30 sorbitol tetraoleate
laurate; PEG-60 sorbitol tetrastearate; PEG-5 tricapryl citrate;
PEG-5 tricetyl citrate; PEG-5 trilauryl citrate; PEG-5
trimethylolpropane trimyristate; PEG-5 trimyristyl citrate; PEG-5
tristeaiyl citrate; PEG-6 undecylenate; pentadecalacione;
pentaerythrityl dioleate; pentaerythrityl distearate;
pentaerythrityl hydrogenated rosinate; pentaerythrityl
isostearate/caprate/caprylate/adipate; pentaerythrityl rosinate;
pentaerythrityl stearate; pentaerythrityl
stearate/caprate/caprylate/adipate; pentaerythrityl
stearate/lsostearate/adipate/hydroxystearate; pentaerythrityl
tetraabietate; pentaerythrityl tetraacetate; pentaerityl
tetrabehenate; petaerythrityl tetracaprylate/tetracaprate;
pentaerythrityl tetracocoate; pentaerythrityl tetraisononanoate;
pentaerythrityl tetralaurate; pentaerythrityl tetramyristate;
pentaerythrityl tetraoctanoate;
pentaerythrityl tetraoleate; pentaerythirityl tetrapelargonate;
petaerythrityl tetrastearate; pentaerythrityl trioleate;
phenoxyethylparaben; phylosteryl macadamiate; potassium
butylparaben; potassium deceth-4 phosphate; potassium ethylparaben;
potassiuim methylparaben; potassium propylparaben; PPG-2
isoceleth-20 acetate; PPG-14 laureth-60 alkyl dicarbamate; PPG-20
methyl glucose ether acetate; PPG-20 methyl glucose ether
distearate; PPG-2 myristyl ether propionate; PPG-14 palmeth-60
alkyl dicarbamate; pregnenolone acetate; propylene glycol alginate;
propylene glycol behenate; propylene glycol caprylate; propylene
glycol Ceteth-3 acetate; propylene glycol Ceteth-3 propionate;
propylene glycol citrate; propylene glycol cocoate; propylene
glycol dicaprate; propylene glycol dicaproate; propylene glycol
dicaprylate; propylene glycol dicocoate; propylene glycol
diisononanoate; propylene glycol diisostearate; propylene glycol
dilaurate; propylene glycol dioctanoate; propylene glycol dioleate;
propylene glycol dipelargonate; propylene glycol distearate;
propylene glycol diundecanoate; propylene glycol hydroxystearate;
propylene glycolisoceteth-3 acetate; propylene glycol isostearate;
propylene glycol laurate; propylene glycol linoleate; propylene
glycol linolenate; propylene glycol myristate; propylene glycol
myristyl ether acetate; propylene glycol oleate; propylene glycol
oleate se; propylene glycol ricinoleate; propylene glycol soyate;
propylene glycol stearate; propylene glycol stearate se; propyl
gallate; propylparaben; pyricarbate; pyridoxine dicaprylate;
pyridoxine dilaurate; pyridoxine dioctenoate; pyridoxine
dipalmitate; pyridoxine glycyrrhetinate; pyridoxine tripalmitate;
raffmose myristate; raffinose oleate; resorcinol acetate; retinyl
acetate; retinyl linoleate; retinyl palmitate; retinyl propionate;
riboflavin tetraacetate; ribonolaclone; siloxanetriol phytate;
silybum marianum ethyl ester; sodium behenoyl lactylate; sodium
butylparaben; sodium caproyl lactylate; sodiumn cocoyl lactylate;
sodium dilaureth-7 citrate; sodium ethylparaben; sodium
ethyl-2-sulfolaurate; sodium isostearoyl lactylate; sodium
laureth-7 tartrate; sodium lauroyl lectylate; sodium methylparaben;
sodium methyl 2-sulfolaurate; sodium oleoyl lactylate; sodium
panteheine sulfonate; sodium phytate; sodium propylparaben; sodium
stearoyl lactylate; sorbeth-2 cocoate; sorbeth-6 hexastearate;
sorbeth-3 isostearate; sorbityl acetate; soybean palmitate; soy
sterol acetate; stearamide dea-distearate; stearamide
diba-stearate; stearamide mea-stearate; steareth-5 stearate;
stearoyl lactylic acid; stearyl acetate; stearyl acetyl glutamate;
stearyl beeswax; stearyl behenate; stearyl caprylate; stearyl
citrate; stearyl erucate; stearyl glycol isostearate; stearyl
glycyrrhetinate; stearyl heptanoate; stearyl lactate; stearyl
linoleate; stearyl octanoate; stearyl stearalte; stearyl stearoyl
stearate; sucrose cocoate; sucrose dilaurate; sucrose distearate;
sucrose laurate; sucrose myristate; sucrose octaacetate; sucrose
oleate; sucrose palmitate; sucrose polybehenate; sucrose
polycottonseedate; sucrose polylaurate; sucrose polylinoleate;
sucrose polypalmate; sucrose polysoyate; sucrose polystearate;
sucrose ricinoleate; sucrose stearate; sucrose tetrastearate
triacetate; sucrose tribehenate; sucrose tristearate; tallowoyl
ethyl glucoside; tannic acid; TEA-lauroyl lactylate; telmesteine;
terpineol acetate; tetradecyleicosyl stearate; tetrahexyldecyl
ascorbate; tetrahydrofurfuryl ricinoleate; tocophersolan;
tocopheryl acetate; tocopheryl linoleate; tocopheryl
linoleate/oleate; tocopheryl nicotinate; tocopheryl succinate;
tributyl citrate; tri-C
.sub.12-13 alkyl citrate; tri-C.sub.14-15 alkyl citrate;
tricaprylyl citrate; tridecyl behenate; tridecyl cocoate; tridec),
erucate; tridecyl isononanoate; tridecyl laurate; tridecyl
myristate; tridecyl neopentanoate; tfridecyl octanoate; tridecyl
stearate; tridecyl stearoyl stearate; tridecyl trimellitate;
triethylene glycol hydrogenated rosinate; trihexyldecyl citrate;
triisocetyl citrate; triisopropyl trilinoleate; triisostearyl
citrate; triisostearyl trilinoleate; trilactin; trilauryl citrate;
trimethylolpropane tricaprylate/tricaprate; trimethylolpropane
tricocoate; trimethylolpropane trilaurate; trimethylalpropane
trioctanoate; trimethylolpropane tristearate; trimethyl pentanyl
diisobutyrate; trioctyl citrate; trioctyldodecyl borate; trictyl
trimellitate; trioleyl citrate; tripaba panthenol; tripropylene
glycol citrate; tristearyl citrate; tristearyl phosphate; and yeast
palmitate.
[0044] In a preferred embodiment, the ester oils are natural
product oils that are typically found in animal or plant tissues,
including those which have been hydrogenated to eliminate or reduce
unsaturation. These natural product oils that can be employed in
the present invention include compounds that have the following
formula: ##STR4## where R.sub.10 R.sub.11 and R.sub.12 may be the
same or different fatty acid radicals containing from 8 to 22
carbon atoms.
[0045] Suitable natural product oils of the above formula that can
be employed in the present invention include, but are not limited
to: Kernel Oil; Argania Spinosa Oil; Argemone Mexicana Oil; Avocado
(Persea Gratissima) Oil; Babassu (Orbignya Olelfera) Oil; Balm Mint
(Melissa Officinalis) Seed Oil; Bitter Almond (Prunus Amygdalus
Amara) Oil; Bitter Cherry (Prunus Cerasus) Oil; Black Currant
(Ribes Nigrrrm) Oil; Borage (Borago Officinalis) Seed Oil; Brazil
(B3ertholletia Excelsa) Nut Oil; Burdock (Arctium Lappa) Seed Oil;
Butter; C.sub.12-18 Acid Triglyceride; Calophyllurn Tacamahaca Oil;
Camellia Kissi Oil; Camellia Oleifera Seed Oil; Canola Oil;
Caprylic/Capric/Liuric Triglyceride; Caprylic/Capric/Linoleic
Triglyceride; Caprylic/Capric/Myristic/Stearic Triglyceride;
Caprylic/Capric/Stearic Triglyceride; Caprylic/Capric Triglyceride;
Caraway (Canimn Carvi) Seed Oil; Carrot (Daucus Carota Sativa) Oil;
Cashew (Anacardium Occidentale) Nut Oil; Castor (Ricinus Communis)
Oil; Cephalins; Chaulmoogra (Taraktogenos Kurzii) Oil, Chia (Salvia
Hispanica) Oil; Cocoa (Theobrama Cocao) Butter; Coconut (Cocos
Nucifera) Oil; Cod Liver Oil; Coffee (Coffea Arabica) Oil; Corn
(Zea Mays) Germ Oil; Corn (Zea Mays) Oil; Cottonseed (Gossypium)
Oil; C.sub.10-18 Triglycerides; Cucumber (Cucumis Sativus) Oil; Dog
Rose (Rosa Canina) Hips Oil; Egg Oil; Emu Oil; Epoxidized Soybean
Oil; Evening Primrose (Oenothera Biennis) Oil; Fish Liver Oil;
Gevuina Avellana Oil; Glyceryl Triacetyl Hydroxystearate; Glyceryl
Triacetyl Ricinoleate; Glycolipids; Glycosphingolipids; Goat
Butter; Grape (Vitis Vinifera) Seed Oil; Hazel (Croylus Americana)
Nut Oil; Hazel (Corylus Aveilana) Nut Oil; Human Placental Lipids;
Hybrid Safflower (Ceathamus Tinctorius) Oil; Hybrid Sunflower
(Helianthus Annuus) Seed Oil; Hydrogenated Canola Oil; Hydrogenated
Castor Oil; Hydrogenated Castor Oil Laurate; Hydrogenated Castor
Oil Triisostearate; Hydrogenated Coconut Oil; Hydrogenated
Cottonseed Oil; Hydrogenated C.sub.12-18 Triglycerides;
Hydrogenated Fish Oil; Hydrogenated Lard; Hydrogenated Menhaden
Oil; Hydrogenated Milk Lipids; Hydrogenated Mink Oil; Hydrogenated
Olive Oil; Hydrogenated Orange Roughy Oil; Hydrogenated Palm Kernel
Oil; Hydrogenated Palm Oil; Hydrogenated Peanut Oil; Hydrogenated
Rapeseed Oil; Hydrogenated Shark Liver Oil; Hydrogenated Soybean
Oil; Hydrogenated Tallow; Hydrogenated Vegetable Oil; Isatis
Tinctoria Oil; Job's Tears (Coix Lacryma-Jobi) Oil; Jojoba Oil;
Kiwi (Actinidia Chinensis) Seed Oil; Kukui (Aleurites Moluccana)
Nut Oil; Lard; Lauric/Palmitic/Oleic Triglyceride; Linseed (Linum
Usitatissiumum) Oil; Lupin (Lupinus Albus) Oil; Macadamia Nut Oil;
Macadamia Ternifolia Seed Oil; Macadamia Integrifolia Seed Oil;
Maleated Soybean Oil; Mango (Mangifera Indica) Seed Oil; Marmot
Oil; Meadowfoam (Limnanthes fragraAlba) Seed Oil; Menhaden Oil;
Milk Lipids; Mink Oil; Moringa Pterygosperma Oil; Mortierella Oil;
Musk Rose (Rosa Moschata) Seed Oil; Neatsfoot Oil; Neem (Melia
Azadirachta) Seed Oil; Oat (Avena Sativa) Kernel Oil;
Oleic/Linoleic Triglyceride;
Oleic/Palmitic/Lauric/Myristic/L-inoleic Triglyceride;
Oleostearine; Olive (Olea Europaea) Husk Oil; Olive (Olea Europaea)
Oil; Omental Lipdis; Orange Roughy Oil; Ostrich Oil; Oxidized Corn
Oil; Palm (Elaeis Guineensis) Kernel Oil; Palm (Elaeis Guineensis)
Oil; Passionflower (Passiflora Edulis) Oil; Peach (Prunus Persica)
Kernel Oil; Peanut (Arachis Hypogaea) Oil; Pecan (Caiya
Illinoensis) Oil; Pengawar Djambi (Cibotium Barometz) Oil;
Phospholipids; Pistachio (Pistacia Vera) Nut Oil; Placental Lipids;
Poppy (Papaver Orientale) Oil; Pumpkin (Cucurbita Pepo) Seed Oil;
Quinoa (Chenopodium Quinoa) Oil; Rapeseed (Brassica Campestris)
Oil; Rice (Oryza Sativa) Bran Oil; Rice (Oryza Sativa) Germ Oil;
Safflower (Carthamus Tinctorius) Oil; Salmon Oil; Sandalwood
(Santalum Album) Seed Oil; Seabuchthorn (Hippophae Rhamnoides) Oil;
Sesame (Sesamum Indicum) Oil; Shark Liver Oil; Shea Butter
(Butyrospermum Parkii); Silk Worm Lipids; Skin Lipids; Soybean
(Glycine Soja) Oil; Soybean Lipid; Sphingolipids; Sunflower
(Helianthus Annuus) Seed Oil; Sweet Almond (Prunus Amygdalus
Dulcis) Oil; Sweet Cherry (Prunus Avium) Pit Oil; Tali Oil; Tallow;
Tea Tree (Melaleuca Alternifolia) Oil; Telphairia Pedata Oil;
Tomato (Solanum Lycopersicum) Oil; Triarachidin; Tiibehenin;
Tricaprin; Tricaprylin; Trichodesma Zeylanicum Oil; Trierucin;
Triheptanoin; Triheptylundecanoin; Trihydroxymethoxystearin;
Trihydroxystearin; Triisononanoin; Triisopalmitin; Triisostearin;
Trilaurin; Trilinolein; Trilinolenin; Trimyristin; Trioctanoin;
Triolein; Tripalmitin; Tripalmitolein; Triricinolein; Trisebacin;
Tristearin; Triundecanoin; Tuna Oil; Vegetable Oil; Walnut (Juglans
Regia) Oil; Wheat Bran Lipids; and Wheat (Triticum Vulgare) Germ
Oil. In a preferred embodiment, the natural oil product is soybean
oil or coconut oil.
[0046] The amount of natural oil that can be employed in the
present invention varies from about 250 to about 2000 parts by
weight per 100 parts by weight rubber, or block copolymer,
preferably about 400 to about 1000 parts by weight.
[0047] The inventive gel composition may also include various types
of fillers and pigments to pigment the gel and reduce cost.
Suitable fillers include calcium carbonate, clay, talc, silica,
zinc oxide, titanium dioxide and the like. The amount of filler
employed in the present invention usually is in the range of 0 to
30% weight based on the solvent free portion of the formulation,
depending on the type of filler used and the application for which
the gel is intended. An especially preferred filler is titanium
dioxide.
[0048] Another contemplated component of the oil gel composition of
the present invention is a polyolefin homopolymer, branched
homopolymer, or copolymer. These ingredients can be used to
increase the hardness and tear strength of the gel. Preferred
polyolefins are polyethylenes and copolymers of polyethylenes with
monoalkenyl comonomers including, but not limited to: propylene,
butylene, octene, styrene and the like. The melt index of these
polymers can range from less than 1 to more than 3,000 measured at
190.degree. C. Examples are low density polyethylenes made with
Zeigler-Natta catalysts such as Epolene.RTM. C-10 from Eastman
Chemical with a density of 0.906 and a melt flow of 2,250 to
metallocene linear low density polyethylenes such as Exact.RTM.
4023 from Exxon Mobil Chemical with a melt index of 35 and a
density of 0.882 and styrene ethylene copolymers such as
2900TE.RTM. made by Dow Chemical which contains 34% styrene.
Polyolefins will typically be added from 0 to 100 parts per hundred
weight rubber, preferably 10 to 50 parts per hundred weight
rubber.
[0049] The oil gel compositions of the present invention may be
modified further with the addition of other polymers, fillers,
reinforcements, antioxidants, stabilizers, fire retardants, anti
blocking agents, suntan screens, lubricants and other rubber and
plastic compounding ingredients without departing from the scope of
this invention. Such components are disclosed in various patents
including, for example, U.S. Pat. Nos. 3,239,478 and 5,777,043, the
disclosures of which are incorporated by reference.
[0050] The gels of the present invention can be used for a variety
of purposes, such as those disclosed, for example, in U.S. Pat.
Nos. 5,336,708, 5,334,646, and 4,798,853. These include, among
other uses, as a vibration damper, a vibration isolator, a wrapper,
a hand exerciser, a dental floss, a crutch cushion, a cervical
pillow, a bed wedge pillow, a leg rest cushion, a neck cushion, a
mattress, a bed pad, an elbow pad, a dermal pad, a wheelchair
cushion, a helmet liner, a hot or cold compress pad, an exercise
weight belt, an orthopedic shoe sole, a splint, sling or brace
cushion for the hand, wrist, finger, forearm, knee, leg, clavicle,
shoulder, foot, ankle, neck, back and rib or a traction pad. Other
uses include in candles, toys, cables for power or electronic
(telephone) transmission, hydrophone cables for oil exploration at
sea, greases, oil field drilling fluids, and other various
uses.
[0051] The following examples are provided to illustrate the
inventive oil gel composition. These examples are merely exemplary
and are not intended to limit the scope of the invention. Amounts
are in parts by weight or weight percentages unless otherwise
specified. Except for Probe Hardness, the test methods used in the
examples are American Society for Testing Materials (ASTM) test
methods, and the following specific methods were used:
TABLE-US-00001 TEST ASTM No. Melt Viscosity ATSM D-3236 Ring and
Ball Softening Point ASTM D-36 Shore Hardness ASTM D-2240
[0052] For the Probe Hardness test, 90 grams of gel were poured hot
into a 150 ml beaker and cooled to 25 .degree. C. Probe Hardness is
the force in grams required to push a 0.5 inch diameter cylindrical
acrylic probe into the gel to a depth of 4 mm at a rate of 1.0
mm/second. The equipment used for this test was a TA.XT2i Texture
Analyzer with a TA-10 probe from Texture Technologies Corp.,
Scarsdale, N.Y.
EXAMPLE 1
[0053] In this example, various block copolymers were used to gel
various ester oils including those that fall within the scope of
the present invention, and those that fall outside the scope of the
present invention. Specifically, the anionic block copolymers
employed in this example included: Copolymer 1 (a copolymer within
the present invention), Copolymer 2 (another copolymer within the
scope of the present invention) and Copolymer 3 (a copolymer
outside of the present invention). Copolymer 1 was a S-EB/S-S
polymer in which each S end block had a MW of about 29,000 and the
EB/S midblock had a MW of 80,000/50,000. The styrene content of
Copolymer 1 was 57.5% by weight and the styrene content of the EB/S
midblock was 39% by weight. Copolymer 2 was a S-EB/S-S polymer in
which each S end block had a MW of about 9,500 and the EB/S
midblock had a MW of 60,000/20,000. The styrene content of
Copolymer 2 was about 39.5% by weight and the styrene content in
the EB/S midblock was about 25% by weight. Copolymers 1 and 2 had a
1,2/1,4-Bd ratio of about 40/60. Copolymer 3 was a S-EB-S type
polymer having the following block MW 10,000-80,000-10,000; %
weight S of 20.5 and a 1,2/1,4-Bd ratio of 65/35.
[0054] In this example, Cargill.RTM. Soybean Oil (a triglyceride of
C.sub.18 acids), Erucicial.RTM. EG-20 (an eicosyl erucate ester
supplied by Lambert Tech), Finester.RTM. EH-25 (a C.sub.12-15 alkyl
octanoate supplied by Fintex), Finsolv.RTM. TN (a C.sub.12-15 alkyl
benzoate supplied by Fintex) and Neo Heliopan AV.RTM. (an octyl
methoxy cinnamate supplied by Liberty Natural) were used. The first
three ester oils fall within the scope of the present invention,
while the last two ester oils are aromatic oils that fall outside
the scope of the present invention.
[0055] Copolymer 1 was blended into the oils at 7.5% by weight
copolymer and Copolymers 2 and 3 were blended into the oils at 15%
by weight copolymer. 0.1% by weight Irganox.RTM. 1010 (a hindered
phenolic antioxidant supplied by Ciba) was also included in each
blend. The polymers were mixed into the oils by blending for about
1 to 1.5 hour at 130.degree.-170.degree. C. with a Silverson.RTM.
mixer. Table 1 below shows the various oil gels that were prepared
and provides characterization of the resultant oil gels.
TABLE-US-00002 TABLE 1 Gels of Ester Oils Gel 1: 7.5% Gel 2: 15.0%
Gel 3: 15.0% by weight by weight by weight Copolymer 1 + Copolymer
2 + Copolymer 3 + 92.4% by 84.9% by 84.9% by weight oil weight oil
weight oil Soybean Oil Yellow, slight Yellow, slight Yellow,
opaque, haze, solid haze, self- solid rubbery rubbery gel, levels
gel, some free very slight oil oil bleed after 1 month Erucical
.RTM. Yellow, clear, Yellow, slight Yellow, clear, EG-20 solid
rubbery haze, solid solid rubbery gel, no free rubbery gel, gel, no
free oil no free oil oil Finester .RTM. Very slight Bluish haze,
Bluish haze, EH-25 haze, color- colorless, colorless, less, solid
thickened but thickened but rubbery gel, low viscosity low
viscosity no free oil Finsolv .RTM. Colorless, Colorless,
Colorless, very TN very clear, slight haze, slight haze, low
viscosity thickened but thickened but low viscosity low viscosity
Neo Heliopan Thickened, Very slight Low viscosity, AV .RTM. slight
thixo- bluish haze, slight bluish tropy, clear, colorless, haze,
colorless colorless, thixotropic gel, very slight no elasticity
bluish haze
[0056] The results provided in Table 1 illustrate that in soybean
oil, both Copolymer 1 and 2 gave fairly clear blends. Copolymer 1
gave a nice rubbery gel, although it was quite soft. Copolymer 2
thickened soybean oil, but did not gel it at 15% weight. Copolymer
3 was incompatible with soybean oil; it made an opaque gel and the
polymer did not hold oil. In Erucical.RTM. EG-20, all three
polymers gave a nice, clear, rubbery gel with no oil bleed. In
Finester.RTM. EH-25, all three polymers gave a nearly clear blend,
but only Copolymer 1 gelled that oil. In the two aromatic ester
oils, all three polymers were soluble and gave clear blends, but
none of them gave a rubbery gel in the oils.
EXAMPLE 2
[0057] In this example, Copolymer 1 was compared with Copolymer 4
(an S-EB-S type polymer having block MW of 29,000-130,000-29,000, a
styrene % weight of 33 and a 1,2/1,4-Bd ratio of 40/60). The
various esters employed in Example 1 were used in this example as
well. Table 2 includes the formulations and results with Copolymer
1, while Table 3 includes the formulations and results for
Copolymer 4. TABLE-US-00003 TABLE 2 Gels of Ester Oils Composition,
% weight A B C D E Soybean oil 92.4 Erucical .RTM. 92.4 EG-20
Finester .RTM. 92.4 EH-25 Neo Heliopan 92.4 AV .RTM. Finsolv .RTM.
92.4 TN Copolymer 1 7.5 7.5 7.5 7.5 7.5 Irganox .RTM. 0.1 0.1 0.1
0.1 0.1 1010 R&B 67 88 53 Slight Low Softening thixo- visco-
Point, .degree. C. tropy sity Shore 00 0 0 0 Hardness Probe 58 79
37 Hardness, gm Appearance Yellow, Yellow, Very slight Very
Colorless, slight clear, haze, slight very haze, no oil colorless,
bluish clear, slight bleed no oil haze, low oil bleed slight
viscosity bleed thixotropy
[0058] TABLE-US-00004 TABLE 3 Gels of Ester Oils Composition, %
weight F G H I J Soybean oil 92.4 Erucical .RTM. 92.4 EG-20
Finester .RTM. 92.4 EH-25 Neo 92.4 Heliopan AV .RTM. Finsolv .RTM.
TN 92.4 Copolymer 4 7.5 7.5 7.5 7.5 7.5 Irganox .RTM. 1010 0.1 0.1
0.1 0.1 0.1 R&B 90 43 Softening Point, .degree. C. Shore 00 0 0
Hardness Probe 72 68 Hardness, gm Appearance Yellow, Golden, Slight
Hazy, gritty Clear, opaque gel clear haze, surface, low colorless,
floating color- viscosity, no moderate oil less thixotropy
viscosity
[0059] Note that the copolymers behave similarly in all oils except
for soybean oil in which Copolymer 4 was incompatible.
EXAMPLE 3
[0060] In this example, more blends were made with Copolymer 1 to
better understand its capability. Table 4 presents formulations and
results for Copolymer 1 in non-aromatic ester oils of the present
invention. Table 5 shows blends of Copolymer 1 with aromatic oils
for comparative purposes.
[0061] As shown in Table 4, in soybean oil, Copolymer 1 at 9% by
weight still showed a very slight oil bleed. At 12% by weight, no
oil bleed was found. Blends at up to 15% by weight of Copolymer 1
could be made, but it is likely that higher concentrations would be
too viscous to mix with the Silverson.RTM. mixer. The gels in
soybean oil become clearer with increasing Copolymer 1 content.
TABLE-US-00005 TABLE 4 Copolymer 1 in Gels with non-Aromatic Ester
Oils Composition, % weight K L M N O P Q R S T U V W Soybean oil
92.4 90.9 87.9 84.9 Erucical .RTM. 92.4 90.9 87.9 EG-20 Finester
.RTM. 92.4 90.9 87.9 84.9 79.9 74.9 EH-25 Copolymer 1 7.5 9 12 15
7.5 9 12 7.5 9 12 15 20 25 Irganox .RTM. 0.1 0.1 0.1 0.1 0.1 0.1
0.1 0.1 0.1 0.1 0.1 0.1 0.1 1010 R&B 67 71 78 87 88 91 109 53
56 52 54 68 81 Softening Point, .degree. C. Shore 00 0 0 8 12.5 0 0
0 0 0 0 0 13.5 27 Hardness Probe 58 91 190 325 79 95 175 37 59 122
209 433 817 Hardness, gm Oil Bleed Slight Very No No No No No No No
No No No No Out slight
[0062] TABLE-US-00006 TABLE 5 Copolymer 1 in Gels with Aromatic
Ester Oils Composition, % weight X Y Z AA BB CC DD Neo 92.4 90.9
Heliopan AV .RTM. Finsolv .RTM. 92.4 89.9 87.4 84.9 79.9 TN Copoly-
7.5 9 7.5 10 12.5 15 20 mer 1 Irganox .RTM. 0.1 0.1 0.1 0.1 0.1 0.1
0.1 1010 Visco- Low Moder- Low Low Moder- Moder- High sity at ate
ate ate 25.degree. C. Clarity Slight Very Very Very Very thixo-
slight slight slight slight tropy haze haze haze haze
[0063] The results in Table 4 show that Copolymer 1 had excellent
compatibility with Erucical.RTM. EG-20. The blends were optically
clear and showed no oil bleed, even at 7.5% by weight. These blends
gave the highest softening points, but also the highest melt
viscosity.
[0064] The results in Table 4 show that Copolymer 1 also had
excellent compatibility with Finester.RTM. EH-25. These blends
showed good clarity, no oil bleed and they were colorless. These
blends gave much lower softening points than the blends with
soybean oil and Erucical.RTM. EG-20. Softening points remained
fairly low until the Copolymer 1 concentration reached about 20% by
weight. Fortunately, blends in Finester.RTM. EH-25 had relatively
low viscosity so blends can be made with the Silverson.RTM. mixer
at up to 25% by weight of Copolymer 1. Since gel hardness is
directly related to polymer content, this low viscosity allowed
gels to be made with Finester.RTM. EH-25 that have relatively high
hardness.
[0065] The results in Table 5 show that none of the blends made
with the aromatic oils gelled. Blends with Finsolv.RTM. TN at up to
20% by weight of Copolymer 1 were thick but had almost no
thixotropy or elasticity.
EXAMPLE 4
[0066] In this example, an oil gel composition comprising coconut
oil and Copolymer 1 was prepared as outlined in Example 1 above. A
comparison is shown with Copolymer 4. Stirring was performed at
160.degree.-170.degree. C. The coconut oil was 76.degree. Edible
Coconut Oil from Alnoroil Company, Valley Stream, N.Y. The
following formulations were prepared and exhibited the following
properties: TABLE-US-00007 TABLE 6 Oil Gel Compositions with
Coconut Oil Composition, % by weight EE FF GG HH II Coconut Oil
92.4 90.9 87.9 84.9 92.4 Copolymer 1 7.5 9 12 15 Copolymer 4 7.5
Irganox .RTM. 0.1 0.1 0.1 0.1 0.1 101 R&B 67 69 72 87 Softening
Point, .degree. C. Probe 65 160 220 340 Hardness, gm
[0067] When freshly made, Gels EE-HH were clear, rubbery gels at
room temperature. After a few days, the coconut oil crystallized
and the gels became opaque. When freshly made, Gel II was rubbery,
but it was opaque and bled oil badly at room temperature, showing
that the conventional S-EB-S polymer is incompatible with coconut
oil.
[0068] While the present invention has been particularly shown and
described with respect to preferred embodiments thereof, it will be
understood by those skilled in the art that the foregoing and other
changes in forms and details may be made without departing from the
spirit and scope of the present invention. It is therefore intended
that the present invention not be limited to the exact forms and
details described and illustrated, but fall within the scope of the
appended claims.
* * * * *